WO2002055052A1

WO2002055052A1 - Amphiphilic polymer-based self-tanning compositions with at least one monomer having ethylenic unsaturation with a sulphonic group and comprising a hydrophobic part

Info

Publication number: WO2002055052A1
Application number: PCT/FR2002/000029
Authority: WO
Inventors: Karl Boutelet; Didier Candau
Original assignee: L'oreal
Priority date: 2001-01-11
Filing date: 2002-01-04
Publication date: 2002-07-18
Also published as: FR2819183A1; FR2819183B1

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

SELF-TANNING COMPOSITIONS BASED ON AMPHIPHILIC POLYMERS OF AT LEAST ONE ETHYLENICALLY UNSATURATED SULFONIC MONOMER COMPRISING A HYDROPHOBIC PART

The present invention relates to new cosmetic compositions for topical use, more particularly intended for artificial tanning and / or browning of the skin (compositions hereinafter more simply called self-tanning compositions), as well as their use in the aforementioned cosmetic application. More precisely still, it relates to self-tanning compositions with improved stability, which comprise, in a cosmetically acceptable carrier, 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.

It is known that mono- or polycarbonylated 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 for the skin.

Applied to the skin, in particular to the face, these compounds make it possible to obtain a tanning or browning effect of appearance more or less similar to that which may 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 skin reaction generally associated with the aforementioned prolonged exposures (erythema, burns, loss of elasticity, appearance of wrinkles, premature aging of the skin, and the like).

One of the problems encountered with 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 how quickly this coloration develops, are often considered insufficient by 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, thereby causing storage problems and / or storage which generally results in the long term in an undesirable yellowing of the compositions which contain it.

In an attempt to overcome these various drawbacks, it has already been proposed, in 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-methylpropane sulfonic acid

(including "SEPIGEL 305®" marketed by the company SEPPIC). Although such compositions containing this copolymer are advantageous and indeed exhibit improved properties compared to those which are free thereof, 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 to provide new cosmetic compositions based on a self-tanning agent which on the one hand have good self-tanning efficacy on the skin (intensity and color fastness), as well as, on the other hand, excellent stability. .

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

This discovery is the basis of the present invention.

In accordance with one of the objects of the present invention, new cosmetic compositions are therefore now proposed, more particularly intended for artificial tanning of the skin, of the type comprising, in a cosmetically acceptable carrier, 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 or partially or totally neutralized form, 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 sulfonic group, in free or partially or totally neutralized form, and comprising at least one hydrophobic part.

The term “amphiphilic polymer” means 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 contains 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 atoms.

The polymers in accordance with the invention preferably are partially or totally neutralized with an inorganic 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. The amphiphilic polymers in accordance with the invention generally have a number average molecular weight ranging from 1000 to 20,000,000 g / mol, preferably ranging 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 can be crosslinked or non-crosslinked. Preferably, crosslinked amphiphilic polymers are chosen.

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

Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol-diallylether, polyglycol-diallyl ethers, triethylene glycol-divinyl ether, hydroquinone-diall l-ether, di (meth) acrylate of ethylene glycol or tetraethylene glycol, trimethylol propane triacrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, triallylamine, triallylcyanurate, diallylmaleate, tetraallylethylenediamine, tetra-allyloxy-ethane, trimethylol) allyl acrylate, allyl ethers of alcohols from the sugar series or other allyl- or vinyl-ethers of polyfunctional alcohols, as well as allyl esters of phosphoric and / or vinylphosphonic acid derivatives or mixtures of these compounds

More particularly, methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA) will be used. The level of crosslinking will generally vary from 0.01 to 10% by mole and more particularly from 0.2 to 2% by mole relative to the polymer.

The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrene sulfonic acid, (meth) acrylamido (Cι-C ₂₂ ) alkylsulfonic acids, N- (Cι-C ₂₂ ) alkyl (meth) acids. ) acrylamido (Cι-C ₂₂ ) alkylsulfonic like undecyl-acrylamido-methane-sulfonic acid as well as their partially or totally neutralized forms.

More preferentially, the (meth) acrylamido (Cι-C ₂ 2) alkylsuifonic acids such as, for example, acrylamido-methane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid, will be used, 2-acrylamido-2-methylpropane-sulfonic acid, methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2-acrylamido-2,4,4- acid trimethylpentane-sulfonic, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid and their partially or totally neutralized forms.

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

Amphiphilic polymers according to the invention can in particular be chosen from amphiphilic polymers A PS statistics modified by reaction with n-monoalkylamine or di-n-alkylamine C6-C _22, and such as those described in patent application WO00 / 31154 (forming an integral part of the content of the description). These polymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their β-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 amphiphilic copolymers of AMPS and of 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 even more preferably from 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

These same copolymers may also contain one or more hydrophilic ethylenically unsaturated monomers not comprising a fatty chain such as (meth) acrylic acids, their alkyl derivatives substituted in β 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.

These copolymers are described in particular in patent application EP-A-750899, US patent 5089578 and in the following publications by Yotaro Morishima:

"Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. "

- "Miscelle formation of random copolymers of sodium 2- (acrylamido) -2- methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering - Macromolecules 2000, Vol. 33, No. 10 - 3694-3704 "; - "Solution properties of miscelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte: sait effects on rheological behavior - Langmuir, 2000, Vol.16, N ° 12, 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 ”.

The hydrophobic ethylenically unsaturated monomers of these particular copolymers are preferably chosen from the acrylates or acrylamides of formula (I) below:

in which R- | and R3, identical or different, denote a hydrogen atom or a linear or branched C1-Cβ alkyl radical (preferably methyl); Y denotes O or NH; R2 denotes a hydrophobic hydrocarbon radical comprising at least from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms and even more preferably from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and varies from 0 to 100.

The radical R2 is preferably chosen from linear CVC-iβ alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C ₁₂ ) or adamantane (C ₁₀ )); radicals alkylperfluoro C-6 C ₁ 8 (para example the group of formula - (CH ₂₎ ₂ - (CF ₂₎ ₉ -CF _3); the cholesteryl radical (C ₂ ) or a residue of cholesterol ester such as the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene. Among these radicals, more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.

According to a particularly preferred form of the invention, the monomer of formula (I) comprises at least one alkylene oxide unit (x> 1) and preferably a polyoxyalkylene chain. The polyoxyalkylenated chain, preferably, consists of ethylene oxide units and / or propylene oxide units and even more particularly consists of 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, there may be mentioned:

- 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 -Ci ₆ ) alkyl (meth) acrylamide or of (C ₈ -Ci ₆ ) alkyl (meth) acrylate with respect to the polymer, such as those described in application EP-A 750 899;

- Terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n- (C ₆ -Ci ₈ ) alkylacrylamide units, such as those described in US Pat. No. 5,089,578.

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

Mention will be made more particularly of the copolymers consisting of 2- acrylamido-2-methylpropane-sulfonic acid (AMPS) units of formula (II) below:

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

in which x denotes an integer varying from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R | has the same meaning as that indicated above in formula (I) and R4 denotes a linear or branched C ₆ -C ₂₂ and more preferably Cιo-C ₂₂ alkyl.

Particularly preferred polymers are those for which x = 25, R- | denotes methyl and R4 represents n-dodecyl; they are described in the Morishima articles mentioned above.

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

The preferred amphiphilic polymers in accordance with the invention can be obtained according to conventional radical polymerization processes 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 peroxide compounds such as potassium or ammonium persulfate or H2O2 possibly in the presence of reducing agents.

They are especially obtained by radical polymerization in a tert-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. The particle size distribution of the polymer can be determined for example by laser diffraction or image analysis. An interesting distribution for type of polymer 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 can be carried out at a temperature between 0 and 150 ° C, preferably between 10 and 100 ° C, either at atmospheric pressure or under reduced pressure. It can also be carried out under an inert atmosphere, and preferably under nitrogen. According to this process, in particular 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) or one of its sodium or ammonium salts, was polymerized with an ester of (meth) acrylic acid and, of a C-jn-C s alcohol oxyethylenated with 8 moles of ethylene oxide

(GENAPOL® C-080 from HOECHST / CLARIANT), -Oxo C alcohol | 1 oxyethylenated with 8 moles of ethylene oxide (GENAPOL®

UD-080 from HOECHST / CLARIANT),

of a Ci 1 oxo alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOL®

UD-070 from HOECHST / CLARIANT),

of a C-12-C 4 alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOL® LA-070 from the company HOECHST / CLARIANT),

of a C12-C14 alcohol oxyethylenated with 9 moles of ethylene oxide

(GENAPOL® LA-090 from HOECHST / CLARIANT),

of a C12-C4 alcohol oxyethylenated with 11 moles of ethylene oxide

(GENAPOL® LA-110 from HOECHST / CLARIANT), of a C ^ Q-C ^ Q alcohol oxyethylenated with 8 moles of ethylene oxide

(GENAPOL® T-080 from HOECHST / CLARIANT),

-Of a C- | 6-Ci8 alcohol oxyethylenated with 15 moles of ethylene oxide

(GENAPOL® T-150 from HOECHST / CLARIANT),

of a C 1 -C 6 alcohol <| 8 oxyethylenated with 11 moles of ethylene oxide (GENAPOL® T-110 from the company HOECHST / CLARIANT),

of a C ^< QC * [Q alcohol oxyethylenated with 20 moles of ethylene oxide

(GENAPOL® T-200 from HOECHST / CLARIANT),

of a C ^ Q-C ^ Q alcohol oxyethylenated with 25 moles of ethylene oxide

(GENAPOL® T-250 from HOECHST / CLARIANT), -a C18-C22 alcohol oxyethylenated with 25 moles of ethylene oxide and / or an iso alcohol C <| 6- i8 oxyethylenated by 25 moles of ethylene oxide.

The molar concentration in% of the units of formula (II) and of the units of formula (III) in the polymers according to the invention will vary depending on the application. desired cosmetic and rheological properties of the desired formulation. It can vary between 0.1 and 99.9% by moles.

Preferably for the most hydrophobic polymers, the molar proportion of units of formula (I) or (III) varies from 50.1 to 99.9%, more particularly from 70 to 95% and even more particularly from 80 to 90% .

Preferably for slightly hydrophobic polymers, the molar proportion of units of formula (I) or (III) varies 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 can be, for example, alternating, block (including multiblock) or any. According to the invention, it is preferred that the polymers have pendant chains sensitive to heat and the aqueous solution of which has a viscosity which, above a certain threshold temperature, increases or remains practically constant when the temperature increases. More particularly still, polymers are preferred 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 when the temperature increases. With this in mind, 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 water to a phenomenon of demixing by heating resulting in curves having, as a function of the temperature and the concentration, a minimum called LCST (Lower Critical Solution Temperature).

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

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 preferably 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 polycarbonylated compounds such as for example isatin, alloxane, ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4,5 derivatives -diones as described in patent application FR2466492 and WO9735842, dihydroxyacetone (DHA), derivatives of 4,4- dihydroxypyrazolin-5-ones as described in patent application EP903342.

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

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

These self-tanning agents can also be combined with other synthetic or natural skin coloring agents.

Within the meaning of the present invention, the term “skin coloring agent” is intended to mean any compound having a particular affinity for the skin enabling it to impart to the latter a lasting, non-covering coloring (ie having no tends to cloud the skin) and which cannot be removed with water or a solvent, and which resists both rubbing and washing with a solution containing surfactants. Such a long-lasting coloring therefore differs from the surface and temporary coloring provided for example by a makeup pigment.

The additional coloring agents can 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 even Baphia nitida such as those described in patent application EP971683. The coloring agents can also be iron oxide nanopigments the average size of the elementary particles of which is 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 the total weight of the composition

The self-tanning compositions in accordance with the invention may be in the form of creams, milks, gels, gel-creams, oil-in-water emulsions, vesicular dispersions, fluid lotions, in particular fluid lotions vaporizable or any other form generally used in cosmetics, in particular that usually suitable for self-tanning cosmetic compositions.

The compositions in accordance with the present invention may also comprise conventional cosmetic adjuvants in particular chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants, anti-free radical agents, opacifiers, stabilizers , emollients, silicones, α-hydroxy acids, anti- foam, moisturizers, vitamins, insect repellents, substance P antagonists, anti-inflammatories, perfumes, preservatives, surfactants, fillers, polymers other than those of the invention, propellants, basifying 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 can consist of an oil or a wax or their mixtures. By oil is meant a compound which is liquid at room temperature. The term “wax” is intended to mean a compound which is solid or substantially solid at room temperature, and the melting point of which is generally greater than 35 ° C.

As oils, mention may be made of mineral oils (paraffin); vegetable (sweet almond oil, macadamia oil, blackcurrant seed, jojoba); synthetics such as perhydrosqualene, alcohols, fatty acids or esters (such as the benzoate of C ₁₂ -C ₁₅ alcohols sold under the trade name "Finsolv TN" by the company Finetex, octyl palmitate, lanolate d 'isopropyl, triglycerides including those of capric / caprylic acids), fatty esters and ethers oxyethylenated or oxypropylenated; silicone (cyclomethicone, polydimethylsiloxanes or PDMS) or fluorinated; polyalkylenes; and their mixtures.

As waxy compounds, there may be mentioned paraffin, carnauba wax, beeswax, hydrogenated castor oil.

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

The thickeners can be chosen in particular from crosslinked polyacrylic acids, guar gums and modified or unmodified celluloses such as hydroxypropylated guar gum, methylhydroxyethylcellulose and hydroxypropylmethyl cellulose.

The compositions in accordance with the invention may additionally comprise at least one organic photoprotective agent and / or at least one inorganic photoprotective agent active in UVA and / or UVB (absorbers), water-soluble or liposoluble or else insoluble in solvents 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 US 4,367,390, EP863145, EP517104, EP570838, EP796851, EP775698, EP878469 and EP933376; benzophenone derivatives; derivatives of β, β'-diphenylacrylate; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imadazolines; bis-benzoazolyl derivatives as described in patents EP669323 and US 2,463,264; p-aminobenzoic acid derivatives (PABA); derivatives of methylene bis- (hydroxyphenyl benzotriazole) as described in applications US 5,237,071, US 5,166,355, GB2303549, DE19726184 and EP893119; filter polymers and filter silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE19855649; 4,4-diarylbutadienes as described in applications EP0967200 and DE19755649 and their mixtures.

As examples of organic photoprotective agents active in UV-A and / or UV-B, there may be mentioned above designated by their INCI name:

Para-aminobenzoic acid derivatives: - PABA,

- Ethyl PABA,

- Ethyl Dihydroxypropyl PABA,

- Ethylhexyl Dimethyl PABA sold in particular under the name "ESCALOL 507" by ISP, - Glyceryl PABA,

- PEG-25 PABA sold under the name "UVINUL P25" by BASF,

Salicylic derivatives:

- Homosalate sold under the name "EUSOLEX HMS" by RONA / EM INDUSTRIES,

- Ethylhexyl Salicylate sold under the name "NEO HELIOPAN OS" by HAARMANN and REIMER,

- Dipropyleneglycol Salicylate sold under the name "DIPSAL" by SCHER,

- TEA Salicylate, sold under the name "NEO HELIOPAN TS" by HAARMANN and REIMER,

Dibenzoylmethane derivatives:

- Butyl Methoxydibenzoylmethane sold in particular under the trade name "PARSOL 1789" by HOFFMANN LA ROCHE, - Isopropyl 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 β, β'-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,

Benzophenone derivatives: - Benzophenone-1 sold under the trade name "UVINUL 400" by BASF, - Benzophenone-2 sold under the trade name "UVINUL D50" by BASF

- Benzophenone-3 or Oxybenzone, sold under the trade name "UVINUL M40" by BASF,

- Benzophenone-4 sold under the trade name "UVINUL MS40" by BASF,

- Benzophenone-5,

- Benzophenone-6 sold under the trade name "HELISORB 11" by NORQUAY,

- Benzophenone-8 sold under the trade name "SPECTRA-SORB UV-24" BY AMERICAN CYANAMID,

- Benzophenone-9 sold under the trade name UVINUL DS-49 "by BASF,

- Benzophenone-12,

Benzylidene camphor derivative: - 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 Benzalkonium Methosulfate 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,

Benzimidazole derivatives:

- Phenylbenzimidazole 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,

- Diethylhexyl Butamido Triazone sold under the trade name "UVASORB HEB" by SIGMA 3V,

Benzotriazole derivatives

- Drometrizole Trisiloxane sold under the name "SILATRIZOLE" 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: - Menthyl anthranilate sold under the trade name "NEO HELIOPAN MA" by HAARMANN and REIMER,

Imidazoline derivatives:

- Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

Benzalmalonate derivatives:

- Polyorganosiloxane with benzalmalonate functions sold under the trade name "PARSOL SLX" by HOFFMANN LA ROCHE and their mixtures.

The more particularly preferred organic photoprotective agents are chosen from the following compounds: - 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.

The inorganic photoprotective agents are chosen from pigments or else 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 titanium oxide (amorphous or crystallized in rutile form and / or anatase), iron, zinc, zirconium or cerium and their. Conventional coating agents are moreover alumina and / or aluminum stearate. Such metallic oxide nanopigments, 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 the total weight of the composition.

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above and / or their quantities in such a way that the advantageous properties intrinsically attached to the association in accordance with the invention is not, or is not substantially, altered by the proposed addition (s).

The compositions according to the invention can be prepared according to techniques well known to those skilled in the art, in particular those intended for the preparation of emulsions of oil-in-water or water-in-oil type.

This composition can be in particular in the form of an emulsion, simple or complex (O / W, W / O, O / W / O or W / O / W) such as a cream, a milk or in the form of 'a gel or a cream gel, in the form of a lotion, powder, solid stick and possibly be packaged in 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.

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

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

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

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

PREPARATION EXAMPLES:

Preparation of ethoxylated (meth) acrylic esters.

They can in particular be obtained by the action of glycidyl (meth) acrylate or (meth) acrylic acid or of an alkyl (meth) acrylate or of a (meth) acryloyl halide on an ethoxylated fatty alcohol. There may be mentioned, by way of nonlimiting examples, the following preparations: a) from glycidyl methacrylate and GENAPOL T-250 b) from (meth) acrylic acid and GENAPOL UD-070 c) from methyl (meth) acrylate and GENAPOL LA-090 d) from (meth) acryloyl chloride and GENAPOL UD-070. a) 500 g of Genapol T-250 and 75 g of glycidyl methacrylate are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. The reaction mixture is heated to the temperature of 100 ° C. for 2 hours, and excess glycidyl methacrylate is removed by distillation under reduced pressure. The monomer obtained can be used for polymerization without further purification. b) 500 g of Genapol UD-070, 100 g of (meth) acrylic acid and acid are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. p-toluenesulfonic as a catalyst. The reaction mixture is heated at reflux for 2 hours, and the excess acid and water formed during the reaction are separated by distillation under reduced pressure. The monomer obtained can be used for polymerization without further purification. c) 500 g of Genapol LA-090, 100 g of methyl (meth) acrylate and 20 g of tetraisopropoxide are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. titanium. The reaction mixture is heated at reflux for 2 hours, and after separation by distillation of the alcohol formed, the ester is distilled which remains under reduced pressure. The monomer obtained can be used for polymerization without further purification. d) 500 g of Genapol UD-070, 110 g of (meth) acryloyl chloride and 50 g of carbonate of carbonate are introduced into a one liter three-necked reactor equipped with a stirrer, a thermometer and a reflux condenser. sodium. The reaction mixture is heated at reflux for 2 hours, and the excess acid chloride is separated by distillation under reduced pressure. The monomer obtained can be used for polymerization without further purification.

Polymerization according to the precipitation method in tert-butanol

500 ml of tert-butanol and the calculated quantity of AMPS are introduced into a 2-liter reactor fitted with a reflux condenser, a gas outlet, a thermometer and a stirrer. The mixture is neutralized by introducing NH3, 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 60 ° C., the initiator (AIBN) is introduced to initiate the polymerization.

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

As described above, the following polymers were prepared:

(from the following reactants in quantities expressed in grams)

(1) as described in the publication: MORISHIMA Y., Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese J. of Poiymer Sci., Vol. 18, no.40: 323-336, 2000.

Procedure

1. Mix C + B and heat to 70 ° C.

2. Mix D + A and heat to 70 ° C.

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

Procedure

4. Mix C + B and heat to 70 ° C.

5. Mix D + A and heat to 70 ° C.

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

Examples 3 and 4

Similar results were obtained by replacing the copolymer acrylamido-2-methyl-2-propane-sulfonic / n-dodecylacrylamide neutralized by the soda of the example above by a copolymer crosslinked by allyl methacrylate consisting of 90 % by weight of AMPS units neutralized by NH3 and 10% by weight of GENAPOL T-250 methacrylate units [units of formula (III) in which R <| = CH3, R4 = C- | gC- | 8 and x = 25], or by a copolymer crosslinked with allyl methacrylate consisting of 80% by weight of AMPS units neutralized by

NH3 and 20% by weight of GENAPOL T-250 methacrylate units [units of formula (III) in which R- CHβ, R4 = C- | β-C- | 8 and x = 25].

Claims

I. Cosmetic composition for topical use usable for artificial tanning and / or browning of the skin, characterized in that it contains in a cosmetically acceptable carrier at least one self-tanning agent and at least one amphiphilic polymer comprising at least one unsaturated monomer ethylenic with sulfonic group, in free form or partially or totally neutralized, and comprising at least one hydrophobic part.

2. Composition according to claim 1, wherein the hydrophobic part of the amphiphilic polymer contains from 6 to 50 carbon atoms.

3. Composition according to claim 2, wherein the hydrophobic part of the amphiphilic polymer contains from 6 to 22 carbon atoms.

4. Composition according to claim 3, wherein the hydrophobic part of the amphiphilic polymer contains from 6 to 18 atoms

5. Composition according to claim 4, wherein the hydrophobic part of the amphiphilic polymer comprises from 12 to 18 carbon atoms.

6. Composition according to any one of claims 1 to 5, wherein the amphiphilic polymers are partially or totally neutralized with an inorganic base or an organic base.

7. Composition according to any one of claims 1 to 6, where the * amphiphilic polymers have a number average molecular weight ranging from 1000 to 20,000,000 g / mole.

8. Composition according to claim 7, wherein the number average molecular weight varies from 20,000 to 5,000,000 g / mole.

9. Composition according to claim 8, in which the number average molecular weight varies from 100,000 to 1,500,000 g / mole.

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 a temperature of 25 ° C, a viscosity measured with a Brookfield viscometer, needle 7, ranging from 20,000 mPa.s to 100,000 mPa.s.

I I. 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.

14. Composition according to Claim 13, characterized in that the crosslinking agent (s) are chosen from compounds with olefinic polyunsaturation.

15. Composition according to claim 14, characterized in that the crosslinking agent (s) 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 crosslinking rate preferably varies from 0.01 to 10%) in moles and more particularly from 0.2 to 2% in moles relative to to the polymer.

17. Composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from vinylsulfonic acid, styrene sulfonic acid, (meth) acrylamido acids (Cι-C ₂₂ ) alkylsulfonic, N- (Cι- C ₂₂ ) alkyl (meth) acrylamido (Cι-C ₂₂ ) alkylsulfonic acids and their partially or totally neutralized forms.

18. Composition according to Claim 17, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from acrylamido-methane-sulfonic acid, acrylamido-ethane-sulfonic acid, acrylamido-propane-sulfonic acid , 2-acrylamido-2-methylpropane-sulfonic acid, methacrylamido-2-methylpropane-sulfonic acid, 2-acrylamido-n-butane-sulfonic acid, 2-acrylamido 2,4,4- trimethylpentane-sulfonic, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptane-sulfonic acid, and their partially or fully neutralized forms.

19. Composition according to any one of claims 17 or 18, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is 2-acrylamido-2-methylpropane-sulfonic acid (AMPS), as well as its forms partially or totally neutralized.

20. Composition according to Claim 19, characterized in that the amphiphilic polymers are chosen from random polymers of AMPS modified by reaction with an n-mono (C6-C ₂₂ ) alkylamine or a di-n- (C ₆ - C ₂₂ ) alkylamine.

21. Composition according to any one of claims 19 or 20, characterized in that the amphiphilic polymers of AMPS additionally contain at least one ethylenically unsaturated monomer not comprising a fatty chain.

22. Composition according to claim 20, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their alkyl derivatives substituted in β, and their esters obtained with monoalcohols or mono- or polyalkylene glycols or alternatively among (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

23. Composition according to any one of claims 1 to 19, characterized in that the amphiphilic polymers of AMPS are chosen from amphiphilic copolymers of AMPS and of at least one hydrophobic ethylenically unsaturated monomer comprising at least one 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 part contains from 12 to 18 carbon atoms.

27. Composition according to any one of claims 23 to 26, characterized in that the hydrophobic ethylenically unsaturated monomer is chosen from acrylates or acrylamides of formula (I) below:

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

28. Composition according to claim 27, characterized in that the hydrophobic radical R ₂ is chosen from alkyl radicals in Cβ-C-is, linear, branched or cyclic; alkylperfluorinated Cβ-C-is radicals; the cholesteryl radical or a cholesterol ester; aromatic polycyclic groups.

29. Composition according to any one of claims 27 or 28 characterized in that the monomer of formula (I) additionally comprises at least one alkylene oxide unit (x> 1).

30. Composition according to any one of claims 27 to 29, characterized in that the monomer of formula (I) additionally comprises at least one polyoxyalkylenated chain.

31. Composition according to claim 30, characterized in that the polyoxyalkylenated chain consists of ethylene oxide units and / or propylene oxide units.

32. Composition according to claim 31, characterized in that the polyoxyalkylenated chain consists only of ethylene oxide units.

33. Composition according to any one of claims 27 to 32, characterized in that the number of oxyalkylenated units varies from 3 to 100.

34. Composition according to claim 33, characterized in that the number of oxyalkylenated units varies from 3 to 50.

35. Composition according to claim 34, characterized in that the number of oxyalkylenated units varies 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 (C ₈ -Ci ₆ ) alkyl (meth) acrylamide or of (C ₈ -Ci ₆ ) alkyl (meth) acrylate, with respect to the polymer;

- terpolymers comprising from 10 to 90% by mole of acrylamide units, from 0.1 to 10% by mole of AMPS units and from 5 to 80% by mole of n- (C ₆ -i ₈ ) alkylacrylamide units, relative to the polymer.

37. Composition according to any one of claims 23 to 28, characterized in that the amphiphilic AMPS polymer is chosen from:

- the non-crosslinked copolymers of partially or totally neutralized AMPS and of n-dodecyl methacrylate. - crosslinked or non-crosslinked copolymers of partially or fully neutralized AMPS and of n-dodecylmethacrylamide.

38. Composition according to Claims 23 to 35, characterized in that the amphiphilic polymer of AMPS is chosen from copolymers consisting of 2-acrylamido-2-methylpropane-sulfonic acid units (AMPS) of formula (II) below:

in which x denotes an integer varying from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; Ri has the same meaning as that indicated above in formula (I) and R ₄ denotes a linear or branched C6-C22 and more preferably Cι ₀ -C ₂ alkyl 2-

39. Composition according to claim 38, characterized in that x = 25, Ri is methyl and R is n-dodecyl.

40. Composition according to claim 27 or 38, characterized in that the molar proportion in% of the units of formula (I) or of the units of formula (III) in the polymers varies from 50.1 to 99.9%.

41. Composition according to claim 27 or 38, characterized in that the molar proportion in% of the units of formula (I) or of the units of formula (III) in the polymers varies 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, even more preferably from 0.1 to 5% by weight, and more particularly still 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 polycarbonylated compounds.

44. Composition according to claim 43, in which the self-tanning agent is chosen from isatin, alloxane, ninhydrin, glyceraldehyde, mesotartric aldehyde, glutaraldehyde, erythrulose, pyrazolin-4 derivatives, 5- diones, dihydroxyacetone (DHA), 4,4-dihydroxypyrazolin-5-ones derivatives.

45. Composition according to claim 44, in which the self-tanning agent is dihydroxyacetone (DHA).

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. Composition according to 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.

49. Composition according to any one of the preceding claims, characterized in that it additionally comprises at least one other type of synthetic or natural coloring agent for the skin.

50. Composition according to claim 49, in which the additional coloring agent is chosen from "insoluble" red wood extracts of the genus Pterocarpus and of the genus Baphia; iron oxide nanopigments, the average size of the elementary particles of which is less than 100 nm.

51. Composition according to any one of the preceding claims, characterized in that it also comprises, in addition, conventional cosmetic adjuvants chosen from fatty substances, organic solvents, ionic or nonionic thickeners, softeners, antioxidants , anti-free radical agents, opacifiers, stabilizers, emollients, silicones, α-hydroxy acids, anti-foaming agents, hydrating agents, vitamins, insect repellants, 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 further comprises at least one organic photoprotective agent and / or at least one inorganic photoprotective agent active in UVA and / or in UVB.

53. Composition according to claim 52, in which the organic photoprotective agents are chosen from anthranilates; cinnamic derivatives; dibenzoylmethane derivatives; salicylic derivatives, camphor derivatives; triazine derivatives; benzophenone derivatives; derivatives of β, β'-diphenylacrylate; benzotriazole derivatives; benzalmalonate derivatives; benzimidazole derivatives; imadazolines; bis-benzoazolyl derivatives; p-aminobenzoic acid derivatives (PABA); methylene bis- (hydroxyphenyl benzotriazole) derivatives; filter polymers and filter silicones such as those described in particular in application WO-93/04665; dimers derived from α-alkylstyrene; 4,4-diarylbutadiene or their mixtures.

54. Composition according to claim 53, in which the organic photoprotective agents are chosen from: - 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 their mixtures.

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 nanopigments coated or not, of titanium oxide, of iron, of zinc, of zirconium or of cerium and their mixtures.

57. Composition according to any one of claims 52 to 56, in which 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 artificially tanning and / or browning the skin, characterized in that it consists in applying to the latter an effective amount 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 to improve the coloring and / or the stability of a self-tanning agent as defined in claims 1, 43 to 47 contained in a composition cosmetic intended for artificial tanning and / or browning of the skin.