FR2819183A1 - SELF-BONDING COMPOSITIONS BASED ON AMPHIPHILIC POLYMERS OF AT LEAST ONE SULFONICALLY GROUPED ETHYLENE UNATURATION MONOMER COMPRISING A HYDROPHOBIC PART - Google Patents

Abstract

The invention relates to novel cosmetic compositions for topical use, primarily intended for artificial skin tanning and/or browning, comprising, in a cosmetically acceptable medium, a self-tanning agent and at least one amphiphilic polymer containing at least one monomer having ethylenic unsaturation with a sulphonic group, in free form or partially or totally neutralised, and comprising at least one hydrophobic part. The inventive compositions are very stable and produce a more homogeneous colour. The invention also relates to the use for said compositions in the aforementioned cosmetic application.

Description

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v- : COMPOSITIONS AUTOBRONZANTES A BASE DE POLYMERES AMPH ! PH ! LES D'AU MOINS UN MONOMERE A INSATURATION ETHYLENIQUE A GROUPEMENT SULFONIQUE ET COMPORTANT UNE PARTIE HYDROPHOBE La présente invention concerne de nouvelles compositions cosmétiques à usage topique plus particulièrement destinées au bronzage et/ou au brunissage artificiels de la peau (compositions ci-après dénommées plus simplement compositions auto bronzantes), ainsi que leur utilisation dans l'application cosmétique susmentionnée. Plus précisément encore, elle concerne des compositions auto bronzantes à stabilité améliorée, qui comprennent, dans un support cosmétiquement acceptable, au moins un agent autobronzant, et au moins un polymère amphiphile comportant au moins un monomère à insaturation éthylénique à groupement suifonique, sous forme libre ou partiellement ou totalement neutralisée, et comprenant au moins une partie hydrophobe.

v-: AUTOBRONIZING COMPOSITIONS BASED ON AMPH POLYMERS! PH! The present invention relates to novel cosmetic compositions for topical use, more particularly intended for the artificial tanning and / or browning of the skin (compositions hereinafter referred to as "the most"). simply self-tanning compositions), as well as their use in the aforementioned cosmetic application. More specifically, it relates to self-tanning compositions with improved stability, which comprise, in a cosmetically acceptable support, at least one self-tanning agent, and at least one amphiphilic polymer comprising at least one unsaturated ethylenically unsaturated monomer, in free form. or partially or totally neutralized, and comprising at least one hydrophobic part.

It is known that mono-or polycarbonyl compounds such as for example isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, dihydroxyacetone (DHA) are particularly interesting products which are commonly used in cosmetics as artificial tanning agents of the skin.

Applied on the skin, especially on the face, these compounds can achieve a tanning effect or browning appearance more or less similar to that which can result from prolonged exposure to the sun (natural tanning) or under a lamp UV. Such use also has the advantage of completely avoiding the risks of cutaneous reaction generally attached to the aforementioned prolonged exposures (erythema, burns, loss of elasticity, appearance of wrinkles, premature aging of the skin, and others).

One of the problems encountered with the current self-tanning cosmetic compositions and in particular those based on DHA is that the intensity of the coloration obtained on the skin and / or its behavior over time (resistance to washing in particular) and / or the speed with which this coloration develops, are often considered as insufficient by the users.

Another difficulty lies in the fact that DHA has an unfortunate tendency, more or less pronounced depending on the nature of the medium in which it is formulated, to deteriorate over time, thus causing problems of storage and / or conservation that generally result in the long term undesirable yellowing of compositions that contain it.

In an attempt to obviate these various drawbacks, it has already been proposed, in the patent application FR-A-2,698,267 in the name of the Applicant, to associate the DHA with a particular copolymer acting as a thickener, namely a crosslinked copolymer of acrylamide / 2-acrylamido-2-methylpropanesulphonic acid (including the "SEPIGEL 305" 'marketed by the company SEPPIC).

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Although such compositions containing this copolymer are of interest and actually have improved properties compared to those which are free from it, they do not yet give completely satisfactory results in terms of their stability, in terms of water resistance. and the homogeneity of the color obtained.

The present invention aims at providing new cosmetic compositions based on a self-tanning agent which have on the one hand a good self-tanning effectiveness on the skin (intensity and color retention), as well as, on the other hand, excellent stability. .

Thus, following important research conducted on the subject, it has now been found by the Applicant, and this in a completely unexpected and surprising way, that it is possible to improve the skin color attached to the self-tanning compositions prior art and their stability, by introducing into the latter at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing sulfonic group, in free form or partially or completely neutralized, and comprising at least one hydrophobic part.

This discovery is the basis of the present invention.

According to one of the objects of the present invention, it is now proposed new cosmetic compositions more particularly intended for artificial tanning of the skin, of the type comprising, in a cosmetically acceptable support, at least one self-tanning agent and at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group, in free form or partially or totally neutralized, and comprising at least one hydrophobic part.

The polymers in accordance with the invention are amphiphilic polymers comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free or partially or totally neutralized form, and comprising at least one hydrophobic part.

Amphiphilic polymer is understood to mean any polymer comprising both a hydrophilic part and a hydrophobic part and in particular a fatty chain.

The hydrophobic part present in the polymers of the invention preferably comprises from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms, even more preferably from 6 to 18 carbon atoms, and more particularly from 12 to 18 carbon atoms. atoms.

The polymers according to the invention are preferably neutralized partially or totally by a mineral base (sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- and tri-ethanolamine, an aminomethylpropanediol, N-methyl -glucamine, basic amino acids such as arginine and lysine, and mixtures thereof.

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FLes polymères amphiphiles conformes à l'invention ont en général un poids moléculaire moyen en nombre allant de 1000 à 20 000 000 g/mole, de préférence allant de 20 000 à 5 000 000 et plus préférentiellement encore de 100 000 à 1 500 000 g/mole.

The amphiphilic polymers according to the invention generally have a number average molecular weight ranging from 1000 to 20,000,000 g / mole, preferably from 20,000 to 5,000,000 and even more preferably from 100,000 to 1,500,000 g. /mole.

The amphiphilic polymers according to the invention may be crosslinked or non-crosslinked. Preferably, crosslinked amphiphilic polymers are chosen.

When they are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for crosslinking the polymers obtained by radical polymerization.

There may be mentioned, for example, divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol dinyl ether, hydroquinone diallyl ether, di (meth) acrylate ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylene-bis-acrylamide, methyl en-bis-methacryl) amide,! a tria!) ytamine,! e tria! iy! cyanurate, ie diatiy! my ! eate,! tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane-diallylether, allyl (meth) acrylate, allylic ethers of alcohols of the series of sugars or other allyl- or vinyl-ethers of polyfunctional alcohols, as well as the allylic esters of the phosphoric and / or vinylphosphonic acid derivatives or the mixtures of these compounds. Methylenebisacrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA) will be used more particularly. The degree of crosslinking will vary generally from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.

The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrene sulphonic acid, (meth) acrylamido (C1-C22) alkylsultonic acids and N- (C1-C22) alkyl (meth) acrylamido acids. (C1-C22) alkylsulfonic acids such as undecyl-acrylamido-methanesulfonic acid and their partially or totally neutralized forms.

alkylsulfoniques tels que par exemple l'acide acrylamido-méthane-sulfonique, l'acide acrylamido-éthane-sulfonique, l'acide acrylamido-propane-sulfonique, l'acide 2-acrylamido-2-méthylpropane-sulfonique, l'acide méthacrylamido-2méthy ! propane-sutfonique, !'acide 2-acry) am ! do-n-butane-su ! fonique, Fac ! de 2acrylamido-2, 4, 4-triméthylpentane-sulfonique, l'acide 2-méthacrylamido-dodécylsultonique, l'acide 2-acrylamido-2, 6-diméthyl-3-heptane-sulfonique ainsi que leurs formes partiellement ou totalement neutralisées. More preferably, the (meth) acrylamido (C 1 -C 22) acids will be used.

alkylsulfonic acids such as for example acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido acid, 2methy! propane-sulfonic acid, 2-acrylate) am! do-n-butane-su! fonic, Fac! 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsultonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or completely neutralized forms.

More particularly, the monomer 2-acrylamido-2-methylpropanesulphonic acid (AMPS) and its partially or completely neutralized forms will be used.

The amphiphilic polymers according to the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or a C6-C22 di-n-alkylamine, and such as those described in the patent application. WO00 / 31154 (forming an integral part of the content of the description). These polymers may also contain other

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vmonomères hydrophiles éthyléniquement insaturés choisis par exemple parmi les acides (méth) acryliques, leurs dérivés alkyl substitués en p ou leurs esters obtenus avec des monoalcools ou des mono-ou poly-alkylèneglycols, les (méth) acrylamides, la vinylpyrrolidone, l'anhydride maléique, l'acide itaconique ou l'acide maléique ou les mélanges de ces composés.

hydrophilic ethylenically unsaturated monomers chosen for example from (meth) acrylic acids, their p-substituted alkyl derivatives or their esters obtained with monoalcohols or mono or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride , itaconic acid or maleic acid or mixtures of these compounds.

The preferred polymers of the invention are chosen from AMPS amphiphilic copolymers and at least one hydrophobic ethylenically unsaturated monomer comprising at least one hydrophobic part having from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms. carbon and more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

These same copolymers may also contain one or more ethylenically unsaturated hydrophilic monomers not comprising a fatty chain, such as (meth) acrylic acids, their ss-substituted alkyl derivatives or their esters obtained with monoalcohols or mono or polyalkylene glycols. , (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof.

These copolymers are described in particular in patent application EP-A-750899, patent US 5089578 and in the following Yotaro Morishima publications: Self-assembling amphiphilic polyelectrolytes and their nanostructures.
Chinese Journal of Polymer Science Vol. 18, NO40, (2000), 323-336. - Miscellanous formation of random copolymers of 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromoler in water as studied by fluorescence and dynamic light scattering-Macromolecules 2000,
Flight. 33, No. 10-3694-3704; - Solutions properties of micelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior-
Langmuir, 2000, Vol. 16, NO12, 5324-5332)); Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers - Polym. Preprint,
Div. Polym. Chem. 1999, 40 (2), 220-221.

particuliers sont choisis de préférence parmi les acrylates ou les acrylamides de formule (1) suivante :

The hydrophobic monomers with ethylenic unsaturation of these copolymers

particular are preferably chosen from acrylates or acrylamides of formula (1) below:

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Fdans laquelle R1 et R3, identiques ou différents, désignent un atome d'hydrogène ou un radical alkyle linéaire ou ramifié en Ci-Ce (de préférence méthyle) ; Y désigne 0 ou NH ; R2 désigne un radical hydrocarboné hydrophobe comportant au moins de 6 à 50 atomes de carbone et plus préférentiellement de 6 à 22 atomes de carbone et encore plus préférentiellement de 6 à 18 atomes de carbone et plus particulièrement de 12 à 18 atomes de carbone ; x désigne un nombre de moles d'oxyde d'alkylène et varie de 0 à 100.

F in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is 0 or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

The radical R2 is preferably chosen from linear (e.g. n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (e.g. cyclododecane (C12) alkyl radicals. or adamantane (Clo)); C6-C18 perfluorinated alkyl radicals (for example the group of formula - (CH2) 2- (CF2) 9-CF3); the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, linear alkyl radicals, and more particularly the n-dodecyl radical, are more particularly preferred.

According to a particularly preferred form of the invention, the monomer of formula (1) comprises at least one alkylene oxide unit (x> 1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly ethylene oxide units. The number of oxyalkylenated units generally varies from 3 to 100 and more preferably from 3 to 50 and even more preferably from 7 to 25.

Among these polymers, mention may be made of: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 16) alkyl (meth) units acrylamide or (C 8 -C 16) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A-750 899; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-C18) units; kylacrylamide, such as those described in US-5089578.

Mention may also be made of copolymers of completely neutralized AMPS and of dodecyl methacrylate, as well as copolymers of uncrosslinked and crosslinked AMPS and ndodecylmethacrylamide, such as those described in the Morishima articles cited above.

More particularly, copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

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Fdans laquelle X+ est un proton, un cation de métal alcalin, un cation alcalino- 1 terreux ou l'ion ammonium, et de motifs de formule (ici) suivante :

dans laquelle x désigne un nombre entier variant de 3 à 100, de préférence de 5 à
80 et plus préférentiellement de 7 à 25 ; R1 a la même signification que celle indiquée ci-dessus dans la formule (1) et R4 désigne un alkyle linéaire ou ramifié en Co-Css et plus préférentiellement en Clo-C22.

F in which X + is a proton, an alkali metal cation, an alkaline earth cation or ammonium ion, and units of the following formula (here):

in which x denotes an integer ranging from 3 to 100, preferably from 5 to
80 and more preferably 7 to 25; R1 has the same meaning as that indicated above in the formula (1) and R4 denotes a linear or branched alkyl in Co-Css and more preferably in Clo-C22.

Particularly preferred polymers are those where x = 25, R1 is methyl and R4 is n-dodecyl; they are described in the articles of
Morishima mentioned above.

 The polymers for which X + denotes sodium or ammonium are more particularly preferred.

 The preferred amphiphilic polymers according to the invention can be obtained according to the conventional methods of radical polymerization in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, ABAH (2, 2- azobis- [2-amidinopropane] hydrochloride), organic peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc ..., inorganic peroxidized compounds such as potassium persulfate or ammonium or H 2 O 2 optionally in the presence of reducing agents.

 They are especially obtained by radical polymerization in tent-butanol medium in which they precipitate.

By using precipitation polymerization in tert-butanol, it is possible to obtain a particle size distribution of the polymer which is particularly favorable for its uses.

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The distribution of the particle size of the polymer can be determined, for example, by laser diffraction or image analysis.

An interesting distribution for polymer type and determined by image analysis is as follows: 60, 2% less than 423 microns, 52.0% less than 212 microns, 26.6% less than 106 microns, 2, 6 % less than 45 microns and 26.6% greater than 850 microns.

The reaction may be conducted at a temperature between 0 and 150oC, preferably between 10 and 100oC, either at atmospheric pressure or under reduced pressure. It can also be carried out under an inert atmosphere, and preferably under nitrogen.

,-d'un alcool en C-jg-Cg oxyéthyiéné par 8 moles d'oxyde d'éthylène (GENAPOL T-080 de la société HOECHST/CLARIANT), -d'un alcool en C16-C18 oxyéthyléné par 15 moles d'oxyde d'éthylène (GENAPOL# T-150 de la société HOECHST/CLARIANT),

,-d'un alcool en C-C-) g oxyéthyiéné par 11 moles d'oxyde d'éthylène (GENAPOL T-110 de la société HOECHST/CLARIANT), -d'un alcool en C16-C18 oxyéthyléné par 20 moles d'oxyde d'éthylène (GENAPOL# T-200 de la société HOECHST/CLARIANT),

,-d'un alcool en C-jg-Cg oxyéthyténé par 25 moles d'oxyde d'éthylène (GENAPOL T-250 de la société HOECHST/CLARIANT), -d'un alcool en C-) g-Cs oxyéthyiéné par 25 moles d'oxyde d'éthylène et/ou d'un alcool iso C16-C18 oxyéthyléné par 25 moles d'oxyde d'éthylène. According to this process, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its sodium or ammonium salts, with a (meth) acrylic acid ester, has been polymerized and, -d a C10-C18 alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOL'E'C-080 from the company HOECHST / CLARIANT), -a C11 oxo alcohol oxyethylenated with 8 moles of oxide of ethylene oxide; ethylene (GENAPOL UD-080 from the company HOECHST / CLARIANT), -an oxo C11 oxyethylenated with 7 moles of ethylene oxide (GENAPOLO # UD-070 HOECHST / CLARIANT), -of a C12-C14 alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOL # LA-070 from Hoechst / Clariant), of a C12-C14 alcohol oxyethylenated with 9 moles of ethylene oxide (GENAPOL # LA-090 from the company HOECHST / CLARIANT), a C12-C14 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL # LA-110 from the company HOECHST / CLARIANT),

of a C 1 -C 8 -alkyl oxyethylenated with 8 moles of ethylene oxide (GENAPOL T-080 from the company HOECHST / CLARIANT), of a C16-C18 alcohol oxyethylenated with 15 moles of ethylene oxide (GENAPOL # T-150 from the company HOECHST / CLARIANT),

of an alcohol in CC 2) oxyethylenated with 11 moles of ethylene oxide (GENAPOL T-110 from the company HOECHST / CLARIANT), of a C16-C18 alcohol oxyethylenated with 20 moles of oxide ethylene (GENAPOL # T-200 from HOECHST / CLARIANT),

of a C 1 -C 8 -alkyl oxyethylenated with 25 moles of ethylene oxide (GENAPOL T-250 from the company HOECHST / CLARIANT), -a C-) g-Cs alcohol oxyethylenated by 25 moles of ethylene oxide and / or an iso C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide.

The molar concentration in% of the units of formula (II) and of units of formula (III) in the polymers according to the invention will vary according to the application

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r cosmétique souhaitée et des propriétés rhéologiques de la formulation recherchées. Elle peut varier entre 0, 1 et 99, 9% en moles.

desired cosmetic and rheological properties of the desired formulation. It can vary between 0, 1 and 99, 9 mol%.

Preferably for the most hydrophobic polymers, the molar proportion of units of formula (1) or (here) varies from 50, 1 to 99, more particularly from 70 to 95% and even more particularly from 80 to 90%.

Preferably for the low hydrophobic polymers, the molar proportion of units of formula (1) or (III) ranges from 0.1 to 50%, more particularly from 5 to 25% and even more particularly from 10 to 20%.

The distribution of the monomers in the polymers of the invention may be, for example, alternating, block (including multiblock) or any.

According to the invention, it is preferred that the polymers have pendant heat-sensitive chains and whose aqueous solution has a viscosity which, above a certain threshold temperature, increases or remains substantially constant as the temperature increases.

Even more particularly, polymers whose aqueous solution has a viscosity which is low below a first threshold temperature and which, above this first threshold temperature, increases towards a maximum when the temperature increases, and which, at above a second threshold temperature decreases again as the temperature increases. In this context, it is preferred that the viscosity of the polymer solutions below the first threshold temperature is from 5 to 50%, in particular from 10 to 30% of the maximum viscosity at the second threshold temperature.

These polymers, preferably, lead in the water to a demixing phenomenon by heating resulting in curves having, as a function of temperature and concentration, a minimum called LCST (Lower Critical Solution Temperature).

The viscosities (measured at 25 ° C. on the Brookfield needle 7 viscometer) of the 1% aqueous solutions are preferably 20,000 mPa. s at 100,000 mPa. s and more particularly 60,000 mPa. s at 70,000 mPa. s.

g) ycéra ! déhyde, t'atdéhyde mésotartrique, la glutaraldéhyde, l'érythrulose, les dérivés de pyrazolin-4, 5-diones telles que décrits dans la demande de brevet FR2466492 et W09735842, la dihydroxyacétone (DHA), les dérivés de 4,4-

1 The amphiphilic polymers in accordance with the invention are present in the compositions in concentrations ranging from 0.01 to 30% by weight, more preferably from 0.1 to 10%, even more preferentially from 0.1 to 5% by weight, and more particularly still from 0.5 to 2% by weight. The self-tanning agents are generally chosen from mono or polycarbonyl compounds! such as isatin, alloxane, ninhydrin,

g) ycera! dehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4,5-diones derivatives as described in patent application FR2466492 and WO9735842, dihydroxyacetone (DHA), 4,4-dione derivatives,

1

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Fdihydroxypyrazolin-5-ones telles que décrits dans la demande de brevet EP903342.

Dihydroxypyrazolin-5-ones as described in patent application EP903342.

In a particularly preferred embodiment of the invention, dihydroxyacetone (DHA) will be used more particularly.

These self-tanning agents may be combined with at least one synthetic direct dye or natural and / or at least one indole derivative such as those described in patents EP425324 and EP456545.

These self-tanning agents may also be associated with other synthetic or natural skin coloring agents.

For the purpose of the present invention, the term "skin coloring agent" will be understood to mean any compound having a particular affinity for the skin, enabling it to give the latter a durable, non-covering coloring (ie not having tendency to opacify the skin) and which is eliminated with neither water nor with the aid of a solvent, and which is resistant to both rubbing and washing with a solution containing surfactants. Such durable coloration is therefore distinguished from the superficial and momentary coloration provided for example by a makeup pigment.

The additional coloring agents may also be chosen for example from plant extracts such as, for example, "insoluble" red wood extracts of the genus Pterocarpus and of the genus Baphia such as Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida as described in patent application EP971683.

The coloring agents may also be iron oxide nanopigments with an average elementary particle size of less than 100 nm, such as those described in patent application EP966953.

The self-tanning agents are generally present in the compositions according to the invention in proportions ranging from 0.1 to 10% by weight relative to the total weight of the composition, and preferably from 0.2 to 8% by weight relative to total weight of the composition The self-tanning compositions in accordance with the invention can be in the form of creams, milks, gels, gel-creams, oil-in-water emulsions, vesicular dispersions, fluid lotions, in particular vaporizable fluid lotions or any other form generally used in cosmetics, in particular that which is usually suitable for self-tanning cosmetic compositions.

The compositions in accordance with the present invention may furthermore comprise conventional cosmetic adjuvants, chosen in particular from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers , emollients, silicones, α-hydroxy acids, anti-inflammatory agents,

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Fmousse, les agents hydratants, les vitamines, les agents répulsifs contre les insectes, les antagonistes de substance P, les anti-inflammatoires, les parfums, les conservateurs, les tensioactifs, les charges, les polymères autres que ceux de l'invention, les propulseurs, les agents alcalinisant ou acidifiants, les colorants ou tout autre ingrédient habituellement utilisé dans le domaine cosmétique et/ou dermatologique, en particulier pour la fabrication de compositions auto bronzantes sous forme d'émulsions.

Foam, moisturizing agents, vitamins, insect repellents, substance P antagonists, anti-inflammatories, fragrances, preservatives, surfactants, fillers, polymers other than those of the invention, propellants, alkalinizing or acidifying agents, dyes or any other ingredient usually used in the cosmetic and / or dermatological field, in particular for the manufacture of self-tanning compositions in the form of emulsions.

The fatty substances may consist of an oil or a wax or mixtures thereof. By oil is meant a liquid compound at room temperature. By wax is meant a solid or substantially solid compound at room temperature, and whose melting point is generally greater than 35OC.

As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed oil, jojoba oil); synthetic compounds such as perhydrosqualene, alcohols, acids or fatty esters (such as the C12-C15 alcohol benzoate sold under the trade name "Finsolv TN" by the company Finetex, octyl palmitate, isopropyl lanolate , triglycerides, including those of capric / caprylic acids), oxyethylenated or oxypropylene-silicone (cyclomethicone, polydimethylsiloxane or PDMS) or fluorinated esters and fatty ethers; polyalkylenes; and their mixtures.

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

Among the organic solvents, mention may be made of lower alcohols and polyols having at most 8 carbon atoms.

The thickeners may be chosen in particular from crosslinked polyacrylic acids, guar gums and modified or unmodified celluloses such as hydroxypropyl guar gum, methylhydroxyethylcellulose and hydroxypropylmethylcellulose.

The compositions according to the invention may further comprise at least one organic photoprotective agent and / or at least one inorganic photoprotective agent active in the UVA and / or UVB (absorbers), water-soluble or fat-soluble or solvent-insoluble. commonly used cosmetics.

The organic photoprotective agents are in particular chosen from anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives, camphor derivatives; triazine derivatives such as those described in patent applications US4,367, 390, EP863145, EP517104, EP570838, EP796851, EP775698, EP878469 and EP933376; benzophenone derivatives; ss, ss'-diphenylacrylate derivatives; benzotriazol derivatives; benzalmalonate derivatives; benzimidazole derivatives; imadazolines bis-benzoazolyl derivatives as described in patents EP669323 and US 2,463,264; p-aminobenzoic acid derivatives (PABA); methylene bis- (hydroxyphenylbenzotriazole) derivatives as described in US5,237, 071, US5, 166,355, GB2303549, DE19726184 and EP893119;

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Fles polymères filtres et silicones filtres tels que ceux décrits notamment dans la demande WO-93/04665 ; les dimères dérivés d'a-aikyistyrène tels que ceux décrits dans la demande de brevet DE19855649 ; les 4, 4-diarylbutadiènes tels que décrits dans les demandes EP0967200 et DE19755649 et leurs mélanges.

Filter polymers and silicone filters such as those described in particular in the application WO-93/04665; dimers derived from α-aikyistyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in Applications EP0967200 and DE19755649 and mixtures thereof.

et REIMER, Dérivés du dibenzovfméthane : - Butyl Methoxydibenzoyimethane vendu notamment sous le nom commercial PARSOL 1789 par HOFFMANN LA ROCHE, - tsopropyl Dibenzoylmethane, Dérivés cinnamiques : - Ethylhexyl Methoxycinnamate vendu notamment sous le nom commercial PARSOL MCX par HOFFMANN LA ROCHE, - Isopropyl Methoxy cinnamate, - Isoamyl Methoxy cinnamate vendu sous le nom commercial NEO HELIOPAN
E 1000 par HAARMANN et REIMER, - Cinoxate, - DEA Methoxycinnamate, - Diisopropyl Methylcinnamate, - Glyceryl Ethylhexanoate Dimethoxycinnamate Dérivés de ss,ss'-diphénylacrylate : - Octocrylene vendu notamment sous le nom commercial UVINUL N539 par
BASF, - Etocrylene, vendu notamment sous le nom commercial UVINUL N35 par
BASF, Dérivés de la benzophénone : - Benzophenone-1 vendu sous le nom commercial UVINUL 400 par BASF, As examples of organic photoprotective agents active in the UV-A and / or UV-B, mention may be made above under their INCI name: Derivatives of para-aminobenzoic acid: - PABA, - Ethyl PABA Ethyl Dihydroxypropyl PABA, Ethylhexyl Dimethyl PABA sold in particular under the name ESCALOL 507 by ISP, Glyceryl PABA, PEG-25 PABA sold under the name UVINUL P25 by BASF, Salicylic derivatives: Homosalate sold under the name Eusolex HMS by RONA / EM
INDUSTRIES, - Ethylhexyl Salicylate sold under the name NEO HELIOPAN OS by
HAARMANN and REIMER, - Dipropylene glycol salicylate sold under the name DIPSAL by SCHER, - TEA Salicylate, sold under the name NEO HELIOPAN TS by HAARMANN

and REIMER, Derivatives of dibenzovfmethane: Butyl Methoxydibenzoyimethane sold in particular under the trade name PARSOL 1789 by Hoffmann La Roche, tsopropyl dibenzoylmethane, cinnamic derivatives: Ethylhexyl methoxycinnamate sold in particular 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, - Cinoxate, - DEA Methoxycinnamate, - Diisopropyl Methylcinnamate, - Glyceryl Ethylhexanoate Dimethoxycinnamate Derivatives of ss, ss'-diphenylacrylate: - Octocrylene sold in particular under the trade name UVINUL N539 by
BASF, Etocrylene, sold in particular under the trade name UVINUL N35 by
BASF, Derivatives of benzophenone: Benzophenone-1 sold under the trade name UVINUL 400 by BASF,

<Desc / Clms Page number 12>

-----------Benzophenone-2 vendu sous le nom commercial UVINUL D50 par BASF Benzophenone-3 ou Oxybenzone, vendu sous le nom commercial UVINUL M40 par BASF, Benzophenone-4 vendu sous le nom commercia ! UViNUL MS40 par BASF, Benzophenone-5, Benzophenone-6 vendu sous le nom commercial HELISORB 11 par
NORQUAY, Benzophenone-8 vendu sous le nom commercial SPECTRA-SORB UV-24
PAR AMERICAN CYANAMID, Benzophenone-9 vendu sous le nom commercial UVINUL DS-49 par BASF, - Benzophenone-12, Dérivé du benzvlidène camphre : - 3-Benzylidene camphor fabriqué sous le nom MEXORYL SD par CHIMEX, - 4-Methylbenzylidene camphor vendu sous le nom EUSOLEX 6300 par
MERCK, - Benzylidene Camphor Sulfonic Acid fabriqué sous le nom MEXORYL SL par CHIMEX, - Camphor Benzaikonium Methosu ! fate fabriqué sous le nom MEXORYL SO par CHIMEX,

--Terephthalylidene Dicamphor Sulfonic Acid fabriqué sous le nom MEXORYL SX par CHIMEX, - Polyacrylamidomethyl Benzylidene Camphor fabriqué sous le nom MESORYL SW par CHIMEX, Dérivés de benzimidazole : enzimidazole Sulfonic Acid vendu notamment sous le nom commercial EUSOLEX 232 par MERCK, - Benzimidazilate vendu sous le nom commercial NEO HELIOPAN AP par
HAARMANN et REIMER, Dérivés de triazine : - Anisotriazine vendu sous le nom commercial TINOSORB S par CIBA
SPECIALTY CHEMICALS, - Ethylhexyl triazone vendu notamment sous le nom commercial UVINUL
T150 par BASF, - Diethylhexyl Butamido Triazone vendu sous le nom commercial UVASORB HEB par SIGMA 3V,

Dérivés de benzotriazole : - Drometrizole Trisiloxane vendu sous le nom SILATRIZOLE par RHODIA CHIMIE, - Methylène bis-Benzotriazolyl Tetramethylbutylphénol, vendu sous forme solide sous le nom commercial MIXXIM BB/100 par FAIRMOUNT CHEMICAL ou sous forme micronisé en dispersion aqueuse sous le nom commercial TINOSORB M par CIBA SPECIALTY CHEMICALS, Dérivés anthraniliques :

----------- 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
AMERICAN CYANAMID, Benzophenone-9 sold under the trade name UVINUL DS-49 by BASF, Benzophenone-12, Derivative of benzylidene camphor: 3-Benzylidene camphor manufactured under the name MEXORYL SD by CHIMEX, 4-Methylbenzylidene camphor sold under the name EUSOLEX 6300 by
MERCK, - Benzylidene Camphor Sulfonic Acid manufactured under the name MEXORYL SL by CHIMEX, - Camphor Benzaikonium Methosu! fate manufactured under the name MEXORYL SO by CHIMEX,

--Terephthalylidene Dicamphor Sulfonic Acid manufactured under the name MEXORYL SX by CHIMEX, - Polyacrylamidomethyl Benzylidene Camphor manufactured under the name Mesoryl SW by Chimex, derivatives of benzimidazole: enzimidazole Sulfonic Acid sold in particular under the trade name Eusolex 232 by Merck, - Benzimidazilate sold under the trade name NEO HELIOPAN AP by
HAARMANN and REIMER, Triazine derivatives: - Anisotriazine sold under the trade name TINOSORB S by CIBA
SPECIALTY CHEMICALS, - Ethylhexyl triazone sold in particular under the trade name UVINUL
T150 by BASF, - Diethylhexylbutamido triazone sold under the trade name UVASORB HEB by SIGMA 3V,

Derivatives of benzotriazole: - Drometrizole Trisiloxane sold under the name Silatriazole by Rhodia Chimie, - Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold in solid form under the trade name MIXXIM BB / 100 by FAIRMOUNT CHEMICAL or in micronized form in aqueous dispersion under the trade name TINOSORB M by CIBA SPECIALTY CHEMICALS, Anthranilic Derivatives:

<Desc / Clms Page number 13>

r Menthyl anthranilate vendu sous le nom commercial NEO HELIOPAN MA par HAARMANN et REIMER,
Dérivés d'imidazoline - Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,
Dérivés de benzalmalonate : - Polyorganosiloxane à fonctions benzalmalonate vendu sous la dénomination commerciale PARSOL SLX par HOFFMANN LA ROCHE et leurs mélanges.

Menthyl anthranilate sold under the trade name NEO HELIOPAN MA by HAARMANN and REIMER,
Imidazoline Derivatives - Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,
Derivatives of benzalmalonate: - Polyorganosiloxane containing benzalmalonate functions sold under the trade name Parsol SLX by Hoffmann La Roche and their mixtures.

 The most preferred organic photoprotective agents are chosen from the following compounds: Ethylhexyl salicylate, Butyl Methoxydibenzoytmethane, Ethylhexyl Methoxycinnamate, Octocrylene, Phenylbenzimidazole Sulfonic Acid, Terephthalylidene Dicamphor Sulfonic, Benzophenone-3, Benzophenone-4, Benzophenone-5,4-methylbenzylidene camphor, Benzimidazilate, Anisotriazine, Ethylhexyl triazone, - Diethylhexyl butamido triazone, - Methylene bis-benzotriazolyl tetramethylbutylphenol, - Drometrizole trisiloxane, and mixtures thereof.

 The inorganic photoprotective agents are chosen from pigments or even nanopigments (average size of the primary particles: generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm) of coated or uncoated metal oxides such as, for example, nanopigments of titanium oxide (amorphous or crystallized in rutile and / or anatase form), iron, zinc, zirconium or cerium and their. Conventional coating agents are, moreover, alumina and / or aluminum stearate. Such nanopigments of metal oxides, coated or uncoated, are in particular described in patent applications EP518772 and EP518773.

 The photoprotective agents are generally present in the compositions according to the invention in proportions ranging from 0.1 to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.2 to 15% by weight relative to to the total weight of the composition.

Of course, those skilled in the art will take care to choose the optional additional compound or compounds mentioned above e or their amounts so that the advantageous properties intrinsically attached to the association in accordance with

<Desc / Clms Page number 14>

Fl'invention ne soient pas, ou substantiellement pas, altérées par la ou les adjonctions envisagées. Les compositions selon l'invention peuvent être préparées selon les techniques bien connues de l'homme de l'art, en particulier celles destinées à la préparation d'émulsions de type huile-dans-eau ou eau-dans-huile.

The invention is not, or not substantially, impaired by the addition or additions contemplated. The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art, in particular those intended for the preparation of oil-in-water or water-in-oil type emulsions.

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

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

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

The invention also relates to a cosmetic treatment method for tanning and / or artificially browning the skin, characterized in that it consists in applying thereon an effective amount of a composition as defined above.

The invention also relates to the use of an AMPS amphiphilic polymer comprising at least one fatty chain as defined above in order to improve the coloration and / or stability of a self-tanning agent such as those defined above. top content in a cosmetic composition for artificial tanning and / or browning of the skin.

Concrete but non-limiting examples illustrating the invention will now be given.

PREPARATION EXAMPLES Preparation of ethoxylated (meth) acrylic esters

They may especially be obtained by the action of glycidyl (meth) acrylate or of (meth) acrylic acid or of an alkyl (meth) acrylate or a (meth) acryloyl halide on an ethoxylated fatty alcohol. By way of non-limiting examples, mention may be made of the following preparations: a) from glycidyl methacrylate and from GENAPOL T-250 b) from (meth) acrylic acid and from GENAPOL UD-070 c) from methyl (meth) acrylate and GENAPOL LA-090 d) from (meth) acryloyl chloride and GENAPOL UD-070. a) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol T-250 and 75 g of glycidyl methacrylate are introduced. The reaction mixture is heated to a temperature of 100.degree.

<Desc / Clms Page number 15>

r pendant 2 heures, et on élimine l'excès de méthacrylate de glycidyl par distillation sous pression réduite. Le monomère obtenu peut être utilisé pour la polymérisation sans purification ultérieure. b) Dans un réacteur tricol d'un litre équipé d'un agitateur, d'un thermomètre et d'un condensateur à reflux, on introduit 500g de Genapol UD-070,100g d'acide (méth) acrylique et de l'acide p-toluènesulfonique comme catalyseur. On chauffe le mélange réactionnel au reflux pendant 2 heures, et l'on sépare l'excès d'acide et d'eau formée au cours de la réaction par distillation sous pression réduite. Le monomère obtenu peut être utilisé pour la polymérisation sans purification ultérieure. c) Dans un réacteur tricol d'un litre équipé d'un agitateur, d'un thermomètre et d'un condensateur à reflux, on introduit 500g de Genapol LA-090, 100g de (méth) acrylate de méthyle et 20g de tétraisopropoxyde de titane. On chauffe le mélange réactionnel au reflux pendant 2 heures, et après séparation par distillation de l'alcool formé, on distille l'ester qui reste sous pression réduite. Le monomère obtenu peut être utilisé pour la polymérisation sans purification ultérieure. d) Dans un réacteur tricol d'un litre équipé d'un agitateur, d'un thermomètre et d'un condensateur à reflux, on introduit 500g de Genapol UD-070, 11 os de chlorure de (méth) acryloyl et 50g de carbonate de sodium. On chauffe le mélange réactionnel au reflux pendant 2 heures, et l'on sépare l'excès de chlorure d'acide par distillation sous pression réduite. Le monomère obtenu peut être utilisé pour la polymérisation sans purification ultérieure.

for 2 hours, and the excess glycidyl methacrylate is removed by distillation under reduced pressure. The monomer obtained can be used for the polymerization without further purification. b) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol UD-070,100 g of (meth) acrylic acid and p-acid are introduced. -toluenesulphonic as catalyst. The reaction mixture was refluxed for 2 hours, and excess acid and water formed during the reaction were distilled off under reduced pressure. The monomer obtained can be used for the polymerization without further purification. c) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol LA-090, 100 g of methyl (meth) acrylate and 20 g of tetraisopropoxide are introduced. titanium. The reaction mixture is heated at reflux for 2 hours, and after separation of the alcohol formed by distillation, the ester which remains under reduced pressure is distilled off. The monomer obtained can be used for the polymerization without further purification. d) In a one-liter one-liter reactor equipped with a stirrer, a thermometer and a reflux condenser, 500 g of Genapol UD-070, 11 bones of (meth) acryloyl chloride and 50 g of carbonate are introduced. sodium. The reaction mixture was refluxed for 2 hours, and the excess acid chloride was distilled off under reduced pressure. The monomer obtained can be used for the polymerization without further purification.

Polymerization according to the precipitation method in tert-butanol In a 2-liter reactor equipped with a reflux condenser, a gas inlet, a thermometer and a stirrer, 500 ml of tert-butanol are introduced. and the calculated amount of AMPS. The mixture is neutralized by introducing NH 3, and the monomer prepared above is added to the reaction mixture. The reaction mixture is made inert by passing nitrogen or argon and when the internal temperature has reached 60oC, the initiator (AIBN) is introduced to initiate the polymerization.

After a few minutes, the polymer thus prepared precipitates. The mixture is refluxed for 2 hours, and the polymer is separated from the solvent by suction filtration and then dried under reduced pressure.

As described above, the following polymers were prepared: (from the following reactants in amounts expressed in grams)

<Desc / Clms Page number 16>

<Tb>
<tb> Methacrylate <SEP> from <SEP> Genapol <SEP> T-250 <SEP> 10 <SEP> 20 <SEP> 30 <SEP> 97
<tb> ........
<Tb>

AMPS <SEP> neutralized <SEP> with <SEP> 90 <SEP> 80 <SEP> 90 <SEP> 3
<tb> NH3
<tb> Methylene-bis-acrylamide <SEP> 1, <SEP> 5
<tb> (crosslinking)
<tb> Methacrylate <SEP> of allyl <SEP> 1,7
<tb> (crosslinking) ....................
<Tb>

TMPTA <SEP> (crosslinker) <SEP> 1.8 <SEP> 1.8
<tb> Azobisisobutyronitrile <SEP> (initiator) <SEP> 1
<tb> Peroxide <SEP> dilauryl <SEP> (initiator) ........ <SEP> 1 <SEP> 1 <SEP> 1
<tb> Tert-butanol <SEP> 300 <SEP> 300 <SEP> 300 <SEP> 300
<Tb>

<Tb>
<tb> Example <SEP> 1 <SEP> grams
<tb> GLYCEROL
<tb> 4
<tb> PROPYLENE <SEP> GLYCOL
<tb> 4
<tb> ACID <SEP> ETHYLENE <SEP> DIAMINE <SEP> 4
<tb> PHASE <SEP> A <SEP> TETRACETIC, <SEP> SALT <SEP> DISODIUM
<tb> 0.1
<tb> (Dissolvine <SEP> NA2 <SEP> from <SEP> Akzo)
<tb> DIHYDROXYACETONE <SEP> 5
<tb> PRESERVATIVES <SEP> qs
<tb> COCOATE <SEP> DE <SEP> DECYLE
<tb> PHASE <SEP> B
<tb> (Tegosoft <SEP> DC <SEP> of <SEP> at <SEP> Goldschmidt) <SEP> 7
<tb> PHASE <SEP> C <SEP> Copolymer <SEP> of AMPS <SEP> and <SEP> of <SEP> Methacrylate <SEP> of <SEP> 1. <SEP> 25
<tb> PHASE <SEP> C <SEP> 1.25
<tb> dodecyl <SEP> 25 <SEP> OE (1)
<tb> PHASE <SEP> D <SEP> WATER <SEP> qsp <SEP> 100 <SEP> g
<Tb>
(1) as described in the publication: MORISHIMA Y., Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese J. of Polymer Sci., Vol. 18, No. 40: 323-336, 2000.

Procedure 1. Mix C + B and heat to 70oC.

2. Mix D + A and heat to 70oC.

3. Mix (C + B) with (A + D) stirring type MORITZ and allow to cool with stirring.

<Desc / Clms Page number 17>

<Tb>
<tb> Example <SEP> 2 <SEP> Grams
<tb> GLYCEROL
<tb> 4
<tb> PROPYLENE <SEP> GLYCOL
<tb> 4
<tb> ACID <SEP> ETHYLENE <SEP> DIAMINE <SEP> 4
<tb> PHASE <SEP> A <SEP> TETRACETIC, <SEP> SEEL <SEP> DISODIUM <SEP> 0. <SEP> 1
<tb> (Dissolvine <SEP> NA2 <SEP> from <SEP> Akzo)
<tb> 5
<tb> DIHYDROXYACETONE
<tb> qs
<tb> CONSERVERS
<tb> COCOATE <SEP> DE <SEP> DECYLE
<tb> (Tegosoft <SEP> DC <SEP> of <SEP> at <SEP> Goldschmidt) <SEP> 7
<tb> PHASE <SEP> C <SEP> AMPS / N-dodecylacrylamide <SEP> (3.5 / 96.5%)
<tb> PHASE <SEP> C <SEP> 1.5
<tb> neutralized <SEP> to <SEP> 100% <SEP> with <SEP> NaOH
<tb> PHASE <SEP> D <SEP> WATER <SEP> qsp <SEP> 100 <SEP> g
<Tb>

Mode opératoire 4. Mélanger C+B et chauffer à 700C.

Procedure 4. Mix C + B and heat to 700C.

5. Mix D + A and heat to 70 C.

6. Mix (C + B) with (A + D) stirring type MORITZ and allow to cool with stirring.

Examples 3 and 4 Similar results were obtained by replacing the acrylamido-2-methyl-2-propanesulfonic acid / n-dodecylacrylamide acid copolymer neutralized by the sodium hydroxide of the above example with a copolymer crosslinked with methacrylate. allyl consisting of 90% by weight of NH3 neutralized AMPS units and 10% by weight of GENAPOL T-250 methacrylate units [units of formula (here) in which R1 = CH3, R4 = C16-C18 and x = 25] or by a copolymer crosslinked with allyl methacrylate consisting of 80% by weight of NH3 neutralized AMPS units and 20% by weight of GENAPOL T-250 methacrylate units [units of formula (III) in which R1 = CH3 , R4 = C-) 6-C18 and x = 25].

Claims (59)

 N. Cosmetic composition for topical use usable for the artificial tanning and / or browning of the skin, characterized in that it contains in a cosmetically acceptable support at least one self-tanning agent and at least one amphiphilic polymer comprising at least one monomer ethylenically unsaturated sulfonic group, in free form or partially or completely neutralized, and comprising at least one hydrophobic portion.

 v ----- 1 CLAIMS 1

2. The composition of claim 1, wherein the hydrophobic portion of the amphiphilic polymer has from 6 to 50 carbon atoms. 3. Composition according to claim 2, wherein the hydrophobic part of the amphiphilic polymer comprises from 6 to 22 carbon atoms. 4. Composition according to claim 3, wherein the hydrophobic part of the amphiphilic polymer comprises from 6 to 18 atoms. 5. The composition of claim 4, wherein the hydrophobic portion of the amphiphilic polymer has from 12 to 18 carbon atoms. 6. Composition according to any one of claims 1 to 5, wherein the amphiphilic polymers are partially or completely neutralized with a mineral base or an organic base. 7. Composition according to any one of claims 1 to 6, wherein the amphiphilic polymers have a number average molecular weight ranging from 1000 to 20 000 000 g / mol. The composition of claim 7 wherein the number average molecular weight is from 20,000 to 5,000,000 g / mol. The composition of claim 8, wherein the number average molecular weight ranges from 100,000 to 1,500,000 g / mol. 10. Composition according to any one of the preceding claims, characterized in that an aqueous solution at 1% by weight of said polymers has at 25 C a viscosity measured by Brookfield viscometer, needle 7, ranging from 20,000 mPa. . s at 100,000 mPa. s. 11. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are prepared by radical polymerization by precipitation in tert-butanol.  12. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are crosslinked or non-crosslinked. 13. Composition according to claim 12, characterized in that the amphiphilic polymers are crosslinked. <Desc / Clms Page number 19>  r 14. Composition according to Claim 13, characterized in that the one or more crosslinking agents are chosen from olefinically polyunsaturated compounds.

15. Composition according to Claim 14, characterized in that the crosslinking agent (s) is (are) chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). 16. Composition according to any one of claims 13 to 15, characterized in that the degree of crosslinking preferably ranges from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer. 17. Composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer containing sulfonic group is chosen from vinylsulfonic acid, styrene sulfonic acid, (meth) acrylamido (C 1 -C 22) acids. alkylsulphonic acids, N- (C 1 -C 22) alkyl (meth) acrylamido (C 1 -C 22) alkylsulphonic acids and their partially or totally neutralized forms. 18. A composition according to claim 17, characterized in that the ethylenically unsaturated monomer containing sulfonic group is selected from acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid,

 acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2acrylamido-n-butanesulfonic acid, 2-acrylamido acid 2, 4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acryfamido-2,6-dimethyl-3-heptanesulfonic acid, and their partially or completely neutralized forms. 19. Composition according to any one of claims 17 or 18, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its forms partially or completely neutralized. 20. Composition according to Claim 19, characterized in that the amphiphilic polymers are chosen from random polymers of AMPS modified by reaction with a n-mono (C6-C22) alkylamine or a di-n- (C6C22) alkylamine. 21. Composition according to any one of claims 19 or 20, characterized in that the AMPS amphiphilic polymers additionally contain at least one ethylenically unsaturated monomer having no fatty chain. 22. The composition as claimed in claim 21, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their alkyl substituted derivatives and their esters obtained with monoalcohols or monohydric alcohols. - or polyalkylene glycols <Desc / Clms Page number 20>  Of course (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof. l 23. Composition according to any one of claims 1 to 19, characterized in that the AMPS amphiphilic polymers are chosen from amphiphilic copolymers of AMPS and at least one hydrophobic ethylenically unsaturated monomer comprising at least a part. hydrophobic having from 6 to 50 carbon atoms.

24. Composition according to Claim 23, characterized in that the hydrophobic part contains from 6 to 22 carbon atoms. 25. Composition according to Claim 24, characterized in that the hydrophobic part contains from 6 to 18 carbon atoms. 26. Composition according to claim 25, characterized in that the hydrophobic portion comprises from 12 to 18 carbon atoms. 27. Composition according to any one of claims 23 to 26, characterized in that the hydrophobic monomer ethylenically unsaturated is selected from acrylates or acrylamides of formula (1) below:

 in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is 0 or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.  28. Composition according to Claim 27, characterized in that the hydrophobic radical R2 is chosen from linear, branched or cyclic C 6 -C 18 alkyl radicals; perfluorinated alkyl radicals of Ce-C18; the cholesteryl radical or a cholesterol ester; polycyclic aromatic groups. 29. Composition according to any one of claims 27 or 28, characterized in that the monomer of formula (1) additionally comprises at least one alkylene oxide unit (x> 1). <Desc / Clms Page number 21>  F- 30. Composition according to any one of claims 27 to 29, characterized in that the monomer of formula (1) further comprises at least one polyoxyalkylene chain.

31. The composition as claimed in claim 30, characterized in that the polyoxyalkylene chain consists of ethylene oxide units and / or propylene oxide units. 32. Composition according to Claim 31, characterized in that the polyoxyalkylenated chain consists solely of ethylene oxide units. 33. Composition according to any one of claims 27 to 32, characterized in that the number of oxyalkylenated units ranges from 3 to 100. 34. Composition according to claim 33, characterized in that the number of oxyalkylenated units ranges from 3 to 50. 35. Composition according to claim 34, characterized in that the number of oxyalkylenated units ranges from 7 to 25. 36. Composition according to any one of claims 23 to 28, characterized in that the amphiphilic AMPS polymer is chosen from: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (Cs-C1e) alkyl (meth) acrylamide units or (Cs-C1e) alkyl (meth) acrylate units, based on the polymer; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-18) alkylacrylamide units, relative to the polymer . 37. Composition according to any one of claims 23 to 28, characterized in that the AMPS amphiphilic polymer is chosen from: - uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecyl methacrylate. crosslinked or uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide. 38. Composition according to claims 23 to 35, characterized in that the AMPS amphiphilic polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of the following formula (II):

<Desc / Clms Page number 22>  in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R 1 has the same meaning as that indicated above in formula (1) and R 4 denotes a linear or branched C 6 -C 22 and more preferably C 10 -C 22 alkyl.

 r ------------------------------------------------- in which X + is a proton, an alkali metal cation, an alkaline earth metal cation or the ammonium ion, and units of the following formula (III):

39. Composition according to claim 38, characterized in that x = 25, Ri is methyl and R4 is n-dodecyl. 40. A composition according to claim 27 or 38, characterized in that the molar proportion in% of the units of formula (1) or units of formula (III) in the polymers ranges from 50.1 to 99.9%. 41. A composition according to claim 27 or 38, characterized in that the molar proportion in% of units of formula (1) or units of formula (here) in the polymers ranges from 0.1 to 50%. 42. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are present in concentrations ranging from 0.01 to 30% by weight, more preferably from 0.1 to 10% by weight, and even more preferably from 0.1 to 5% by weight, and more particularly from 0.5 to 2% by weight relative to the total weight of the composition. 43. Composition according to any one of the preceding claims, characterized in that the self-tanning agent is chosen from mono-or polycarbonyl compounds. 44. A composition according to claim 43, wherein the self-tanning agent is chosen from isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4,5-dione derivatives. , dihydroxyacetone (DHA), 4,4-dihydroxypyrazolin-5-ones derivatives. 45. The composition of claim 44, wherein the self-tanning agent is dihydroxyacetone (DHA). <Desc / Clms Page number 23>  v 46. Composition according to any one of the preceding claims, characterized in that the self-tanning agent is present in proportions ranging from 0.1 to 10% by weight relative to the total weight of the composition.

47. The composition of claim 46, characterized in that the self-tanning agent is present in proportions ranging from 0.2 to 8% by weight relative to the total weight of the composition. 48. Composition according to any one of the preceding claims, characterized in that it additionally comprises at least one synthetic or natural direct dye or at least one indole derivative.

 l 49. Composition according to any one of the preceding claims, characterized in that it additionally comprises at least one other type of coloring agent for the synthetic or natural skin. 50. The composition of claim 49, wherein the additional coloring agent is selected from the "insoluble" red wood extracts of the genus Pterocarpus and the genus Baphia; nanopigments of iron oxide whose average size of the elementary particles is less than 100 nm. 51. Composition according to any one of the preceding claims, characterized in that it additionally comprises, in addition, conventional cosmetic adjuvants chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners and antioxidants. , anti-free radical agents, opacifiers, stabilizers, emollients, silicones, α-hydroxy acids, anti-foam agents, moisturizers, vitamins, insect repellents, substance P antagonists, anti-inflammatories, perfumes, preservatives, surfactants, fillers, photoprotective agents, polymers other than those of the invention, propellants, basifying or acidifying agents, dyes. 52. Composition according to any one of the preceding claims, characterized in that it additionally comprises, in addition, at least one organic photoprotective agent and / or at least one inorganic photoprotective agent active in the UVA and / or in the UVB. 53. The composition of claim 52, wherein the organic photoprotective agents are selected from anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives, camphor derivatives; triazine derivatives; benzophenone derivatives; p (3'-diphenylacrylate derivatives, benzotriazol derivatives, benzalmalonate derivatives, benzimidazol derivatives, imadazolines, bis-benzoazolyl derivatives, p-aminobenzoic acid (PABA) derivatives; methylene bis (hydroxyphenylbenzotriazole) derivatives filter and silicone screening polymers, dimers derived from α-alkylstyrene, 4,4-diarylbutadiene or mixtures thereof. 54. The composition of claim 53, wherein the organic photoprotective agents are chosen from: <Desc / Clms Page number 24>  Ethylhexyl Salicylate, Butyl Methoxydibenzoylmethane, Ethylhexyl Methoxycinnamate, Octocrylene, Phenylbenzimidazole Sulfonic Acid, Terephthalylidene Dicamphor Sulfonic, Benzophenone-3, Benzophenone-4, Benzophenone-5,4-Methylbenzylidene camphor, Benzimidazilate, Anisotriazine, Ethylhexyl triazone, Diethylhexyl Butamido Triazone, Methylene bis-Benzotriazolyl Tetramethylbutylphenol, Drometrizole Trisiloxane, and mixtures thereof.

55. Composition according to claim 52, in which the inorganic photoprotective agents are chosen from pigments or nanopigments of coated or uncoated metal oxides. 56. Composition according to claim 55, in which the inorganic photoprotective agents are chosen from coated or uncoated nanopigments, titanium oxide, iron oxide, zinc oxide, zirconium oxide or cerium oxide, and mixtures thereof. 57. Composition according to any one of claims 52 to 56, wherein the photoprotective agents are present in the compositions in proportions ranging from 0.1 to 20% by weight relative to the total weight of the composition, and preferably ranging from 0.2 to 15% by weight relative to the total weight of the composition. 58. Cosmetic treatment method for tanning and / or artificially browning the skin, characterized in that it consists in applying thereto an effective quantity of a composition as defined in any one of the preceding claims. 59. Use of an amphiphilic polymer as defined in any one of claims 1 to 42 for improving the coloration and / or the stability of a self-tanning agent as defined in claims 1.43 to 47 contained in a composition cosmetic for artificial tanning and / or browning of the skin.