AU750044B2

AU750044B2 - Cosmetic composition comprising at least one silicone/ acrylate copolymer and at least one photoprotective agent

Info

Publication number: AU750044B2
Application number: AU56484/00A
Authority: AU
Inventors: Christine Dupuis
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1999-09-16
Filing date: 2000-09-05
Publication date: 2002-07-11
Anticipated expiration: 2020-09-05
Also published as: EP1321127A3; RU2200536C2; DE60007046T2; KR100364308B1; EP1084696A1; FR2798587B1; CA2319930A1; ATE255876T1; BR0004322A; DE60007046D1; EP1321127A2; JP2004323535A; JP2001131017A; FR2798587A1; CN1295832A; CA2319930C; AU5648400A; ES2211474T3; EP1084696B1; PL342563A1

Abstract

Cosmetic composition comprises a silicone-acrylate copolymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a silicone having oxyalkylene groups and a photo protective agent selected from a list of substances. Cosmetic composition comprises a silicone-acrylate copolymer produced by radical polymerization of an ethylenically unsaturated monomer in the presence of a silicone having oxyalkylene groups and a photo protective agent selected from: (1) dibenzoylmethanes; (2) benzylidene camphor derivatives of formula (I); (3) benzimidazoles and benzoxazoles of formula (II); (4) benzophenone-functional silanes or polyorganosiloxanes; (5) anthranilates; (6) benzotriazoles, benzotriazole silicones; and (7) triazines particularly 2,4,6-tris-p-(2'-ethylhexyl-1'-acyl carbonyl)anilino-1,3,5-triazine, salicylates particularly methyl or octyl salicylates, p-(dimethyl)amino benzoates, alkyl 2-cyano-3,3-diphenylacrylates, metal oxide nanopigments; (8) 3,4'-methyl benzylidene camphor, 3-benzylidene camphor, the methyl sulfate of (3,4'-trimethylammonium)-benzylidene camphor and the acid of 3-(4'-sulfobenzylidene) camphor. R7, R9 = H, halo, OH, (un)saturated 1-10C alkyl, (un)saturated 1-10C alkoxy or SO3H; R10 = H or SO3H; R8 = OH or OR11; R11 = (un)saturated 1-10C alkyl or a group of formula (i)-(iii); W = O or NH; R17 = H or SO3H; R18 = (un)saturated 1-10C alkoxy, 5-R19-2-benzoxazolyl or 5-R19-1H-imidazol-2-yl; R19 = H or SO3H. R12 = H or SO3H; Z = O or NH; R13-R16 = H, halo, OH, (un)saturated 1-10C alkyl, (un)saturated 1-10C alkoxy or SO3H. An Independent claim is also included for a hair styling method using the above composition.

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s):

L'OREAL

Invention Title: COSMETIC COMPOSITION COMPRISING AT LEAST ONE SILICONE/ACRYLATE COPOLYMER AND AT LEAST ONE PHOTOPROTECTIVE AGENT The following statement is a full description of this invention, including the best method of performing it known to me/us: COSMETIC COMPOSITION COMPRISING AT LEAST ONE SILICONE/ACRYLATE COPOLYMER AND AT LEAST ONE PHOTOPROTECTIVE AGENT The invention relates to a cosmetic composition comprising at least one specific silicone/acrylate copolymer and at least one photoprotective agent. The invention also relates to a cosmetic process, in particular a process for fixing 10 and/or holding the hairstyle by using the said composition, as well as to the use of this composition for the manufacture of a cosmetic formulation intended in particular for holding and/or shaping the hairstyle.

According to the invention, the term "photoprotective agent" is generally intended to denote any compound or combination of compounds which is(are) known per se and which, by mechanisms, which are also known per se, of absorption and/or reflection and/or scattering of UV-A and/or UV-B radiation, makes it possible to prevent, or at least limit, the contact of the said radiation with the surface of the hair onto which this or these compounds have been applied. In other words, these compounds can be UV-absorbing photoprotective organic screening agents or UV-scattering and/or UV-reflecting mineral (nano)pigments, as well as mixtures thereof.

Among hair products, in particular those intended for shaping and/or holding the hairstyle which are most widely available on the cosmetics market, there may be distinguished spray compositions essentially consisting of a solution, usually an alcoholic or aqueous solution, and one or more materials.

When the compositions are intended for fixing and/or holding the hairstyle, these materials are generally polymeric resins, whose function is to form welds between the hairs, and these are also known as oooo fixing materials, mixed with various cosmetic o oo adjuvants. These compositions are generally packaged either in a suitable aerosol container placed under pressure with the aid of a propellant, or in a pumpdispenser bottle.

Se Hair gels and hair mousses which are generally applied to wet hair before blow-drying or setting the hair are also known. A drying or blowdrying operation is then carried out in order to shape and fix the hairstyle. These gels or mousses can also contain polymeric resins.

It is known that light radiation with wavelengths of between 280 nm and 400 nm damage the hair when a person is exposed to this radiation for too long. In particular, rays with wavelengths of between 280 nm and 320 nm, which are known as UV-B rays, embrittle the hair and degrade its various constituents, in particular keratin.

UV-A rays, with wavelengths of between 320 rnm and 400 nm, are themselves capable of modifying the natural colour of the hair, in particular in the case of light-coloured hair. UV-A rays also cause a loss of elasticity of the hair, which becomes dry and brittle, especially at the tips.

Hair compositions comprising photoprotective agents capable of screening out UV-A and UV-B rays have already been proposed. However, these hair compositions 10 are not entirely satisfactory, since too small a eeoc proportion of photoprotective agents become fixed to .the hair. Consequently, the protection actually obtained, after applying the hair composition to the hair, is far from equal to the expected protection.

What is more, the photoprotective agents which were initially fixed to the hair do not remain thereon long enough to give the person suitable and long-lasting protection. The hair is thus subjected to natural solar radiation, i.e. radiation containing harmful UV-A and UV-B rays, only a short time after applying the hair composition to the hair.

There is thus a need to find cosmetic compositions, in particular for holding and/or fixing the hairstyle, which do not have the set of drawbacks mentioned above, and which in particular fix the hairstyle well, while at the same time screening out solar radiation sufficiently and affording good cosmetic properties.

4 The Applicant has discovered, surprisingly and unexpectedly, that when certain silicone/acrylate copolymers are combined with photoprotective agents, it is possible to obtain cosmetic compositions which satisfy the requirements expressed above.

One subject of the invention is a cosmetic composition comprising, in a cosmetically acceptable medium, at least one silicone/acrylate copolymer and at least one photoprotective agent, the silicone/acrylate 10 copolymer being obtained by radical-mediated polymerization of at least one ethylenically unsaturated monomer in the presence of at least one silicone derivative comprising oxyalkylene groups.

Another subject of the invention relates to a cosmetic hair process, in particular a process for fixing and/or holding the hairstyle using the said composition.

Yet another subject of the invention relates to the use of this composition for the manufacture of a cosmetic hair formulation which is intended in particular for holding and/or shaping the hairstyle.

The silicone/acrylate copolymers particularly targeted by the present invention are those described in International patent application WO 99/04750. In particular, the copolymer sold by BASF under the name Luviflex Silk is preferred. This polymer is a grafted copolymer of tert-butyl acrylate/methacrylic acid and silicone copolyol.

Preferably, the monomer corresponds to formula (Ia): X-C-CR =CHR 6 (la) 0 in which: X is chosen from the group comprising OH, OM, OR 8 NH2, NHR and N(R 8 2 10 M is a cation chosen from Na K Mg",

NH

4 alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium; the radicals R 8 may be identical or different and are chosen from the group comprising 15 hydrogen, linear or branched Ci to C 40 alkyl groups, mono- or polyhydroxylated Ci to C 40 alkyl groups, optionally substituted with one or more alkoxy, amino or carboxyl groups, hydroxylated polyethers, and N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 20 2-ethoxyethyl, hydroxypropyl, methoxypropyl and ethoxypropyl groups;

R

7 and R 6 are chosen, independently of each other, from the group comprising hydrogen, linear or branched C 1 to C 8 alkyl groups, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl groups, and CN, COOH and COOM groups.

In particular, the monomers of formula (Ia) are acrylic acid and its salts, esters or amides.

The esters may be derivatives of linear C 1 to C 40 alkyls, of branched C 3 to C 40 alkyls or of C 3 to C 40 carboxylic alcohols, of polyfunctional alcohols containing 2 to 8 hydroxyls, such as ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol, of amino alcohols or of alcohol ethers such as methoxymethanol and ethoxyethanol, or polyalkylene glycols.

The monomers of formula (Ia) may also be 10 chosen from N,N-dialkylaminoalkyl acrylates and methacrylates and N-dialkylaminoalkyl-acrylamides and -methacrylamides, the amide group possibly being unsubstituted, N-alkyl- or N-alkylamino-monosubstituted or N,N-dialkylamino-disubstituted, the alkyl or alkylamino groups being derived from linear C 1 to C 40 or branched C 3 to C 40 carboxylic units.

The monomers of formula (Ia) which can be used may also be substituted compounds derived from acrylic acid or its salts, esters or amides. Mention may be made, for example, of methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid.

Other monomers which are particularly suitable are C 1 to C 40 vinyl and allyl esters, linear C 3 to C 40 carboxylic acids or C 3 to C 40 carboxycyclic acids, vinyl or allyl haldides, vinyllactams, preferably vinylpyrrolidone and vinylcaprolactam, heterocyclic compounds substituted with vinyl or allyl groups, preferably vinylpyridine, vinyloxazoline and allylpyridine, N-vinylimidazoles, diallylamines, vinylidene chloride, carbon-based unsaturated compounds, such as styrene or isoprene, and acrylic or methacrylic acid derivatives quaternized with epichlorohydrin.

Other monomers which may finally be mentioned are N-vinylimidazoles, diallylaxines, vinylidene chloride, carbon-based unsaturated compounds 0:0* such as styrene and isoprene, and acrylic or 10 methacrylic acid derivatives quaternized with 0* epichlorohydrin.

0**e Monomers which are most particularly preferred are acrylic, methacrylic and ethacrylic acid; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-thylhexyl and decyl acrylate; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl 0**0 methacrylate; methyl, ethyl, propyl, n-butyl, isobutyl, **t-butyl, 2-ethylhexyl and decyl ethacrylate; 2,3-ihydroxypropyl acrylate; 2,3-dihydroxypropyl methacrylate; 2-dihydroxyethyl acrylate; hydroxypropyl acrylate; 2-hydroxyethyl methacrylate; 2-hydroxyethyl ethacrylate; 2-methoxyethyl acrylate; 2-ethoxyethyl methacrylate; 2-ethoxyethyl ethacrylate; hydroxypropyl methacrylate; glyceryl monoacrylate; glyceryl monomethacrylate; polyalkylene glycol (meth)acrylates, unsaturated sulphonic acids, acrylamide, methacrylamide, ethacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, 1-vinylimidazole, N,N-dimethylaminoethyl (meth)acrylate, maleic acid, fumaric acid, maleic anhydride and its monoesters, crotonic acid, itaconic acid, vinyl ethers, vinylformamide, vinylamine, vinylpyridine, vinylimidazole, vinylfuran, styrene, styryl sulphonate and allyl alcohol, and mixtures thereof.

The monomer can also contain silicon or fluorine atoms or alternatively thio groups. The monomers can be neutralized if they contain acid 10 groups, this being carried out before or after the polymerization, and partially or totally, so as to adjust the solubility or the degree of dispersion in water to the desired level. Agents serving for the o*4 "neutralization which may be used are mineral bases, such as sodium carbonate, and organic bases such as amino alcohols, for instance alkanolamines such as methanolamine, 2-amino-2-methyl-l-propanol or S. triethanolamine, and diamines such as lysine.

The monomers can also be quaternized when they contain a basic nitrogen atom. If they contain at least two ethylenic double bonds, the monomers can be partially crosslinked.

The silicone derivatives are in particular the compounds known under the INCI name of dimethicone copolyols or silicone surfactants. Mention may be made of those sold under the brand names Abil® by Goldschmidt, Alkasil® by Rh6ne-Poulenc, silicone Polyol Copolymer® by Genesee, Besil® by Wacker, Silwet® by OSI or Dow Corning 190® by Dow Corning.

Among the preferred monomers are those which have the formula I below: in which formula

R

2 is chosen from CH 3 and the group 3 2

R

3 is chosen from CH3 and the group R 2

R

4 is chosen from hydrogen, CH 3 and the groups FR1- -H3

\CTRI'

amncroy rslhnte rus n fc0 ei R 6is an organic C 1 to C 4 0 group which can contain amino, carboxyl or sulphonated groups, and if c=0, R 6 is the anion of an inorganic acid; the radicals R 1 may be identical or different and are chosen from C 1 to C 20 aliphatic hydrocarbons, C 3 to C 20 aliphatic or cycloaliphatic hydrocarbons, and the groups R 5 corresponding to the formula below: [lacuna] Among the preferred silicone derivatives (b) are those which have the formula I below: ^Ri~ Fl RI R3- -j Q 1

I

xY

R

1 R~,-al ^R L A i L- in which formula

R

2 is chosen from CH 3 and the group 0 9900 0.

0 R is chosen from CH 3 and the group R 2

R

4 is chosen from hydrogen, CH 3 and the 15 groups

RF

1 St~-

L"

C-H

3 xi fj u c

R

6 is a C 1 to C 40 organic group which can contain amino, carboxyl or sulphonate groups, and if c=0, R 6 is the anion of an inorganic acid; the radicals R 1 may be identical or different and are chosen from C 1 to C 20 aliphatic hydrocarbons, C 3 to C 20 aliphatic or cycloaliphatic hydrocarbons, and the groups R 5 corresponding to the formula below: i 0 *0 n is an integer between 1 and 6, x and y are integers chosen such that the molecular weight of the polysiloxane is between 300 and 30,000, a and b are integers between 0 and 50, and c is 0 or 1.

R

1 is preferably chosen from methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl groups, cycloaliphatic radicals, in particular cyclohexyl groups, aromatic groups, in particular phenyl or naphthyl groups, and mixtures of aromatic and aliphatic radicals, such as benzyl and phenylethyl, and also tolyl and xylyl.

The preferred radicals R 4 are those having the formula -(CO)c-R 6

R

6 being an alkyl, cycloalkyl or aryl containing 1 to 4 carbon atoms which can contain additional groups such as NH 2 COOH and/or SO 3

H.

The preferred radicals R 6 are those for which c=0, which are phosphates or sulphates.

The silicone derivatives which are particularly preferred are those having the general formula below: x- y H

M

The relative proportion of derivative in the copolymer is generally from 0.1% to 50% and preferably from 1% to 20% by weight.

The preferred copolymers are the watersoluble silicone/acrylate copolymers or those whose dispersibility in water is such that, in a 15 water/ethanol mixture dosed at 50/50 by volume, they are soluble in a proportion of greater than 0.1 g/l and preferably greater than 0.2 g/l.

The composition advantageously comprises, as a relative percentage by weight of the composition, from 0.1% to 20% of silicone/acrylate copolymer and preferably from 0.5% to The composition advantageously comprises, as a relative percentage by weight of the composition, from 0.1% to 20% of photoprotective agent, and preferably from 0.2% to Among the UV-A-active organic screening agents which can be used according to the invention, mention may be made of: dibenzoylmethane derivatives; the UV-A-active screening agents of formula I below:

R

R-

(I)

in which: R and R 9 which may be identical or different, denote a hydrogen, a halogen, an OH radical, .a saturated or unsaturated, linear or branched Ci-Cio alkyl radical; a saturated or unsaturated, linear or 15 branched Ci-Clo alkoxy radical or an HSO 3 group;

R

10 denotes hydrogen or HSO 3

R

8 denotes hydroxyl; a group OR 11 in which

R

11 denotes a saturated or unsaturated, linear or branched CI-Clo alkyl radical; or a group of the following structure:

S

1 2 in which R 12 denotes hydrogen or HSO 3 or alternatively a group of the following formula:

COOR

1 3 14 or alternatively a group of the following formula:

*N

R 16 10 in which: Z denotes an oxygen atom or an -NHradical; R13, R14, R15 and R16, which may be identical or different, denote a hydrogen, a halogen, an OH radical, a saturated or unsaturated, linear or branched

C

1 -Cio alkyl radical; a saturated or unsaturated, linear or branched CI-Cio alkoxy radical or an HSO 3 group; the UV-A-active screening agents of the benzimidazole or benzoxazole type of formula (II) below:

R,

R

1 8 in which: W denotes an oxygen atom or an -NHradical, S.

R

17 denotes hydrogen or HSO 3

R

18 denotes a linear or branched alkoxy radical containing from 1 to 10 carbon atoms approximately or a group of the following formula: Rig N in which Y represents an oxygen atom or an -NH- radical and R 19 denotes hydrogen or HSO 3

R

1 9 denotes hydrogen or HSO 3 benzophenone derivatives such as those of formula (III) below:

OH

1 I in which:

R

20 denotes hydrogen or a saturated or unsaturated, linear or branched C 1 -Cio alkyl radical;

R

21 and R 22 which may be identical or different, denote a hydrogen, a halogen, an OH radical, a saturated or unsaturated, linear or branched Ci-Cio alkyl radical; a saturated or unsaturated, linear or branched C 1 -Clo alkoxy radical or an HSO 3 group;

R

23 denotes hydrogen; OH; a saturated or unsaturated, linear or branched Ci-Cio alkyl radical or 10 a saturated or unsaturated, linear or branched CI-Clo alkoxy radical;

*R

24 denotes OH, a hydrogen atom or a saturated or unsaturated, linear or branched Ci-Clo alkyl radical; silane derivatives or polyorganosiloxanes containing a benzophenone group, such as those described in documents EP-A-0 389 377, FR-A-2 657 351 and EP-A-0 655 453; anthranilates; benzotriazoles and benzotriazole silicones; mixtures thereof.

Benzotriazoles or benzotriazole derivatives which are preferably used are those of formula (I) below: 17 N OH

I

(I)

A

in which: A denotes hydrogen or a divalent radical

-L-W-

5 Y, which may be identical or different, are chosen from Ci-C 1 i alkyl radicals, halogens, Ci-Cio alkoxy radicals and sulphonic groups, it being understood that, in the latter case, two adjacent radicals Y on the same aromatic nucleus can together 10 form an alkylidenedioxy group in which the alkylidene group contains 1 or 2 carbon atoms; with the proviso that the alkyl radicals Y are other than a sulphonic group when A is other than hydrogen; n is 1, 2 or 3; 15 L is a divalent radical of formula (II) below: p-CH-CH-

(II)

z in which: X represents O or NH, Z represents hydrogen or a Ci-C 4 alkyl radical, inclusive, 18 n is an integer between 0 and 3 m is 0 or 1, p represents an integer between1 and W is a radical of formula or 10 inclusive; below: R R R ~R R R

R

Si RSi---

I

R

I

-Si -0

I

U

-Si(R )3 in which: R, which may be identical or different, are chosen from C 1 -Clo alkyl, phenyl and 3,3,3-trifluoropropyl radicals, at least 80%, in numerical terms, of the radicals R being methyl, B, which may be identical or different, are chosen from the radicals R and the radical V of the following formula: 19 N OH Ng

(Y)

N

L

in which Y, n and L have the same meanings indicated above; r is an integer between 0 and 50 inclusive, 5 and s is an integer between 1 and 20 inclusive, and if s=0, at least one of the two radicals B denotes V; o* u is an integer between 1 and 6 inclusive, and t is an integer between 0 and 10 inclusive, it being understood that t u is greater than or equal to 3.

The benzotriazole derivatives of formula (I) *too are screening agents that are already known per se.

They are described and prepared according to the too. syntheses indicated in patents US-4 316 033 and US-4 328 346; EP-B-0 354 145 and EP-B-0 392 883 and EP-B-0 660 701 (forming an integral part of the content of the description).

Among the dibenzoylmethane derivatives which fall particularly suitably into the context of the present invention, mention may be made in particular, in a non-limiting manner, of: 2-methyldibenzoylmethane 4 -methyldibenzoylmethane 4- isopropyldibenzoylmethane 4-tert-butyldibenzoylmethane 2, 4-dimethyldibenzoylmethane 4,4' -diisopropyldibenzoylmethane 4, 4 -direthoxydibenzoylmethane 4-tert-butyl-4' -methoxydibenzoylmethane 2-methyl-5-isopropyl-4' -methoxy- 0000 0 10 dibenzoylmethane -2-methyl-5-tert-butyl-4 '-methoxy- **:dibenzoylmethane 2, 4-dimethyl-4 '-methoxydibenzoylmethane 6-dimethyl-4-tert-butyl-4 '-methoxydibenzoylmethane Among the dibenzoylmethane derivatives 0 .00.mentioned above, the one most particularly preferred for use according to the present invention is 4-(tert- 0::..,butyl) -4 -methoxydibenzoylmethane, in particular the product sold under the trade name "Parsol 1789' by the company Givaudan, this screening agent thus corresponding to the following structural formula: 0 0

H

3 C H a

OCH

3

H

3 C

CH

3 Another preferred dibenzoylmethane derivative according to the present invention is 4-isopropyldibenzoylmethane, screening agent sold under the name "Eusolex 8020" by the company Merck and corresponding to the following structural formula: 0 0 11 II

H

3 C C CH2 C HC

CH

3 The compounds of structures above are described, respectively, in US patent 4 585 597 and patent applications FR 2 236 515, 2 282 426, 2 645 148, 2 430 938 and 2 592 380.

One compound of formula which is 10 particularly preferred is benzene-l,4-bis(3methylidene-10-camphorsulphonic acid), such as the product sold under the name Mexoryl SX by the company

S

Chimex.

Benzene-1,4-bis(3-methylidene-l0- 15 camphorsulphonic acid) and its various salts (compound which are described in particular in patent applications FR-A-2 528 420 and FR-A-2 639 347, are screening agents that are already known per se (broadband screening agents) and that are in fact capable of absorbing ultraviolet rays with wavelengths of between 280 nm and 400 nm, with absorption maxima between 320 nm and 400 nm, in particular at about 345 nm. These screening agents correspond to the following general formula: DS

SO

3

D

0 in which D denotes a hydrogen atom, an alkali metal or a radical NH(R 25 )3 in which the radicals R 25 which may be identical or different, denote a hydrogen atom, a Ci-C 4 alkyl or hydroxyalkyl radical or a group Mn+/n, M"n denoting a multivalent metal cation in which n is equal to 2, 3 or 4, M n preferably denoting a metal 6 cation chosen from Ca 2 Zn 2 Mg2+, Ba2+, A13+ and Zr 4 It is clearly understood that the compounds of formula 10 above can give rise to the "cis-trans" isomer around one or more double bond(s) and that all the n isomers fall within the context of the present invention.

Examples of specific benzimidazole compounds 6** corresponding to formula (II) which may be mentioned are: 0 benzene-1,4-bis(benzimidazol-2-yl-5sulphonic acid), benzene-1,4-bis(benzoxazol-2-yl-5-sulphonic acid); as well as the partially or totally neutralized forms thereof.

Among the benzophenone derivatives of formula (III) which may be mentioned more particularly are those chosen from the group consisting of: 2,4 -dihydroxybenzophenone (benzophenone-l), such as the product sold under the name Uvinul 400 by

BASF;

2, 2' -tetrahydroxybenzophenone (benzophenone-2), such as the product sold under the name Uvinul D50 by BASF; 2 -hydroxy-4-methoxybenzophenone, also known as oxybenzone (benzophenone-3), such as the product sold under the name Uvinul M40 by BASF; 2 acid, also known as sulisobenzone (benzophenone-4), such as the product sold under the name Uvinul MS40 by BASF; as well as the sodium sulphate form thereof 2,2' -dihydroxy-4, 4' -dimethoxybenzophenone (benzophenone-6), such as the product sold under the name Helisorb 11 by Norquay; -chloro-2 -hydroxybenzophenone (benzophenone-7); 2,2k -dihydroxy-4-methoxybenzophenone, also known as dioxybenzone or benzophenone-8, such as the product sold under the name Spectra-Sorb UV-24 by American Cyanamid; the disodium salt of 2,2'-dihydroxy-4,4'dimethoxybenzophenone-5, 5'-disulphonic acid or benzophenone-9, such as the product sold under the name Uvinul DS49 by BASF; 2-hydroxy-4-methoxy-4'-methylbenzophenone benzophenone-11, such as the product sold under the name Uvinul M493 by BASF; -2-hydroxy-4-(octyloxy)benzophenone (benzophenone-12).

Among the anthranilates which can be used according to the invention, mention may be made most 10 particularly of menthyl anthranilate, such as the product sold under the name Neo Heliopan MA by the company Haarmann Reimer.

As UV-B screening agents which are particularly used in the context of the present 15 invention, mention may be made of the triazine derivatives described in particular in US patent 4 617 390 and patent applications EP-A-087 098, EP-A-0 517 104, EP-A-0 570 838 and EP-A-0 796 851.

2,4,6-Tris[p-(2'-ethylhexyl-l' -oxycarbonyl)anilino]- 20 1,3,5-triazine, sold in particular under the trade name "Uvinul T 150" by the company BASF, is known in particular.

Cinnamic acid derivatives such as isopentyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl diisopropylcinnamate, isoamyl 4-methoxycinnamate and diethanolamine 4-methoxycinnamate are also advantageously used.

Among the cinnamic acid derivatives mentioned above, the one most particularly preferred for use according to the present invention is 2-ethylhexyl p-methoxycinnamate, sold in particular under the trade name "Parsol MCX" by the company Givaudan.

Alkyl 2-cyano-3,3-diphenylacrylates can also be used, and preferably octocrylidene sold under the name Uvinul N 539 by the company BASF.

Photoprotective agents which can also 10 advantageously be used are alkyl, ethyl, propyl, octyl or glyceryl para-aminobenzoates or paradimethylaminobenzoates. 3,4 -methylbenzylidenecamphor, 3-benzylidenecamphor, benzylidenecamphor 3,4'trimethylammonium methylsulphate and 15 sulphobenzylidene)camphor and its salts can also be used.

Photoprotective agents which are most particularly preferred are 2-ethylhexyl p-methoxycinnamate, triazine derivatives, and in particular 2,4,6-tris[p-(2-ethylhexyl-l-acycarbonyl)]anilino- 1,3,5-triazine, salicylates, and in particular methyl or octyl salicylates, para-aminobenzoates or paradimethylaminobenzoates, alkyl 2-cyano-3,3-diphenylacrylate and metal oxide nanopigments, or mixtures thereof.

The cosmetic compositions according to the invention can also contain as photoprotective agents, pigments or nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably 10 nm and 50 nm) of coated or uncoated metal oxides such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and/or anatase form), of iron oxide, of zinc oxide, of zirconium oxide or of cerium oxide, which are all UV photoprotective agents that are well known per se.

Conventional coating agents are, moreover, alumina and/or aluminium stearate. Such coated or uncoated metal oxide nanopigments are described in particular in patent applications EP-A-0 518 772 and EP-A-0 518 773.

The cosmetically acceptable medium preferably consists of water or one or more cosmetically acceptable solvents such as alcohols or water/solvent(s) mixtures, the solvents preferably being CI-C 4 alcohols.

Among these alcohols which may be mentioned are ethanol and isopropanol. Ethanol is particularly preferred.

20 The composition of the invention can also contain at least one additive chosen from anionic, cationic, nonionic and amphoteric surfactants, fragrances, screening agents, preserving agents, proteins, vitamins, polymers other than those of the invention, plant, mineral or synthetic oils and any other additive conventionally used in cosmetic compositions.

Needless to say, a person skilled in the art will take care to select the optional compound(s) to be added to the composition according to the invention such that the advantageous properties intrinsically associated with the composition in accordance with the invention are not, or are not substantially, adversely affected by the addition envisaged.

These compositions may be packaged in various forms, in particular in pump-dispenser bottles or in aerosol containers, in order to ensure application of the composition in vaporized form or in the form of a eooe mousse. Such packaging forms are indicated, for "example, when it is desired to obtain a spray, a lacquer or a mousse for fixing or treating hair. The 15 compositions in accordance with the invention can also be in the form of creams, gels, emulsions, lotions or waxes.

When the composition according to the invention is packaged in aerosol form in order to 20 obtain a lacquer or a mousse, it comprises at least one propellant which may be chosen from volatile hydrocarbons such as n-butane, propane, isobutane and pentane, a halogenated hydrocarbon and mixtures thereof. Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen or compressed air can also be used as propellant. Mixtures of propellants can also be used.

Dimethyl ether is preferably used.

The propellant is advantageously present in a concentration of between 5% and 90% by weight relative to the total weight of the composition in the aerosol device, and more particularly at a concentratioiof between 10% and The compositions in accordance with the invention are particularly suitable for dry or wet hair, as styling products.

The compositions in accordance with the 10 invention can be applied to the skin, the nails, the lips, the hair, the eyebrows and the eyelashes.

oooo ~The invention will be illustrated more fully with the aid of the non-limiting example which follows.

All the percentages are relative percentages **15 by weight with respect to the total weight of the composition, and a.m. means active material.

oe

EXAMPLE:

Luviflex Silk (BASF)( 1 2 g Uvunul MS 40 1 g Ethanol 20 g AMP qs pH=7 Water qs 100 g Composition A is applied to a lock of 5 g of European natural chestnut hair. After drying, the lock feels soft and is protected against the harmful effects of the sun.

Silicone/acrylate copolymer sold by the company BASF (t-butyl acrylate/methacrylic acid/PDMS polyether) It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or in any other country.

For the purposes of this specification it will be clearly understood that the word "comprising" means "including but not limited to", and that the word "comprises" has a corresponding meaning.

a e

Claims

1. Cosmetic composition comprising, in a cosmetically acceptable medium, at least one silicone/acrylate copolymer and at least one photoprotective agent, the silicone/acrylate copolymer being obtained by radical-mediated polymerization of at least one ethylenically unsaturated monomer in the presence of at least one silicone derivative (b) 10 comprising oxyalkylene groups.

2. Composition according to Claim 1, characterized in that the monomer corresponds to S* formula (Ia): X-C-CR 7 =CHR 6 (Ia) 0 in which: X is chosen from the group comprising OH, g 20 OM, OR 8 NH2, NHR 8 and N(R 8 2 M is a cation chosen from Na', Mg"+, NH 4 alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium; the radicals R 8 may be identical or different and are chosen from the group comprising hydrogen, linear or branched C 1 to C 40 alkyl groups, mono- or polyhydroxylated C 1 to C 40 alkyl groups, optionally substituted with one or more alkoxy, amino or carboxyl groups, hydroxylated polyethers, and N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl and ethoxypropyl groups; R 7 and R 6 are chosen, independently of each other, from the group comprising hydrogen, linear or branched Ci to C 8 alkyl groups, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl groups, and CN, COOH and COOM groups. 10 3. Cosmetic composition according to Claim characterized in that the silicone derivative (b) corresponds to the formula below: 3 2. Sin which formula u R is chosen from CH 3 and the group R is chosen from hydrogen, CH 3 and the group R 4 is chosen from hydrogen, CH 3 and the groups L RI R 6 is an organic C 1 to C 40 group which can contain amino, carboxyl or sulphonate groups, and if c=0, Re is the anion of an inorganic acid; 5 the radicals R 1 may be identical or different and are chosen from C 1 to C 20 aliphatic S. hydrocarbons, C 3 to C 2 0 aliphatic or cycloaliphatic hydrocarbons, and the groups R 5 corresponding to the formula below: 5= (CH2 -O La b n is an integer between 1 and 6, *as x and y are integers chosen such that the molecular weight of the polysiloxane is between 300 and 30,000, a and b are integers between 0 and 50, and c is 0 or 1.

4. Composition according to Claim 1, characterized in that the monomer is chosen from C 1 to C 40 vinyl and allyl esters, linear C 3 to C 40 carboxylic acids or C 3 to C 40 carboxycyclic acids, vinyl or allyl haldides, vinyllactams, preferably vinylpyrrolidone and vinylcaprolactan, heterocyclic compounds substituted with vinyl or allyl groups, preferably vinylpyridine, vinyloxazoline and allylpyridine, N-vinylimidazoles, diallylamines, vinylidene chloride, carbon-based unsaturated compounds, such as styrene or isoprene, and acrylic or methacrylic acid derivatives quaternized with epichiorohydrin. 10 5. Composition according to Claim 1, characterized in that the monomer is chosen from the group comprising acrylic, methacrylic and ethacrylic acid; methyl, ethyl, propyl, n-butyl, oooo e 6isobutyl, t-butyl, 2-ethylhexyl and decyl acrylate; o o methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 0 0: 2-ethyihexyl and decyl methacrylate; methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl and decyl ethacrylate; 2,3-dihydroxypropyl acrylate; 000:00 2,3-dihydroxypropyl methacrylate; 2-dihydroxyethyl acrylate; hydroxypropyl acrylate; 2-hydroxyethyl methacrylate; 2-hydroxyethyl ethacrylate; 2-methoxyethyl acrylate; 2-ethoxyethyl methacrylate; 2-ethoxyethyl ethacrylate; hydroxypropyl methacrylate; glyceryl monoacrylate; glyceryl monomethacrylate; polyalkylene glycol (meth)acrylates, unsaturated sulphonic acids, acrylanide, methacrylamide, ethacrylanide, N,N-dimethylacrylamide, N-ethyl- acrylamide, N-ethylmethacrylamide, 1-vinylimidazole, 34 N,N-dimethylaminoethyl (meth)acrylate, maleic acid, fumaric acid, maleic anhydride and it monoesters, crotonic acid, itaconic acid, vinyl ethers, vinylformamide, vinylamine, vinylpyridine, vinylimidazole, vinylfuran, styrene, styryl sulphonate and allyl alcohol, and mixtures thereof.

6. Composition according to any one of the preceding claims, characterized in that the silicone derivatives are chosen from dimethicone copolyols and silicone surfactants.

7. Composition according to any one of the preceding claims, characterized in that it comprises, as a relative percentage by weight, from 0.1% to 20% of silicone/acrylate copolymer.

8. Composition according to claim 7, characterized in that it comprises, as a relative percentage by weight, ***from 0.5% to 10% of this copolymer.

9. Composition according to any one of claims 1 to 8, characterized in that the photoprotective agent is chosen from: dibenzoylmethane derivatives; the UV-A-active screening agents of formula I below: R* 7 O 0 in which: Hs\shonal\KeeP\SPECI\56484-o .1 SPECI.doc 13/05/02 R 7 and R 9 which may be identical or different, denote a hydrogen, a halogen, an OH radical, a saturated or unsaturated, linear or branched Ci-C 1 i alkyl radical; a saturated or unsaturated, linear or branched Ci-Clo alkoxy radical or an HSO 3 group; Ro 1 denotes hydrogen or HSO 3 Rs denotes hydroxyl; a group OR 11 in which R 11 denotes a saturated or unsaturated, linear or branched C 1 -Clo alkyl radical; or a group of the 10 following structure: alternatively a group of the following N R 1 2 or alternatively a group of the following 15 formula: formula: R16 in which: Z denotes an oxygen atom or an -NH- radical; R 13 R 14 R 1 5 and R 1 6 which may be identical or different, denote a hydrogen, a halogen, an Of radical, a saturated or unsaturated, linear or branched C 1 -Cio alkyl radical; a saturated or unsaturated, linear or branched C 1 -C 10 alkoxy radical or an HS03 group; the UV-A-active screening agents of the benzimidazole or benzoxazole type of formula (II) 10 below: R S- W denotes an oxygen atom or an -NH- radical, R denotes hydrogen or HS3;(II) R 18 in denotes a linear or branched alkoxywhich: radical containing from 1 to 10 carbon atoms approximately or a group of the following formula: in which Y represents an oxygen atom or an radic-NH- radical and R9 denotes hydrogen or HS3; R 17 denotes hydrogen or HSO 3 RI 8 denotes a linear or branched alkoxy radical containing from 1 to 10 carbon atoms approximately or a group of the following formula: in which Y represents an oxygen atom or an -NH- radical and R 19 denotes hydrogen or HSO 3 R 19 denotes hydrogen or HSO 3 benzophenone derivatives such as those of formula (III) below: R24 OH R3 Y ORm R2 R21 in which: R 20 denotes hydrogen or a saturated or unsaturated, linear or branched C 1 -Cjo alkyl radical; R 21 and R 22 which may be identical or different, denote a hydrogen, a halogen, an OH radical, a saturated or unsaturated, linear or branched Ci-Cio 10 alkyl radical; a saturated or unsaturated, linear or branched Ci-Cio alkoxy radical or an HSO 3 group; R 23 denotes hydrogen; OH; a saturated or unsaturated, linear or branched Ci-Cio alkyl radical or a saturated or unsaturated, linear or branched Ci-Clo 15 alkoxy radical; R 24 denotes OH, a hydrogen atom or a saturated or unsaturated, linear or branched Ci-Clo alkyl radical; silane derivatives or polyorganosiloxanes containing a benzophenone group; anthranilates; benzotriazoles and benzotriazole silicones; mixtures thereof. 38 Composition according to any'one of Claims 1 to 8, characterized in that the photoprotective agent is chosen from cinnamic acid derivatives, 2-ethylhexyl p-methoxycinnamate, triazine derivatives, and in particular 2,4,6-tris[p-(2- salicylates, and in particular methyl or octyl salicylates, para-aminobenzoates or para- dimethylaminobenzoates, alkyl 2-cyano-3,3-diphenyl- acrylate and metal oxide nanopigments, or mixtures thereof.

11. Composition according to any one of Claims 1 to 8, characterized in that the photoprotective agent is chosen from 3,4'-methyl- 15 benzylidenecamphor, 3-benzylidenecamphor, benzylidenecamphor 3,4'-trimethylammonium methylsulphate and 3-(4'-sulphobenzylidene)camphor and its salts.

12. Composition according to any one of the preceding claims, characterized in that it also contains at least one additive chosen from anionic, *0* o cationic, nonionic and amphoteric surfactants, fragrances, preserving agents, proteins, vitamins, polymers other than those of the invention, and plant, mineral or synthetic oils.

13.. Process for holding or shaping the hairstyle, characterized in that it uses a composition R accordance with any one of Claims 1 to 12.. 39

14. Use of a composition according to any one of claims 1 to 12, for the manufacture or a cosmetic product, in particular a hair product. Use according to any one of claims 1 to 12, for the skin, the nails, the lips, the hair, the eyebrows and the eyelashes.

16. Cosmetic compositions, uses and processes involving them, substantially with reference to the following example. Dated this 13 th day of May 2002 L'OREAL By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia H,\shona1\Keep\SPECI\S6484-OO.1 SPECI.doC 13/05/02