FR2830750A1 - Cosmetic cleansing or make-up remover composition includes a make-up removing oil and an amphiphilic polymer derived from an ethylenically unsaturated sulfonate monomer - Google Patents

Abstract

Cosmetic cleansing or make-up remover composition comprising an oil phase dispersed in an aqueous phase includes a make-up removing oil and an amphiphilic polymer derived from an ethylenically unsaturated sulfonate monomer. An Independent claim is also included for a cosmetic make-up removing or cleansing method comprising applying the above composition to the skin, lips and/or eyes.

Description

<Desc / Clms Page number 1>

The invention relates to a cosmetic make-up removal and / or cleaning composition in the form of an oil-in-water emulsion comprising a particular amphiphilic polymer and at least one cleansing oil. This composition is used in particular for removing makeup and / or cleaning the skin, lips and / or eyes.

Cleansers and facial cleansers in the form of emulsions, conventionally used today have disadvantages that are not the same depending on the direction of the emulsion. In the case of water-in-oil emulsions, very effective for removal / cleansing because the fatty phase is directly available to dissolve the various fatty substances present on the skin or from makeup, their use is uncomfortable because of the fat and heavy sensation brought by this external fatty phase that remains on the skin.

In the case of oil-in-water (O / W) emulsions, the external aqueous phase brings freshness. On the other hand, the oily phase being the internal phase, it is not directly available for dissolving the fatty substances and, as a result, the removal of makeup is less effective. However, for the cleansing of the face and more especially for the make-up removal which consists in removing all the make-up products, the women seek to obtain a make-up removal as efficient as possible.

To improve the effectiveness of a cleansing composition in the form of an O / W emulsion, it is necessary to introduce a large amount of fatty phase (oily phase) since it is the latter which ensures good dissolution of the solid particles. that make up the makeup. However, when a large amount of oils is introduced into a gelled aqueous phase with a conventional aqueous gelling agent, the stability of the composition is compromised beyond a certain amount of oil, and it is then necessary to add a Emulsifying surfactant, which is present in a sufficient amount, will stabilize the emulsion. However, for reasons of safety, especially when the composition is used for removing make-up from the eyes, it is important to use emulsions which do not contain emulsifying surfactants. To ensure the stability of the emulsions without emulsifying surfactant, it is known to gel the external aqueous phase. However, when a large quantity of oils is introduced into a gelled aqueous phase with a conventional aqueous gelling agent, the stability of the composition is compromised beyond a certain amount of oil if it is not added in addition. an emulsifying surfactant. And it is all the more difficult to make emulsions without emulsifying surfactant with a high oil content, that the medium is fluid.

Moreover, if certain gelling agents such as crosslinked acrylic copolymers (Pemulen for example) make it possible to emulsify more than 20% by weight of oil, the compositions obtained have poor cosmetic properties because the feel is heavy and sticky, so little appreciated by users.

<Desc / Clms Page number 2>

Also, there remains the need for a cosmetic composition cleaning and / or make-up remover in the form of an oil-in-water emulsion, which is stable and effective while not containing emulsifying surfactant and having good cosmetic properties.

The Applicant has now found an amphiphilic polymer to achieve these objectives, regardless of the viscosity of the composition, that is to say that it is fluid or thick.

The subject of the present invention is a cosmetic cleaning and / or make-up removing composition, comprising an oily phase dispersed in an aqueous phase, characterized in that it comprises (1) an amphiphilic polymer comprising at least one ethylenically unsaturated monomer with a grouping sulfonic acid, in free form or partially or totally neutralized and comprising at least one hydrophobic part, and (2) at least one cleansing oil.

The composition being a cosmetic composition, it comprises a physiologically acceptable medium. In the present application, the term "physiologically acceptable medium" means a medium that is compatible with all keratin materials such as the skin, including the scalp, the nails, the mucous membranes, the eyes and the hair, or any other cutaneous zone of the body.

The composition of the invention, although free of any emulsifying agent, has excellent stability, regardless of its viscosity and regardless of the oil content, and, moreover, it has a very good removal efficiency. Moreover, the cosmetic feel of the composition according to the invention is very pleasant: there is no sticky effect, and it is fresh when applied to the skin.

The composition according to the invention preferably has a viscosity ranging from 0.2 Pa.s (or 2 poise) to 23 Pa.s (230 poise), preferably from 0.2 Pa.s (2 poise) to 15 Pa. s. (150 poises), this viscosity being measured at room temperature (25 ° C.) with the RM180 Rheomat apparatus from METTLER.

The composition according to the invention generally has a pH ranging from 3 to 8 and better still from 4.5 to 7.

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

<Desc / Clms Page number 3>

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, more preferably still from 6 to 18 carbon atoms, and more particularly from 12 to 18 carbon atoms. carbon atoms.

Preferably, the polymers in accordance with the invention are partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, aqueous ammonia) or an organic base such as mono-, di- or tri-ethanolamine, an aminomethylpropanediol, the N- methylglucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds.

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

le diallylmaléate, la tétraallyléthylènediamine, le tétra-allyloxy-éthane, le triméthylolpropane-diallyléther, le (méth) acrylate d'allyle, les éthers allyliques d'alcools de la série des sucres, ou d'autres allyl-ou vinyl-éthers d'alcools polyfonctionnels, ainsi que les esters allyliques des dérivés de l'acide phosphorique et/ou vinylphosphonique, ou les mélanges de ces composés. Examples that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate. trimethylol propane triacrylate, methylene-bisacrylamide, methylene-bis-methacrylamide, triallylamine, triallylcyanurate,

diallyl maleate, tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane-diallylether, allyl (meth) acrylate, allyl ethers of alcohols of the series of sugars, or other allyl or vinyl ethers of polyfunctional alcohols, as well as allylic esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures of these compounds.

According to a preferred embodiment of the invention, the crosslinking agent is chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). The degree of crosslinking generally varies 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, styrenesulphonic acid, (meth) acrylamido (C1-C22) alkylsulphonic acids and N- (C1-C22) alkyl- (meth) acrylamido acids. (C1-C22) alkylsulphonic acids such as undecyl-acrylamidomethanesulfonic acid, as well as their partially or totally neutralized forms, and mixtures thereof.

<Desc / Clms Page number 4>

méthacry) amido-2-méthytpropane-sutfonique, t'acide 2-acryiamido-n-butane- sulfonique, l'acide 2-acrylamido-2, 4, 4-triméthylpentane-sulfonique, l'acide 2- méthacrylam ido-dodécyl-sulfoniq ue, l'acide 2-acrylamido-2, 6-d iméthyl-3-heptane- sulfonique, ainsi que leurs formes partiellement ou totalement neutralisées, et leurs mélanges. According to a preferred embodiment of the invention, the (meth) acrylamido (C1-C22) alkylsulphonic acids, such as, for example, acrylamido-methanesulphonic acid, the acid, are used as ethylenically unsaturated monomers containing a sulfonic group. acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-

2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulphonic acid, 2-methacrylamido-dodecyl-2-acrylamido acid, sulphonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as their partially or completely neutralized forms, and mixtures thereof.

More particularly, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms are used.

The amphiphilic polymers in accordance with the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or di-n-octylamine C8-C, such as those described in US Pat. Patent Application WO-A-00/31154 (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 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.

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, more preferably from 6 to 22 carbon atoms. carbon, 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 monomers not containing 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, US-A-5089578 and in the following Yotaro Morishima publications: Self-assembly amphiphilic polyelectrolytes and their nanostructures Chinese Journal of Polymer Science Vol. 18, N 40, (2000), 323-336; - Miscellanous formation of random copolymers of 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering-Macromolecules 2000, Vol.

33,? 10-3694-3704;

<Desc / Clms Page number 5>

 - Solution properties of miscellanous networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behaviorLangmuir, 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.

dans laquelle R1 et R3, identiques ou différents, désignent un atome d'hydrogène ou un radical alkyle linéaire ou ramifié en C1-C6 (de préférence méthyle) ; Y désigne 0 ou NH ; R2 désigne un radical hydrocarboné hydrophobe comportant au moins de 6 à 50 atomes de carbone, plus préférentiellement de 6 à 22 atomes de carbone, 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. The hydrophobic monomers with ethylenic unsaturation of these particular copolymers are preferably chosen from acrylates, alkyl acrylates, acrylamides or alkyl acrylamides of formula (1) below:

in which R1 and R3, which are 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, more preferably 6 to 22 carbon atoms, 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 R 2 is preferably chosen from linear C 6 -C 18 alkyl (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C) radicals). or adamantane (C1o)); CS-C18 perfluorinated alkyl radicals (for example the group of formula - (CH2- (CF2) g-CF3), the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic groups; Such radicals, such as naphthalene or pyrene, are more particularly preferred linear alkyl radicals and more particularly the n-dodecyl or n-hexadecyl radical.

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 several alkylene oxide units (x> 1) constituting 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 (or number of moles of alkylene oxide) generally varies from 3 to 100, more preferably from 3 to 50 and even more preferably from 7 to 25.

<Desc / Clms Page number 6>

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 1 -C 4) alkyl units (meth) acrylamide or (C 8 -C 18) 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-C1g) alkylacrylamide units, such as those described in US-A-5,089,578.

Mention may also be made of copolymers of completely neutralized AMPS and of dodecyl methacrylate, n-hexadecyl and / or n-octadecyl, as well as copolymers of AMPS and n-dodecylmethacrylamide, which are non-crosslinked and crosslinked, such as those described in the articles of Morishima quoted above.

dans laquelle X+ est un proton, un cation de métal alcalin, un cation alcalinoterreux ou l'ion ammonium, et de motifs de formule (lis) 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 Cg-C et p ! us préférentietiement en Co-C. There may be mentioned more particularly the copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

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

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

in Cg-C and p! preferentially in Co-C.

<Desc / Clms Page number 7>

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. Other preferred polymers are those wherein x = 25, R1 is methyl and R4 is n-hexadecyl (C16) or n-octadecyl (C18) or mixtures thereof.

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 by conventional methods of radical polymerization in the presence of one or more initiators, such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile, 2,2-dihydrochloride. azobis- [2-amidinopropane] (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 or ammonium persulfate, or H 2 O 2 optionally in the presence of reducing agents.

The polymers may in particular be obtained by radical polymerization in 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 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 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.

- d'un atcoot en C-C oxyéthy) éné par 9 moles d'oxyde d'éthylène (GENAPOL LA-090 de la société HOECHST/CLARIANT), 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 in particular. a C 10 -C 18 alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOL C-080 from the company Hoechst / Clariant), - a C11 oxo alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOLO UD -080 from the company HOECHST / CLARIANT), - a C10 oxo alcohol oxyethylenated with 7 moles of ethylene oxide (GENAPOLO UD-070 from the company HOECHST / CLARIANT), - an alcohol in CC oxyethylenated by 7 moles of ethylene oxide (GENAPOLO LA-070 from the company HOECHST / CLARIANT),

an atcoot in oxyethyl CC) with 9 moles of ethylene oxide (GENAPOL LA-090 from the company HOECHST / CLARIANT),

<Desc / Clms Page number 8>

- d'un atcoo ! en Cig-Cg oxyéthyténé par 25 moles d'oxyde d'éthylène (GENAPOL T-250 de la société HOECHST/CLARIANT), - d'un atcoot en Cg-C oxyéthyténé par 25 moles d'oxyde d'éthylène et/ou d'un alcool iso-C16-C18 oxyéthyléné par 25 moles d'oxyde d'éthylène. a C12-C14 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL LA-110 from the company HOECHST / CLARIANT), a C16-C18 alcohol oxyethylenated with 8 moles of oxide of ethylene (GENAPOLO T-080 from the company HOECHST / CLARIANT), - a C16-C18 alcohol oxyethylenated with 15 moles of ethylene oxide (GENAPOL T-150 from the company HOECHST / CLARIANT), - a C16-C18 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOLO T-110 from the company HOECHST / CLARIANT), - of a C-C18 alcohol oxyethylenated with 20 moles of ethylene oxide (GENAPOL T -200 from HOECHST / CLARIANT),

- an atcoo! C 6 -C 20 ethylene oxide (GENAPOL T-250 manufactured by HOECHST / CLARIANT), an C 5 -C 6 atcoot oxyethylenated with 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 varies according to the desired cosmetic application and the 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 in units of formula (1) or (III) ranges from 50.1 to 99.9%, more particularly from 70 to 95% and even more particularly from 80 to 90%. .

Preferably for the low hydrophobic polymers, the molar proportion in 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%. monomers in the polymers of the invention may be, for example, alternating, block (including multiblock) or any.

According to another embodiment of the invention, the polymers may have pendent chains that are sensitive to heat and whose aqueous solution has a viscosity which, beyond a certain threshold temperature, increases, or remains practically constant, when the temperature increases. It is then 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). Viscosities (measured at 25 C in the Brookfield needle viscometer 7) of aqueous solutions with

<Desc / Clms Page number 9>

 1% of such polymers are preferably 20,000 mPa. s at 100,000 mPa. s and more particularly 60,000 mPa. s at 70,000 mPa. s.

The amphiphilic polymers in accordance with the invention are present in the compositions in amounts ranging from 0.01% to 20% by weight of active material, more preferably from 0.1% to 10% of active material, and still more preferably from 0.1% to 10% by weight. 5% by weight of active material and more particularly from 0.5 to 2% by weight of active material relative to the total weight of the composition. Preferably, the amphiphilic polymer is introduced into the aqueous phase of the emulsion according to the invention.

The composition according to the invention comprises an amount of aqueous phase ranging from 50 to 95% by weight and preferably from 60 to 80% by weight relative to the total weight of the composition. The aqueous phase comprises water and any other water-soluble compound that may be present, such as in particular water-soluble solvents and active agents.

As water-soluble solvents, mention may be made in particular of lower alcohols and polyols. Lower alcohol is understood to mean alcohols containing from 1 to 8 and more particularly from 1 to 6 carbon atoms, such as ethanol. Examples of polyols that may be mentioned include glycerine, propylene glycol and polyethylene glycols (PEG-8 for example). These alcohols and / or polyols may be present in the composition in an amount ranging preferably from 0.1 to 25% and from 1 to 15% of the total weight of the composition.

The oily phase of the composition according to the invention contains at least one makeup-removing oil chosen from fatty acid esters comprising at least 8 carbon atoms, preferably from 9 to 26 carbon atoms and better still from 12 to 22 carbon atoms. .

The cleansing oil may be chosen in particular from: (1) esters obtained from straight or branched chain fatty acids comprising at least 9 carbon atoms and straight or branched chain alcohols containing from 1 to 17 carbon atoms carbon; (2) esters obtained from straight or branched chain acid having 1 to 17 carbon atoms and straight or branched chain fatty alcohol having at least 9 carbon atoms; (3) esters obtained from benzoic acid and straight or branched chain fatty alcohol having at least 9 carbon atoms; and (4) their mixtures.

The esters are preferably mono- or di-esters.

The fatty chains having at least 9 carbon atoms generally comprise from 9 to 26 carbon atoms and better still from 12 to 22 carbon atoms.

<Desc / Clms Page number 10>

Preferably, the makeup-removing oil is chosen from the group of esters which contain no unsaturation and / or no ether or hydroxyl group. Even more advantageously, the makeup removal oil is a saturated ester which contains no ether or hydroxyl group.

l'octanoate d'octyldodécyle, le néopentanoate d'isodécyle, le myristate d'éthyle, le propionate de myristyle, l'éthyl-2 hexanoate d'éthyl-2 hexyle, l'octanoate d'éthyl-2 hexyle, le caprate/caprylate d'éthyl-2 hexyle, le palmitate de méthyle, le myristate de butyle, le myristate d'isobutyle, le palmitate d'éthyle, le laurate d'isohexyle, le

laurate d'hexyle, l'isostéarate d'isopropyle, l'ester d'acide benzoïque et d'alcools en C-Cg (nom CTFA : C12-15 Alkyl Benzoate), et leurs mélanges. Thus, the makeup-removing oil of the composition in accordance with the invention may especially be chosen from the group comprising 2-ethylhexyl palmitate (or octyl palmitate), isononyl isononanoate and isostearyl lactate. , 2-ethyl hexyl myristate (or octyl myristate), isopropyl palmitate, isopropyl myristate, di-isopropyl adipate, di-octyl adipate, hexanoate, 2-ethyl hexyl, ethyl laurate, methyl myristate,

octyldodecyl octanoate, isodecyl neopentanoate, ethyl myristate, myristyl propionate, 2-ethylhexyl-2-hexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprylate, methyl palmitate, butyl myristate, isobutyl myristate, ethyl palmitate, isohexyl laurate,

hexyl laurate, isopropyl isostearate, benzoic acid ester and C -C 8 alcohols (CTFA name: C12-15 Alkyl Benzoate), and mixtures thereof.

The amount of cleansing oil (s) may constitute all or part of the oily phase, for example from 1 to 90% and better still from 5 to 70% of the total weight of the oily phase.

The oily phase may additionally contain all the fatty substances, and in particular non-makeup-removing oils other than those indicated above, conventionally used in the cosmetics field. Other oils that may be present in the oily phase include, for example, hydrocarbon oils; vegetable oils such as apricot kernel oil; synthetic oils; volatile or non-volatile silicone oils and fluorinated oils. The other fatty substances that may be present in the oily phase may be, for example, fatty acids, fatty alcohols and waxes.

By hydrocarbon oil is meant here any oil predominantly comprising carbon and hydrogen atoms.

As hydrocarbon-based oils, mention may be made, for example, of paraffin oils, volatile or not, and their derivatives, liquid petrolatum, polydecenes, hydrogenated polyisobutene such as parleam oil, hydrogenated isoparaffin and isohexadecane. , isododecane, and mixtures thereof.

As silicone oils, mention may be made, for example, of volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexasiloxane; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyitrimethicones, phenyidimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones,

<Desc / Clms Page number 11>

 diphenylmethyldiphenyl trisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; their mixtures.

According to one particular embodiment of the invention, the composition of the invention comprises at least one fatty acid ester comprising at least 8 carbon atoms and at least one oil chosen from hydrocarbon-based oils, silicone oils and their derivatives. mixtures. More preferably, the composition comprises at least one ester, at least one hydrocarbon oil and at least one silicone oil.

The oily phase is present in the composition according to the invention in an amount ranging from 15 to 60% by weight and preferably from 20 to 40% by weight relative to the total weight of the composition.

In a known manner, the composition of the invention may also contain one or more adjuvants, chosen from the usual adjuvants in the cosmetic field, such as hydrophilic or lipophilic active agents, preservatives, antioxidants, perfumes, solvents, fillers, sunscreens, materials (citric acid), lipid vesicles, and mixtures thereof. These adjuvants are used in the usual proportions in the cosmetic or dermatological field, and for example from 0.01 to 30% of the total weight of the composition, and they are, according to their nature, introduced into the aqueous phase or into the oily phase. emulsion, or in vesicles. These adjuvants and their concentrations must be such that they do not modify the desired property for the composition.

notamment les lactoperoxydases, les catalases, les superoxyde dimutases et les extraits végétaux contenant les enzymes précitées ; les levures telles que les Saccharomyces Cerevisiae ; les stéroïdes ; les anti-oxydants et anti-radicaux libres ; les hydratants tels que les polyols (glycérine, sorbitol, sucres), les hydrolysas de protéine, l'urée et les mélanges en contenant ; les amincissants comme la caféine ; les agents anti-élastase et anticollagénase ; les agents de traitement des peaux grasses ; les extraits végétaux et notamment les extraits de plancton ; et leurs mélanges. As active agents that can be used in the composition of the invention, mention may be made, for example, of antibacterials such as octopirox, triclosan and triclocarban; keratolytic and anti-aging agents such as hydroxy acids (α-hydroxy acids and α-hydroxy acids) such as lactic acid, glycolic acid, citric acid, salicylic acid and their derivatives; essential oils ; vitamins and in particular retinol (vitamin A), ascorbic acid (vitamin C), tocopherol (vitamin E), niacinamide (vitamin PP or B3), panthenol (vitamin B5) and their derivatives (esters, for example ); co-enzymes and in particular coenzyme Q10 or ubiquinone; enzymes such as, for example, lipases, proteases, phospholipases, cellulases, peroxidases

in particular lactoperoxidases, catalases, superoxide dimutases and plant extracts containing the aforementioned enzymes; yeasts such as Saccharomyces cerevisiae; steroids; anti-oxidants and anti-free radicals; moisturizers such as polyols (glycerol, sorbitol, sugars), protein hydrolysas, urea and mixtures thereof; slimming as caffeine; anti-elastase and anticollagenase agents; oily skin treatment agents; plant extracts and in particular plankton extracts; and their mixtures.

As salicylic acid derivatives, there may be mentioned in particular n-octanoyl-5-salicylic acid (CTFA name: Capryloyl Salicylic Acid), n-decanoyl-5-salicylic acid, n-dodecanoyl-5-salicylic acid, n-octyl-5 -salicylic, n-heptyloxy-5-

<Desc / Clms Page number 12>

 salicylic, 5-tert-octylsalicylic, 5-butoxy-salicylic, 5-ethoxy-salicylic, 5-methoxysalicylic, 5-propoxysalicylic, 5-methylsalicylic, 5-ethylsalicylic, 5-propylsalicylic, and mixtures thereof. These acids can be optionally salified with a base.

Examples of steroids include, for example, dehydroepiandrosterone (or DHEA), as well as (1) its precursors and biological derivatives, in particular DHEA salts and esters, such as DHEA sulfate and salicylate, hydroxy DHEA, 7-keto DHEA, 7-hydroxy and 7-keto DHEA esters, especially 3-beta-acetoxy-7-oxo DHEA, and (2) its precursors and chemical derivatives, in particular sapogenins such as diosgenin or hecogenin, and / or their derivatives such as hecogenin acetate, and / or natural extracts containing it and in particular extracts of Dioscoreae, such as wild yam (Wild Yam).

According to a particular embodiment of the invention, the active agent is chosen from hydroxy acids, vitamins, plankton extracts and mixtures thereof.

The solar filters (or U.V. filters) possibly present in the composition may be chosen from organic screening agents, physical screening agents such as titanium or zinc oxides and mixtures thereof.

Of course, those skilled in the art will take care to choose the optional compounds to be added to the composition according to the invention in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not or substantially not , altered by the envisaged addition.

The compositions according to the invention may be more or less fluid and may therefore be in the form of lotion, milk or in the form of cream more or less thick. They may constitute in particular skin cleansing products and / or cleaning the skin, lips and / or hair.

caractérisé par le fait que l'on applique sur la peau, les lèvres et/ou les yeux, une composition telle que définie ci-dessus. The present invention also relates to a cosmetic process for removing makeup and / or cleaning the skin, lips and / or eyes,

characterized in that a composition as defined above is applied to the skin, the lips and / or the eyes.

The invention also relates to the cosmetic use of the composition as defined above for removing makeup and / or cleaning the skin, lips and / or eyes.

The following example of compositions according to the invention is given by way of illustration and without limitation. Quantities are given in% by weight unless otherwise stated.

<Desc / Clms Page number 13>

EXAMPLE 1 (According to the Invention): HIE Emulsion A. Oily Phase - Cyclopentadimethylsiloxane 8% - Isododecane 6% - Isononyl Isononylate 6% B. Aqueous Phase - Crosslinked Copolymer of AMPS (*) 1% - Preservatives qs - Water qsp 100% (*) 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 = C16-C18 and x = 25].

Procedure: The copolymer is dispersed in the aqueous phase at 80 ° C. with stirring, and then the oily phase is dispersed in the aqueous gel obtained with stirring.

A gelled white cream is obtained which is supple, homogeneous, smooth and shiny. Under a microscope, it has a regular appearance with sharp edges. This cream has excellent stability after 2 months at 45 C.

EXAMPLE 2 (Comparative Example): HIE Emulsion A. Oily Phase - Cyclopentadimethylsiloxane 8% - Isododecane 6% - Isononyl Isononylate 6% B. Aqueous Phase - AMPS Polymer (Hostacerin AMPS from Cariant) 1% - Preservatives qs - Water qs 100% Procedure: The polymer is dispersed in the aqueous phase at 80 ° C. with stirring, and then the oily phase is dispersed in the aqueous gel obtained with stirring.

A gelled white cream is obtained which is supple, homogeneous, smooth and shiny.

However, under the microscope, the emulsion has an irregular appearance with not always sharp edges. After two months at 45 C, we see under the microscope, that the globules

<Desc / Clms Page number 14>

 oil is fat, that is to say that in some places, the oil globules have joined and have formed a large stain.

Example 3 (Comparative): HIE Emulsion A. Oily phase - Cyclopentadimethylsiloxane 8% - Isododecane 6% - Isononyl isononyl ester 6% - PEG-20 0.25% stearate B. Aqueous phase - Homopolymer of AMPS (HOSTACERIN AMPS) 1 % - Preservatives qs - Water qs 100% Procedure: The copolymer is dispersed in the aqueous phase at 80 ° C. with stirring, then the oily phase is prepared and the oily phase is dispersed in the aqueous gel obtained with stirring.

A gelled white cream is obtained which is supple, homogeneous, smooth and shiny. Under a microscope, it has a regular appearance with sharp edges. This cream has excellent stability after 2 months at 45 C.

The stability and the cleansing effectiveness of the three formulas were evaluated: Stability:

<Tb>
<tb> Tests <SEP> Example <SEP> 1 <SEP> Example <SEP> 2 <SEP> Example <SEP> 3
<tb> (comparative) <SEP> (comparative)
<tb> Polymers <SEP> Copolymer <SEP>: <SEP> Homopolymer <SEP>: <SEP> Homopolymer <SEP>:
<tb> 1% <SEP> 1% <SEP> 1%
<tb> PEG <SEP> stearate - 0, <SEP> 25%
<tb> oily phase <SEP>:
<tb> Cyclopentadimethyl- <SEP> 8% <SEP> 8% <SEP> 8%
<tb> Isiloxane
<tb> Isododecan <SEP> 6% <SEP> 6% <SEP> 6%
<tb> Isononanoate <SEP> 6% <SEP> 6% <SEP> 6%
<tb> isononyl
<tb> Aspect <SEP> at <SEP> microscope <SEP> RAS <SEP> Fat <SEP> globules <SEP> and <SEP> RAS
<tb> after <SEP> 2 <SEP> months <SEP> to <SEP> 450C <SEP> lapses
<Tb>

<Desc / Clms Page number 15>

 Cleansing power: The cleansing power of the examples indicated above was tested, using non-transfer lipstick to check the effectiveness of removing make-up.

The test is carried out as follows: 1) The non-transfer lipstick is applied to the forearm in two round trips over an interval of three centimeters. The superficial fatty part is allowed to dry for 5 minutes; 2) An identical quantity (ie three doses of pump bottle) of each of the compositions is deposited, respectively on the lipstick marks; 3) We spread the cream on each lipstick brand, massaging with the finger, in ten circular motions: 4) We wipe the marks with a cleansing cotton, in a movement from top to bottom: We observe an excellent power makeup remover with the compositions of Examples 1 and 2, and a much less good makeup remover with the composition of Example 3. However, since the composition of Example 2 is less stable, only the composition of the invention has the once an excellent cleansing power and good stability. Moreover, this test surprisingly shows that the addition of surfactant decreases the cleansing power of the composition.

Claims (48)

 1. Cosmetic cleaning and / or make-up removing composition, comprising an oily phase dispersed in an aqueous phase, characterized in that it comprises (1) an amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group, under free form or partially or totally neutralized and comprising at least one hydrophobic part, and (2) at least one cleansing oil. 2. Composition according to Claim 1, characterized in that the hydrophobic part of the amphiphilic polymer comprises from 6 to 50 carbon atoms. 3. Composition according to the preceding claim, characterized in that the hydrophobic portion of the amphiphilic polymer comprises from 6 to 22 carbon atoms. 4. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is neutralized partially or totally by a mineral or organic base. 5. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer has a number average molecular weight ranging from 1000 to 20 000 000 g / mol. 6. Composition according to the preceding claim, characterized in that the number average molecular weight ranges from 20,000 to 5,000,000 g / mol. 7. Composition according to any one of the preceding claims, characterized in that an aqueous solution at 1% by weight of said polymer has at a temperature of 250C a viscosity measured in the Brookfield viscometer, needle 7, ranging from 20,000 mPa. s at 100,000 mPa. s. 8. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is prepared by radical polymerization by precipitation in tert-butanol. 9. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is crosslinked or non-crosslinked. 10. Composition according to the preceding claim, characterized in that the amphiphilic polymer is crosslinked. 11. Composition according to the preceding claim, characterized in that the one or more crosslinking agents are chosen from olefinically polyunsaturated compounds. <Desc / Clms Page number 17> 12. Composition according to the preceding claim, characterized in that the one or more crosslinking agents are selected from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). 13. Composition according to any one of claims 10 to 12, 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. 14. Composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer grouping

 sulfonic acid is chosen from vinylsulfonic acid, styrene sulphonic acid, (meth) acrylamido (C1-C22) alkylsulphonic acids, N- (C1-C22) alkyl (meth) acrylamido (C1-C22) alkylsulphonic acids and their partially or totally neutralized forms, and their mixtures. 15. Composition according to the preceding claim, characterized in that the

 The ethylenically unsaturated monomer containing a sulfonic group is chosen from acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2- acrylamido-2,6-dimethyl-3-heptanesulfonic acid, as well as their partially or completely neutralized forms, and mixtures thereof. 16. Composition according to claim 14 or 15, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its partially or completely neutralized forms. 17. Composition according to the preceding claim, characterized in that the amphiphilic polymer is chosen from the modified statistical polymers of AMPS.

 by reaction with n-monog-catkytamine or di-nCg-catkylamine. 18. Composition according to any one of claims 16 or 17, characterized in that the amphiphilic polymer of AMPS additionally contains at least one ethylenically unsaturated monomer having no fatty chain. 19. Composition according to the preceding claim, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their p-substituted alkyl derivatives, and their esters obtained with moncalcools or polyesters. mono or polyalkylene glycols, or from (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures thereof. 20. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is chosen from <Desc / Clms Page number 18>  amphiphilic copolymers of AMPS and at least one hydrophobic ethylenically unsaturated monomer comprising at least one hydrophobic part having from 6 to 50 carbon atoms. 21. Composition according to the preceding claim, characterized in that the hydrophobic part comprises from 6 to 22 carbon atoms. 22. Composition according to Claim 20 or 21, characterized in that the hydrophobic monomer containing ethylenic unsaturation is chosen from the acrylates, alkyl acrylates, acrylamides or alkyl 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 C4 alkyl radical; Y is 0 or NH; R2 is a hydrophobic hydrocarbon radical having at least 6 to 50 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100. 23. Composition according to the preceding claim, characterized in that the hydrophobic radical R2 is chosen from linear, branched or cyclic C8-C18 alkyl radicals; perfluorinated Ce-C18 alkyl radicals; the cholesteryl radical or a cholesterol ester; polycyclic aromatic groups.

24. Composition according to claim 22 or 23, characterized in that the monomer of formula (1) additionally comprises at least one alkylene oxide unit (x 1). 25. Composition according to any one of claims 22 to 24, characterized in that the monomer of formula (1) further comprises at least one polyoxyalkylene chain. 26. Composition according to the preceding claim, characterized in that the polyoxyalkylene chain is composed of ethylene oxide units and / or propylene oxide units. 27. Composition according to the preceding claim, characterized in that the polyoxyalkylenated chain consists solely of ethylene oxide units. 28. Composition according to any one of claims 22 to 27, characterized in that the number of moles of alkylene oxide ranges from 3 to 100. <Desc / Clms Page number 19> 29. Composition according to the preceding claim, characterized in that the number of moles of alkylene oxide ranges from 3 to 50. 30. Composition according to any one of claims 20 to 22, 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 patterns and from 40 to 85% by weight of patterns

 (C 1 -C 16) alkyl (meth) acrylamide or (C 8 -C 10) -alkylmetracrylate units, based on the polymer, the 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- (C6-1s) alkylacrylamide units, based on the polymer. 31. Composition according to any one of claims 20 to 22, characterized in that the amphiphilic AMPS polymer is chosen from: - uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecyl methacrylate, n-hexadecyl and / or n-octadecyl.  crosslinked or uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide. 32. Composition according to claims 20 to 22, characterized in that the amphiphilic AMPS polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

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

<Desc / Clms Page number 20>  wherein x is an integer ranging from 3 to 100; R1 has the same meaning as indicated above in formula (1) and R4 denotes linear or branched C6-C22 alkyl. 33. Composition according to the preceding claim, characterized in that x = 25, R1 is methyl and R4 is n-dodecyl, n-hexadecyl, n-octadecyl. 34. Composition according to claim 22 or 32, 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%. 35. Composition according to claim 22 or 32, characterized in that the molar proportion in% of the units of formula (1) or units of formula (III) in the polymers ranges from 0.1 to 50%. 36. Composition according to any one of the preceding claims, characterized in that the amount of amphiphilic polymer (s) ranges from 0.01 to 20% by weight of active ingredient and preferably from 0.1 to 10% by weight. % by weight of active material, relative to the total weight of the composition. 37. Composition according to any one of the preceding claims, characterized in that the amount of aqueous phase ranges from 50 to 95% by weight and preferably from 60 to 80% by weight relative to the total weight of the composition. 38. Composition according to the preceding claim, characterized in that the amount of oily phase is from 15 to 60% by weight and preferably from 20 to 40% by weight relative to the total weight of the composition. 39. Composition according to any one of the preceding claims, characterized in that the makeup-removing oil is chosen fatty acid esters having at least 8 carbon atoms. 40. Composition according to any one of the preceding claims, characterized in that the cleansing oil is chosen from esters obtained from straight or branched chain fatty acids containing at least 9 carbon atoms and alcohols. straight or branched chain having from 1 to 17 carbon atoms; esters obtained from straight or branched chain acid having 1 to 17 carbon atoms and straight or branched chain fatty alcohol having at least 9 carbon atoms; esters obtained from benzoic acid and straight or branched chain fatty alcohol having at least 9 carbon atoms; and their mixtures. 41. Composition according to the preceding claim, characterized in that the cleansing oil is chosen from the group 2-ethylhexyl palmitate (or octyl palmitate), isononyl isononanoate, isostearyl lactate , 2-ethylhexyl myristate (octyl myristate), isopropyl palmitate, isopropyl myristate, di-isopropyl adipate, di-octyl adipate, <Desc / Clms Page number 21>  2-ethylhexyl hexanoate, ethyl laurate, methyl myristate, octyldodecyl octanoate, isodecyl neopentanoate, ethyl myristate, myristyl propionate, ethyl-2 2-ethylhexyl hexanoate, 2-ethylhexyl octanoate, 2-ethylhexyl caprate / caprylate, methyl palmitate, butyl myristate, isobutyl myristate, ethyl palmitate , isohexyl laurate, hexyl laurate, isopropyl isostearate, benzoic acid ester and C-Cg alcohols, and mixtures thereof.

42. Composition according to any one of the preceding claims, characterized in that it comprises at least one fatty acid ester comprising at least 8 carbon atoms and at least one oil chosen from hydrocarbon-based oils and silicone oils. and their mixtures. 43. Composition according to the preceding claim, characterized in that the hydrocarbon oil is chosen from paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene, hydrogenated isoparaffin , isohexadecane, isododecane, and mixtures thereof. 44. Composition according to claim 42 or 43, characterized in that the silicone oil is chosen from volatile or nonvolatile polymethylsiloxanes with a linear or cyclic silicone chain, which are liquid or pasty at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones; their mixtures. 45. Composition according to any one of the preceding claims, characterized in that the amount of cleansing oil (s) represents from 1 to 90% and better still from 5 to 70% of the total weight of the oily phase. 46. Composition according to any one of the preceding claims, characterized in that it additionally contains one or more adjuvants chosen from hydrophilic or lipophilic active agents, preservatives, antioxidants, perfumes, solvents, fillers, sunscreens, dyestuffs, basic or acidic agents, lipid vesicles, and mixtures thereof. 47. Cosmetic use of the composition according to any one of the preceding claims for removing makeup and / or cleaning the skin, lips and / or eyes. 48. Cosmetic process for removing makeup and / or cleaning the skin,

 lips and / or eyes, characterized in that is applied to the skin, lips and / or eyes, a composition according to any one of claims 1 to 46.