FR2931357A1 - Composition in the form of oil-in-water, useful e.g. for cosmetic treatment of skin, hair and/or lips, comprises an oily phase dispersed in an aqueous phase and at least one non-crosslinked amphiphilic polymer - Google Patents

Abstract

Composition (I) in the form of oil-in-water comprises an oily phase dispersed in an aqueous phase and at least one non-crosslinked amphiphilic polymer, where the: globules of emulsion have an average particle size of 10-500 microns; oil phase is present at less than 35 wt.% relative to the total weight of the composition; and oil phase comprises at least one cleansing oil comprising esters derived from the reaction of at least one 6C fatty acid, at least one 1-17C alcohol, and/or 6-20C fatty acid ethers.

Description

Oil-in-water emulsion containing an amphiphilic polymer and a cleansing oil

The present application relates to a cosmetic composition for removing make-up and / or cleaning in the form of an oil-in-water emulsion.

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 oil-in-water (O / W) emulsions have the advantage of providing freshness due to the presence of water in the external aqueous phase, but, on the other hand, these products have the disadvantage of being relatively ineffective because the oily phase is the internal phase, it is not directly available to dissolve 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 the most effective possible.

Document FR-2,843,695 describes O / W emulsions containing an amphiphilic AMPS polymer which is not crosslinked and an oil content of greater than 40% by weight. However, such an amount of oily phase results in a greasy and glossy effect when applied to the skin, which can be unacceptable for the user. In addition the makeup removal obtained with these oils is not always completely satisfactory and can be long.

Also, there remains the need for a cosmetic cleansing and / or make-up remover in the form of an oil-in-water emulsion, which is effective in particular for removing make-up from waterproof or transfer-free make-up, comfortable but without leaving a greasy film on the surface. skin, while being stable and having good cosmetic properties.

The Applicant has surprisingly found that oil-in-water emulsions whose average droplet size is between 10 and 500 m, comprising an uncrosslinked amphiphilic polymer and a particular oil meet this need. The emulsions obtained are translucent and can be in the form of fluids as well as consistent creams.

Thus, the present invention relates to a composition for topical application, in the form of an oil-in-water emulsion comprising an oily phase dispersed in an aqueous phase and at least one non-crosslinked amphiphilic polymer, the globules of said emulsion having an average size ranging from from 10 to 500 microns, the oily phase being present in an amount of less than 35% by weight relative to the total weight of the composition and said oily phase comprising at least one cleansing oil chosen from the esters resulting from the reaction of at least a fatty acid having at least 6 carbon atoms and at least one alcohol comprising from 1 to 17 carbon atoms, the fatty acid ethers comprising from 6 to 20 carbon atoms and mixtures thereof.

In the present invention, the amount of oily phase does not include the amount of emulsifiers used according to the invention.

By topical application is meant here an external application on keratinous substances, which are in particular the skin, the scalp, the eyelashes, the eyebrows, the nails, the mucous membranes and the hair.

The composition according to the invention is intended for topical application, it contains a physiologically acceptable medium, that is to say compatible with keratin materials such as skin, mucous membranes, keratinous fibers such as eyelashes, hair and scalp.

The composition according to the invention has the advantage of having good safety and good cosmetic properties, that is to say a homogeneous texture and pleasant to the application. In addition, it is stable over time. An emulsion is stable if no change in its macroscopic, microcoscopic appearance and its physico-chemical characteristics (drop size, pH, viscosity) is observed after storage at room temperature for a period of 15 days.

In the present invention, the mean size of the oily globules is the average effective diameter in volume D [4.3] of said globules, as measured by static light scattering by means of a commercial MasterSizer 2000 type particle size analyzer. Malvern. The data is processed on the basis of Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an effective particle diameter. This theory is described in particular in Van de Hulst, HC, "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957. The mean effective volume diameter D [4.3] is defined as follows: D [4.3] = Ut where V; represents the volume of particles of effective diameter d ;. This parameter is described in particular in the technical documentation of the granulometer. The measurements are carried out at 25 ° C., after dilution of the composition by a factor greater than 100 with osmosis water. The effective diameter is obtained by specifying the refractive indices of the water and the fatty phase depending on its nature.

The average size of the oily globules may range from 10 to 500 m, preferably from 15 to 300 m, more preferably from 15 to 150 m, and better still from 20 to 100 m.

The emulsions according to the invention are translucent, in particular they have a transmittance to light at a wavelength equal to 500 nm, through a 50 m thick sample, at least 1.5 times more an emulsion of the same composition with a droplet diameter of less than 15 m. The transmittance is measured using a Visible Carry 600 UV spectrophotometer at a wavelength equal to 500 nm. The emulsion is placed between two quartz plates, one of which comprises a notch 50 microns deep.

The viscosity of the dispersions obtained can range from very fluid (spray) to very viscous (cream) and is adjusted in particular according to the polymer content introduced and the emulsified oily phase phase. The composition of the invention has a viscosity that may range, for example, from 0.01 Pa.s to 100 Pa.s at a temperature of 25 ° C., the viscosity being measured using a Rhéomat 180 (Société LAMY) , equipped with a mobile MS-R1, MS-R2, MS-R3, MS-R4 or MS-R5 chosen according to the consistency of the composition, rotating at a speed of rotation of 200 t.min-1.

Amphiphilic polymer

By amphiphilic polymer is meant a polymer which comprises at least one part (or sequence) hydrophilic and at least one part (or sequence) hydrophobic. This polymer is water-soluble or water-dispersible.

The polymers of the invention may be block polymers, or so-called comb polymers, which comprise on the one hand at least one water-soluble or water-dispersible polymeric block and, on the other hand, at least one hydrophobic block. The polymers employed in the context of the invention may therefore be block polymers (multiblock), comprising, for example, water-soluble sequences alternating with hydrophobic blocks. These polymers may also be in the form of graft polymers whose skeleton consists of water-soluble or water-dispersible blocks, and carries hydrophobic grafts, the backbone of the graft polymers being uncrosslinked.

By water-soluble or water-dispersible polymer is meant a polymer which, introduced into water at a concentration equal to 1%, leads to a macroscopically homogeneous solution whose transmittance of light, at a wavelength equal to 500 nm, through a sample of 1 cm thick, is at least 10%, which corresponds to an absorbance [abs = -log (transmittance)] less than 1.5. The term "amphiphilic polymer" means a polymer which, introduced in an aqueous solution of 0.05% (by weight), makes it possible to reduce the surface tension of water at 25 ° C. to a value of less than 50 mN / m, and of preferably less than 40 mN / m.

The polymers in accordance with the invention generally have a molar mass by weight ranging from 10,000 to 10,000,000, more preferably from 50,000 to 8,000,000 and even more preferentially from 100,000 to 3,000,000.

The amount (of active material) of amphiphilic polymer in the composition of the invention may range from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and even more preferably from 0.1 to 3% by weight relative to the total weight of the composition. The ratio of the amount of oily phase to the amount of polymer can range from 1 to 200 and preferably from 1 to 150.

A) Water-soluble polymeric sequences

By water-soluble sequences are meant sequences which, introduced into water at a concentration of 1%, lead to a macroscopically homogeneous solution, including the transmittance of light, at a wavelength of 500 nm, through a sample 1 cm thick, is at least 10%, which corresponds to an absorbance [abs = -log (transmittance)] less than 1.5.

These water-soluble sequences may be obtained by radical polymerization of vinyl monomers, or by polycondensation, or may be constituted by existing natural or modified natural polymers.

By way of example, mention may be made of the following water-soluble monomers (a) and their salts, which may be used to form said water-soluble or water-dispersible sequences or units, alone or as a mixture: - (meth) acrylic acid - vinylsulfonic acid and (meth) allylsulfonic acid, - vinylphosphonic acid, - methyl vinylimidazolium chloride, - (meth) acrylamide, - 2-vinylpyridine and 4-vinylpyridine, - acid and maleic anhydride; crotonic acid, itaconic acid; the vinyl alcohol of formula CH 2 = CHOH; N-vinyllactams such as N-vinylpyrrolidone, N-vinylcaprolactam and N-butyrolactam; water-soluble derivatives of styrene, in particular styrene sulphonate; dimethyldiallyl ammonium chloride; N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methylvinylformamide, the water-soluble vinyl monomers of formula (1) below: H 2 C = CR (1) CO X in which: R is chosen from H, -CH3, -C2H5 or -C3H7-X is chosen from: - alkyl oxides of the type -OR 'where R' is a linear or branched, saturated or unsaturated hydrocarbon radical, having 1 to 6 carbons, substituted by at least one halogen atom (iodine, bromine, chlorine, fluorine); a sulphonic group (-SO3), sulphate (-SO4), phosphate (-PO4H2); hydroxy (-OH); ether (-O-); primary amine (-NH2); secondary amine (-NHR1), tertiary (-NR1R2) or quaternary (-N + R1R2R3) with R1, R2 and R3 being, independently of one another, a linear or branched, saturated or unsaturated hydrocarbon radical having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R '+ R, + R2 + R3 does not exceed 7; mention may be made, for example, of quaternized dimethylaminoethyl methacrylate (MADAME), glycidyl (meth) acrylate, hydroxyethyl methacrylate, and ethylene glycol, diethylene glycol or polyalkylene glycol (meth) acrylates,

the groups -NH2, -NHR 'and -NR'R "in which R' and R" are, independently of each other, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 6 carbon atoms, provided that the total number of carbon atoms of R '+ R "does not exceed 7, said R' and / or R" being substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether (-O-), sulfonic (-SO3); sulfate (-SO4-); phosphate (-PO4H2); primary amine (-NH2); secondary amine (-NHR 4), tertiary (-NR 2 R 2) and / or quaternary (-N + R 1 R 2 R 3) with R 1, R 2 and R 3 being, independently of one another, a linear or branched hydrocarbon radical saturated or unsaturated having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R '+ R "+ R, + R2 + R3 does not exceed 7, for example N, N dimethylacrylamide, acrylamido-2-methylpropanesulphonic acid (AMPS), (meth) acrylamido propyltrimethylammonium chloride (APTAC and MAPTAC).

The water-soluble sequences may comprise hydrophobic monomers (b), said hydrophobic monomers being present in an amount sufficiently small for these units to be water-soluble. Examples of hydrophobic monomers (b) are: styrene and its derivatives such as 4-butylstyrene, alpha-methylstyrene and vinyltoluene; vinyl acetate of formula CH2 = CH-OCOCH3; vinyl ethers of formula CH2 = CHOR in which R is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons; acrylonitrile, caprolactone, vinyl chloride and vinylidene chloride, silicone derivatives such as methacryloxypropyltris (trimethylsiloxy) silane and silicone methacrylamides, and hydrophobic vinyl monomers of formula (2). ) next :

In which: R is chosen from H, -CH 3, -C 2 H 5 or -C 3 H 7 -X is chosen from: branched, saturated or unsaturated, having 1 to 6 carbon atoms. the groups -NH2, -NHR 'and -NR'R "in which R' and R" are, independently of each other, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 6 carbon atoms, provided that the total number of carbon atoms of R '+ R "does not exceed 6. For example, methyl methacrylate, ethyl methacrylate, n-butyl (meth) acrylate, (meth) ) tert-butyl acrylate, cyclohexyl acrylate and isobornyl acrylate and 2-hexyl ethyl acrylate.

The water-soluble sequences may be unneutralized or completely or partially neutralized with a mineral or organic base. This base may be chosen, for example, from the sodium, ammonium, lithium, calcium, magnesium, ammonium salts substituted with 1 to 4 alkyl groups bearing from 1 to 15 carbon atoms, or else from the mono-, di- , and triethanolamine, aminoethylpropanediol, N-methylglucamine, and basic amino acids, such as arginine and lysine, and mixtures thereof.

Among the polycondensates and natural or modified natural polymers that may constitute all or part of the water-soluble sequences, mention may be made of: water-soluble polyurethanes, polyethyleneimine, polyethers such as polyoxyethylene and polyoxypropylene, and xanthan gum, in particular that sold under the names Keltrol T and Keltrol SF by Kelco; or Rhodigel SM and Rhodigel 200 from Rhodia; alginates (Kelcosol de Monsanto) and their derivatives such as propylene glycol alginate (Kelcoloid LVF from Kelco); carrots of iota, kappa and lambda type, pectins of different degrees of modification (HM and LM), (2) cellulose derivatives and in particular carboxymethylcellulose (Aquasorb A500, Hercules), hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose and quaternized hydroxyethylcellulose; galactomannans and their derivatives, such as Konjac gum, Gellan, Carob, Fennugrec, Karaya, Tragacanth, acacia, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups (Jaguar XC97- 1, Rhodia), hydroxypropyltrimethylammonium guar chloride, starch derivatives, and mixtures thereof.

The water-soluble polymer blocks have a molar mass of between 1000 g / mol and 10,000,000 g / mol when they constitute the water-soluble backbone of a comb polymer. These water-soluble blocks preferably have a molar mass of between 500 g / mol and 500,000 g / mol when they constitute a block of a multiblock polymer.

B) Hydrophobic sequences By hydrophobic sequences is meant soluble or dispersible sequences in liquid fatty substances at room temperature (25 ° C.) or oils such as alkanes, esters, ethers, triglycerides and / or silicones, fluorinated or a mixture previously mentioned oils.

These sequences, introduced into an oil or an oily mixture, at a concentration of 1%, with stirring at 50 ° C. for 48 hours, lead after return to ambient temperature to a macroscopically homogeneous solution whose light transmittance, at a wavelength equal to 500 nm, through a 1 cm thick sample, is at least 10%, preferably at least 20%.

The oil in question can be of the alkane, ester, triglyceride, ether, silicone or fluorinated type or a mixture of the oils mentioned above.

Examples that may be mentioned include hydrophobic sequences comprising at least: - an alkyl radical containing from 6 to 30 carbon atoms, - a fluorinated or alkylfluorinated C 6 -C 30 radical (for example the group of formula û (CH 2) 2 - (CF 2 9-CF3)), - a cholesteryl radical or a radical derived from cholesterol (for example cholesteryl hexanoate), - one or more aromatic cyclic group (s) such as benzene, naphthalene or pyrene, a silicone or alkylsilicone or alkylfluorosilicone radical. The molar mass of these hydrophobic blocks may be between 100 and 10,000 g / mol, preferably between 200 and 5000 g / mol.

The proportion by weight of the hydrophobic blocks in the final amphiphilic polymer 10 is preferably between 1% and 60%, especially between 2% and 40%, and particularly between 5% and 30% by weight, relative to the final polymer.

Preparation of amphiphilic polymers

The polymers employed in the context of the invention can be easily prepared according to various methods including, for example: • For comb polymers: - Copolymerization: One possibility for preparing comb polymers is to copolymerize for example a macromonomer comprising a sequence Hydrophobic block (hydrophobic sequence previously described with a vinyl end) and a water-soluble vinyl monomer such as acrylic acid or vinyl monomers having formula (I). Grafting: Another possibility is to graft hydrophobic sequences having at least one reactive end to a water-soluble polymer comprising complementary reactive sites.

For block polymers: Coupling reaction: When the final polymer is in the form of a block polymer, it can be prepared by coupling between water-soluble and hydrophobic blocks having at each end complementary reagents. Living Polymerization It is possible to prepare the polymers of the invention by living polymerization of anionic or cationic type, or by controlled radical polymerization. This last synthesis process can be carried out according to various processes such as, for example, the Atom Transfer Radical Polymerization (ATRP) pathway, the radicals method such as nitroxides or the reversible chain transfer pathway. with addition-5 fragmentation (Radical Addition-Fragmentation Chain Transfer) such as the MADIX process (Macromolecular Design via the Interchange of Xanthate). These synthetic methods can be used to obtain the water-soluble blocks and the hydrophobic blocks of the polymers of the invention; they can also be used to synthesize only one of the two types of blocks of the polymer of the invention, the other block being introduced into the final polymer via the initiator used or by a coupling reaction between the water-soluble blocks and hydrophobic.

The amphiphilic polymers that may be used in the composition according to the invention may be chosen in particular from:

1) polymers derived from 2-acrylamido-2-methylpropanesulfonic acid (AMPS)

Amphiphilic polymers comprising: (a) from 80 to 99 mol% of 2-acrylamido-2-methylpropanesulphonic acid (AMPS) unit of formula (3) below: ùCHù H Where I H3 (3) NH CCH2SO3X + CH3

wherein X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion;

(b) and from 1 to 20 mol%, and preferably from 1 to 15 mol% of the following unit of formula (3a): ùCH 2 (3 bis) WhereC O- (CH 2 CH 2 O) - (CH 2 CH (CH 3) O Wherein n and p, independently of one another, denote a number of moles and ranges from 0 to 30, preferably from 1 to 20 with the proviso that n + p is less than or equal to 30, preferably less than 25 and more preferably less than 20; R, denotes a hydrogen atom, a linear or branched C1-C6 alkyl radical (preferably methyl) and R3 denotes a linear or branched alkyl group containing m carbon atoms ranging from 6 to 30, preferably from 10 to 25; carbon atoms.

These polymers according to the invention are preferentially neutralized partially or completely by a mineral base (for example sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- and tri-ethanolamine, an aminomethylpropanediol, the N-methylglucamine, basic amino acids such as arginine and lysine, and mixtures thereof.

Amps amphiphilic polymers used in the composition according to the invention are non-crosslinked.

They 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-azobis [2-amidinopropane hydrochloride] (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 are especially obtained by radical polymerization in tert-butanol medium in which they precipitate. By using the polymerization in tert-butanol, it is possible to obtain a particularly favorable polymer particle size distribution for its uses. The polymerization reaction may be conducted at a temperature between 0 ° C and 150 ° C, preferably between 20 ° C 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.

As polymers derived from AMPS that can be used in the composition according to the invention, mention may be made in particular of the polymers prepared from 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its salts. sodium or ammonium, with an ester of (meth) acrylic acid and: - a C10-C18 alcohol oxyethylenated with 8 moles of ethylene oxide (Genapol C-080 from Clariant), - a C 10 oxo alcohol oxyethylenated with 8 moles of ethylene oxide (Genapol UD-080 from Clariant), - a C 11 oxo alcohol oxyethylenated with 7 moles of ethylene oxide (Genapol UD- 070 from Clariant), - a C12-C14 alcohol oxyethylenated with 7 moles of ethylene oxide (Genapol LA-070 from Clariant), - a C12-C14 alcohol oxyethylenated by 9 moles ethylene oxide (Genapol LA-090 from Clariant), - a C12-C14 alcohol oxyethylenated with 11 moles of ethylene oxide (Genapol LA-110 from the company Clariant) ) - a C16-C18 alcohol oxyethylenated with 8 moles of ethylene oxide (Genapol T-080 from Clariant), - a C16-C18 alcohol oxyethylenated with 11 moles of oxide of ethylene (Genapol T-110 from Clariant), - a C16-C18 alcohol oxyethylenated with 15 moles of ethylene oxide (Genapol T-150 from Clariant), - a C16- alcohol. C18 oxyethylenated with 20 moles of ethylene oxide (Genapol T-200 from Clariant), - a C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide (Genapol T-250 from Clariant) ) - a C18-C22 alcohol oxyethylenated with 25 moles of ethylene oxide, - an iso-C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide. According to a preferred embodiment, the amphiphilic polymer is a copolymer of AMPS and C16-C18 alcohol methacrylate having from 6 to 25 oxyethylenated groups, obtained from methacrylic acid or an acid salt. methacrylic acid and a C16-C18 alcohol oxyethylenated with 6 to 25 moles of ethylene oxide. The amphiphilic polymer can also be a copolymer of AMPS and C12-C14 alcohol methacrylate having from 6 to 25 oxyethylenated groups, obtained from methacrylic acid or a methacrylic acid salt and a C12-C14 alcohol oxyethylenated with 6 to 25 moles of ethylene oxide.

Preferred amphiphilic polymers according to the present invention include: - the uncrosslinked copolymer obtained from 92.65 mole% of AMPS and 7.35 mole% of C16-C18 alcohol methacrylate including 8 oxyethylenated groups (Genapol T-080), such as that marketed by Clariant under the name Aristoflex SNC-the uncrosslinked copolymer obtained from 91.5 mol% of AMPS and 8.5 mol% of C12-C14 alcohol methacrylate having 7 oxyethylenated groups (Genapol LA-070), such as that marketed by Clariant under the name Aristoflex LNC, and mixtures thereof.

These copolymers are suitable for giving stable emulsions and appearing in very varied textures, ranging from sprayable fluid to cream with very good cosmetic qualities. These polymers have the advantage of being insensitive to pH variations for values between 4 and 8, which are the usual values of the cosmetic compositions.

The amphiphilic polymers derived from AMPS can have a molar mass by weight ranging from 50,000 to 10,000,000, more preferably from 100,000 to 8,000,000 and even more preferably from 200,000 to 3,000,000.

The amount (of active material) of amphiphilic polymer based on AMPS may range, in particular, from 0.1 to 1.5% by weight relative to the total weight of the composition according to the invention.

2) Polymers derived from (meth) acrylic acid Amphiphilic polymers may be mentioned comprising: (a) from 80 to 99 mol% of acrylic acid (AA) unit of formula (4) below: (4) in which R is H or CH3, X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion; (b) and from 1 to 20 mol%, and preferably from 1 to 15 mol% of unit of formula ùCH 2 (5) below: R denotes a hydrogen atom, a linear or branched C1-alkyl radical; C6 (preferably methyl) and A denotes an ester or amide group or an oxygen atom. R4 denotes a linear or branched alkyl having a number of carbon atoms ranging from 6 to 30, preferably from 10 to 25 carbon atoms.

The amphiphilic polymers derived from (meth) acrylic acid may have a molar mass by weight ranging from 50,000 to 10,000,000, more preferably from 100,000 to 8,000,000 and even more preferably from 200,000 to 3,000,000.

These polymers are partially or completely neutralized with a mineral base (for example sodium hydroxide, potassium hydroxide, ammonia) or an organic base such as mono-, di- and triethanolamine, aminomethylpropanediol, N-methylglucamine, amino acids basics such as arginine and lysine, and their mixtures.

These amphiphilic polymers derived from (meth) acrylic acid according to the invention are non-crosslinked.

Preferred amphiphilic polymers derived from (meth) acrylic acid include: - the uncrosslinked copolymer obtained from (meth) acrylic acid and steareth-20 methacrylate, sold under the name Aculyn 22 by the Rohm and Haas, - the uncrosslinked copolymer obtained from (meth) acrylic acid and laureth-25 methacrylate, sold under the name Aculyn 25 by Rohm and Haas, the uncrosslinked copolymer obtained from from (meth) acrylic acid and beheneth-25 methacrylate, sold under the name Aculyn 28 by the company Rohm and Haas, R I1 A i R4 (5) - the uncrosslinked copolymer obtained from acid (meth) acrylic and steareth-20 itaconate, sold under the name Structure 2001 by the company National Starch, - the uncrosslinked copolymer obtained from (meth) acrylic acid and itaconate ceteth-20, sold under the name of Structure 3001 by the company National Starch, - the uncrosslinked copolymer obtained from (meth) acrylic acid, aminoacrylate and C10-C30 alkyl PEG 20 itaconate, sold under the name Structure Plus by the company National Starch, - the copolymer no crosslinked obtained from (meth) acrylic acid, methylacrylate and dimethyl meta-isopropenyl benzyl isocyanate ethoxylated alcohol, sold under the name Viscophobe DB 1000 by the company Amerchol.

The amount (of active material) of amphiphilic polymer based on (meth) acrylic acid may range in particular from 0.5 to 5% by weight relative to the total weight of the composition.

3) Block copolymers, in particular diblocks, based on (poly) styrene

These copolymers are advantageously diblock copolymers (block A) - (block B) in which - block A comprises at least units derived from styrene; - Block B comprises at least (a) units derived from acrylic acid in free or salified form and (b) at least units derived from a C 1 -C 4 alkyl acrylate.

These block copolymers, preferably diblocks, are advantageously linear.

More preferably the proportion by weight of the block B with respect to the copolymer is greater than or equal to 50%. The diblock copolymers that can be used in the composition according to the invention are more particularly characterized by the fact that they are diblock copolymers (block A) - (block B) in which: block A comprises at least 90% by weight units derived from styrene, based on the total weight of block A; block B is a statistical block comprising, relative to the total weight of block B, (i) from 34 to 95% by weight of units derived from acrylic acid in acid form or in salified form; (ii) from 5 to 66% by weight of units derived from C1-C4 alkyl acrylate.

In the present application the term diblock copolymer refers to a block copolymer architecture consisting of two blocks, and having substantially no other block sequence.

In the present application, the unit derived from a monomer denotes a unit that can be obtained directly from said monomer by polymerization. Thus, for example, a unit derived from an acrylic or methacrylic acid ester does not cover a unit of formula -CH 2 -CH (COOH) -, or -CH 2 -C (CH 3) (COOH) -, obtained for example by polymerizing an acrylic or methacrylic acid ester and then hydrolyzing. Thus, the unit terminology derived from a monomer is only relative to the final constitution of the polymer and is independent of the polymerization process used to synthesize the polymer.

The ratio by weight between the blocks corresponds to the ratio between the masses of the monomers (or monomer mixtures) used for the preparation of the blocks (taking into account the mass variations related to a subsequent hydrolysis). The proportions by weight of the blocks are the proportions relative to the total diblock copolymer, and correspond to the proportions by weight of the monomers (or mixtures of monomers) used for the preparation of the blocks, with respect to all the monomers used to prepare the diblock copolymer (taking into account mass variations related to subsequent hydrolysis).

Bulk-bound masses and ratios are indicated in acid equivalents (units derived from acrylic acid in acid form, as opposed to salt form of sodium acrylate type).

Preferably, the C 1 -C 4 alkyl acrylate monomer is ethyl acrylate.

According to a preferred form of the invention, the block A and / or the block B comprises up to 10% by weight (in particular from 0.1% to 10% by weight) and preferably up to 5% by weight. (in particular from 0.1% to 5% by weight) of an additional hydrophilic comonomer, ionic or nonionic, relative to the weight of the block A or block B containing said hydrophilic monomer. By hydrophilic monomer is meant a monomer which has affinity for water, and which typically is not capable of forming a two-phase macroscopic solution in distilled water at 25 ° C, at a concentration of 1% in weight.

Among the additional hydrophilic comonomers, ionic or nonionic include, for example, acrylamide, hydroxyethyl (meth) acrylate, methacrylic acid (AMA) and salts thereof. It is more particularly preferred to use methacrylic acid or one of its salts. Block A may also comprise as additional hydrophilic monomer acrylic acid and its salts.

A first family of diblock copolymers according to the invention which is particularly preferred consists of diblock copolymers (block A) - (block B) of the type (1) in which the proportion by weight of block B with respect to the copolymer is between 50 and 85%, and preferably between 50% and 75%.

A second family of diblock copolymers according to the particularly preferred invention consists of diblock copolymers (block A) - (block B) of the type (2) in which the proportion by weight of block B with respect to the copolymer is greater than or equal to at 85%.

Among these diblock copolymers of type (2), two types of copolymers are advantageously distinguished:

- Type (2a): where the proportion by weight of the block B with respect to the copolymer is greater than or equal to 87%, especially greater than or equal to 87% and less than 94%.

- Type (2b): where the proportion by weight of the block B relative to the copolymer is greater than or equal to 94%, in particular ranging from 94% to 97%.

Among these diblock copolymers of type (2a), two types of copolymers are advantageously distinguished:

- Type (2a1): where in block B: - the proportion by weight of units derived from acrylic acid in free or salified form is between 64% (obtained for example by a hydrolysis at a rate of T = 0.7) and 75% (obtained for example by a hydrolysis at a rate of T = 0.8), and the proportion by weight of units derived from the C 1 -C 4 alkyl acrylate. is between 25% (obtained for example by a hydrolysis at a rate of T = 0.8) and 36% (obtained for example by a hydrolysis at a rate of T = 0.7). - Type (2a2): where in block B: the proportion by weight of units derived from acrylic acid in free or salified form is between 75% (obtained for example by a hydrolysis at a rate of T = 0.8) and 95% (obtained for example by a hydrolysis at a rate of T = 0.96), and the proportion by weight of units derived from the C 1 -C 4 alkyl acrylate is included between 5% (obtained for example by a hydrolysis at a rate of T = 0.96) and 25% (obtained for example by a hydrolysis at a rate of T = 0.8).

The diblock copolymers (block A) - (block B) used in the context of the invention can be obtained by a process comprising the following steps:

I) a diblock copolymer (block A) - (block B ') is prepared by a process comprising the following intermediate steps la) and lb): a) a first block A is prepared by bringing into contact: - nT moles d a transfer agent comprising a single transfer group - nA moles of styrene or a mixture of monomers comprising at least 90% by weight of styrene and where nA / nT> 5 and preferably <5000; and optionally a free radical initiator lb), a second block B 'is prepared to obtain a diblock copolymer (block A) - (block B'), by placing in contact with: the block A obtained in the preceding step, nB moles of a C1-C4 alkyl acrylate or a monomer mixture comprising at least 90% by weight of a C1-C4 alkyl acrylate such that nB / nT> 5 and preferably <5000; and optionally an initiator of free radicals,

II) the hydrolysis of the B 'block is then carried out at a molar ratio T of between 0.4 and 0.96 to obtain said diblock copolymer (block A) - (block B). III) optionally, during and / or after step II) a deactivation of transfer groups carried by macromolecular chains and / or a purification of the diblock copolymer (block A) - (block B) and / or a destruction of by hydrolysis and / or deactivation by products and preferably: - T is between 0.4 and 0.96, preferably between 0.7 to 0.8, preferably about 0.75, or about 0 , 90 - nA / nT> 5, and preferably nA / nT <5000, - nB / nT> 5, and preferably nB / nT <5000.

The terminologies of the type (block A) - (block B ') do not, however, exclude the presence of useful chemical groups (transfer groups or residues) for the polymerization, in particular at chain ends. Thus the diblock copolymer can actually have a formula of the R- (block A) - (block B ') - X type (for example X is a transfer group of the formula ûS-CS-Z or a residue of such a group ).

In the present application, the degree of hydrolysis T is defined as the ratio between the number of units derived from acrylic acid or a salt of acrylic acid, and the number of units derived from the alkyl acrylate in Cl. -C4, present in a copolymer before hydrolysis. The number of units derived from the C 1 -C 4 alkyl acrylate is considered to be equal to the amount by number of alkyl acrylate monomer used for the preparation of the copolymer. The number of units derived from acrylic acid or from an acrylic acid salt can be determined by any known method, in particular by acid-base potentiometric titration of the number of COONa groups using a strong acid, by example using hydrochloric acid.

In the present application, the molar mass MA of a mixture of monomers AI and A2 of respective molar masses MAI and MA2, present in respective numbers of nA1 and nA2, denotes the number-average molecular weight MA = MAI nA1 / (nAl + nA2). ) + MA2 nA2 / (nA1 + nA2). The molar mass of a mixture of units in a macromolecular chain or part of a macromolecular chain (a block for example) is similarly defined, with the molar masses of each of the units and the number of each of the units.

In the present application, the measured average molecular weight of a first block or of a copolymer denotes the number-average molecular weight in polystyrene equivalents of a block or of a copolymer, measured by steric exclusion chromatography (SEC). in THF with calibration using polystyrene standards. The average measured molecular weight of a single block in an n-block copolymer is defined as the difference between the measured average molecular weight of the copolymer and the measured average molecular weight of the (n-1) block copolymer from which it is prepared. .

In the present application, the term "transfer agent" is understood to mean an agent capable of inducing a controlled radical polymerization in the presence of unsaturated monomers and possibly of a source of free radicals. Such agents are known to those skilled in the art and include especially compounds comprising a transfer group -S-CS-, for the implementation of polymerization processes known as RAFT and / or MADIX. Such methods and agents are detailed below.

The polymerization process as described above is described in particular in WO 01/16187.

During step I) described above, the preparation of a first block can be carried out starting from monomers or from a mixture of monomers, initiators and / or agents promoting the control of the polymerization ( transfer agents with groups -S-CS-, nitroxides etc ...), then the growth of a second block on the first block to obtain a diblock copolymer with monomers different from those used for the preparation of the previous block, and optionally with addition of initiators and / or agents promoting the control of the polymerization. These methods of preparing block copolymers are known to those skilled in the art. It is mentioned that the copolymer may have, at the end of the chain, a transfer group or a residue of a transfer group, for example a group comprising a ûS-CS- group (for example derived from a Xanthate or a dithioester). or a residue of such a group.

In step II), the units derived from the hydrolyzable monomers of block B 'are hydrolyzed partially to form a block B comprising units derived from acrylic acid or a salt (hydrolysed units), and units derived from the monomer alkyl acrylate (unhydrolyzed units). These two types of units are statistically distributed in block B; it can therefore be considered that block B is a block in the form of a random copolymer comprising units derived from alkyl acrylate and units derived from acrylic acid or from an acrylic acid salt. Naturally, the block B may comprise other units, in minimal amounts, if a monomer mixture is used during the implementation of step 1b).

Block A includes units derived from styrene. Block A can be obtained from a monomer mixture comprising at least 90% by weight, preferably at least 95%, styrene ("St") and a comonomer or several hydrophilic comonomers (s). Block A may thus be a random copolymer comprising at least 90% (in particular from 90% to 99.9% by weight), preferably at least 95% by weight (especially from 95% to 99.9% by weight). units derived from styrene, and up to 10% by weight (in particular from 0.1% to 10% by weight), preferably up to 5% by weight (in particular from 0.1% to 5% by weight) other units derived from hydrophilic co-monomer (s).

Block B 'comprises units derived from a C 1 -C 4 alkyl acrylate. Block B 'can be obtained from a monomer mixture comprising at least 90% (in particular from 90% to 99.9%); preferably at least 95% (especially 95% to 99.9%) by weight of a C 1 -C 4 alkyl acrylate and one or more hydrophilic comonomer (s). Block B 'may thus be a random copolymer comprising at least 90% (in particular from 90% to 99.9%), preferably at least 95% (in particular from 95% to 99.9%), by weight of units derived from C1-C4 alkyl and up to 10% (especially from 0.1% to 10%), preferably up to 5% (in particular from 0.1% to 5%), by weight of other units, derived from hydrophilic co-monomer (s).

Block B obtained from block B 'after hydrolysis, comprises units derived from the hydrolyzable C1-C4 alkyl acrylate, units derived from acrylic acid or a salt, and optionally units derived from a comonomer hydrophilic used during step lb) of growth of the block B ', for example units derived from acrylic acid. Acrylic acid is generally present in block B as a salt. This form generally results from the conditions for carrying out the hydrolysis and the reagents used. It is usually an alkali metal salt such as sodium or potassium. Therefore, block B generally comprises units derived from acrylic acid in the form of sodium or potassium acrylate.

Among the hydrophilic comonomers which may be useful for the preparation of block A and / or of block B ', mention may be made of hydrophilic comonomers capable of stabilizing a monomer emulsion and / or of stabilizing the polymer. obtained by emulsion polymerization. Mention may in particular be made of ionic or nonionic hydrophilic comonomers such as acrylamide, hydroxyethyl (meth) acrylate, methacrylic acid (AMA) and their salts. It is preferred to use methacrylic acid or its salts. Methacrylic acid is not sensitive to hydrolysis. It can, however, be salified during hydrolysis. For the preparation of the block A, it is also possible to use acrylic acid and its salts as hydrophilic comonomer.

Among the hydrolyzable C1-C4 alkyl acrylates, mention is made in particular of ethyl acrylate (EA or AE or AEt).

According to one particular embodiment, the block A and / or the block B 'or B comprises from 0.1 to 10%, preferably from 0.1 to 5%, by weight of hydrophilic comonomer, in particular the acid methacrylic acid or a salt thereof, based on the total weight of block A or block B or B 'containing said hydrophilic comonomer.

Thus, during step la), or may use a monomer mixture comprising at least 90%, preferably at least 95%, by weight of styrene, and up to 10%, preferably up to 5%, by weight of methacrylic acid.

In step 1b), or may use a monomer mixture comprising at least 90%, preferably at least 95%, by weight of C 1 -C 4 alkyl acrylate such as ethyl acrylate, and up to 10%, preferably up to 5% by weight of methacrylic acid or one of its salts.

Some characteristics of the process for preparing the copolymers of the invention are described below.

Step I)

The copolymers according to the invention can be obtained by any known method, whether by radical polymerization, controlled or not, by ring opening polymerization (in particular anionic or cationic), by anionic or cationic polymerization, or by chemical modification of the polymer. a polymer.

Preferably, for the polymerization step I), so-called living or controlled radical polymerization methods are used, and particularly preferably controlled or living radical polymerization methods using a transfer agent comprising a group of transfer of the formula ûS-CS-, in particular known under the names of RAFT or MADIX.

By way of examples of so-called living or controlled polymerization processes, reference can notably be made to: the processes of the applications WO 98/58974, WO 00/75207 and WO 01/42312 which implement a radical polymerization controlled by agents Xanthates type control system, - the radical polymerization process controlled by dithioester or trithiocarbonate type control agents of the application WO 98/01478, - the radical polymerization process controlled by dithiocarbamate type control agents of the WO application. 99/31144, the radical polymerization process controlled by dithiocarbazate type control agents of the application WO 02/26836, - to the radical polymerization process controlled by dithiophosphoroesters type control agents of the application WO 02/10223, - to the process of the application WO 99/03894 which implements a polymerization in the presence of nitroxide precursors, or the pro transferred using other nitroxides or nitroxide / alkoxyamine complexes - to the process of the application WO 96/30421 which uses a radical transfer polymerization (ATRP), - to the radical polymerization process controlled by control agents of type iniferters according to the teachings of Otu et al., Makromol. Chem. Rapid. Commun., 3, 127 (1982), the process of controlled radical polymerization controlled by degenerative transfer of iodine according to the teaching of Tatemoto et al., Jap. 50, 127, 991 (1975), Daikin Kogyo Co. Itd Japan and Matyjaszewski et al., Macromolecules, 28, 2093 (1995), - the radical polymerization process controlled by tetraphenylethane derivatives, disclosed by D. Braun et al. In Macromol. Symp. 111, 63 (1996), or else to the process of radical polymerization controlled by organocobalt complexes described by Wayland et al. In J.Am.Chem.Soc. 116,7973 (1994) - to the radical polymerization process controlled by diphenylethylene (WO 00/39169 or WO 00/37507).

The polymerizations can be carried out in emulsion in water (so-called "latex" process). These processes can use emulsifying agents, most often surfactants. Without wishing to be bound to any theory, it is believed that the emulsion preparation processes lead to the formation of block nodules A, which can influence the physicochemical properties of the copolymer.

The polymerizations may be carried out in the presence of free radical initiators, known to those skilled in the art. For example, sodium persulfate may be used. Initiator quantities of from 5 to 50% by number relative to the amount of transfer agent can typically be used. Step II)

In step II) the respective amounts of the different units in the B block are controlled by the rate of hydrolysis. The composition of block A may remain unchanged during hydrolysis if block A does not comprise hydrolysable units. However, it is not excluded that the block A is slightly modified during the hydrolysis step.

Preferably, the hydrolysis step II) is carried out by adding a strong base such as sodium hydroxide or potassium hydroxide. Typically, a base number ratio is added based on the amount of hydrolyzable monomer used in step 1b), corresponding approximately to the target hydrolysis rate, with possibly an excess of a few percent. For example, a quantity of sodium hydroxide 75% by number of the amount of hydrolyzable ethyl acrylate implemented in step lb) is introduced. The operation is preferably carried out by homogeneous hydrolysis by gradually adding the sodium hydroxide to the copolymer.

The hydrolysis step may notably result in the deactivation and / or the sectioning of certain transfer groups or other groups attached to the macromolecular chains. Step II) can thus generate by-products which it is desirable to eliminate, or generate groups on macromolecular chains that are desirable to chemically modify. Such operations can be implemented during a step III).

Step III) Step III) is a step of deactivation of transfer groups carried by macromolecular chains, and / or purification of the diblock copolymer (block A) - (block B) and / or destruction of by-products of hydrolysis and / or deactivation.

In optional step III), the obtained block copolymers or hydrolysis byproducts may undergo a purification or destruction reaction of certain species, for example by hydrolysis, oxidation, reduction, type processes. pyrolysis, ozonolysis or substitution. An oxidation step with hydrogen peroxide is particularly suitable for treating sulfur species. It is mentioned that some of these reactions or operations may take place in whole or in part during step II). In this case, for these reactions or operations, the two steps are simultaneous. The average molecular weights of the diblock copolymer (block A) - (block B ') before hydrolysis or of each of the blocks are typically a function of the relative amounts of the monomers and of the transfer agent used during stage a). Of course, the average molecular weights of the diblock copolymer (block A) - (block B) after hydrolysis or of each of the blocks are a function of these same relative amounts and also of the degree of hydrolysis, for example a function of the amount of reagent introduced. , usually a base, for this hydrolysis.

For the sake of simplicity, it is common to express the average molecular masses of the blocks in "theoretical" or "target" average molecular weights, considering a complete and perfectly controlled polymerization. In this case a macromolecular chain is formed by transfer agent; to obtain the molecular mass it suffices to multiply the average molar mass of the units of a block by the number of units per block (quantity in number of monomers per quantity in number of transfer agent). In these calculations, the differences induced by small amounts of comonomer such as methacrylic acid can be neglected. The theoretical or target average molecular masses of the B block are expressed by considering a total hydrolysis (the masses are expressed with the fiction of a hydrolysis rate of 1).

The theoretical average molecular weight Mb, 00 of a block is typically calculated according to the following formula: ## EQU1 ## where M is the molar mass of a monomer i, n is the number of moles of the monomer i, nprecursor is the number of moles of functions to which the macromolecular chain of the block will be linked The functions can come from a transfer agent (or a transfer group) or an initiator, a previous block etc. is a preceding block, the number of moles can be considered as the number of moles of a compound to which the macromolecular chain of said previous block has been bonded, for example an agent of

transfer (or a transfer group) or an initiator. In practice, the theoretical average molecular weights are calculated from the number of moles of monomers introduced and the number of moles of introduced precursor.

The theoretical or target average molecular weight of a block copolymer is considered as the addition of the average molecular weights of each of the blocks, considering a total hydrolysis (the masses are expressed with the fiction of a hydrolysis rate of 1), if such hydrolysis has been carried out.

The total target or theoretical mass of a block is defined as the mass of the macromolecular chain, considering a complete and perfectly controlled polymerization. To obtain the total mass it is sufficient to multiply the molar mass of a unit of a block by the number per block of this unit and to add the masses thus obtained for each type of unit in the block. In these calculations, the differences induced by small amounts of co-momoners such as methacrylic acid can be neglected. The theoretical or target total masses of the B block are expressed considering the effect of a partial hydrolysis (for this descriptor the fiction of a degree of hydrolysis of 1) is not used, if such hydrolysis has been performed.

Thus: - the total theoretical or target mass of block A is MAnA; the theoretical or target average molecular weight of block A is: MAnA / nT. the total theoretical or target mass of the block B 'is MBnB; the theoretical or target average molecular weight of the block B 'is: MBnB / nT. the total theoretical or target mass of the block B is T MAA nB + (1-T) MB nB; the theoretical or target average molecular weight of block B is: MAA nB InT (because T = 1 for the theoretical or target average molecular weight) - the theoretical or target total mass of the block copolymer is MAnA + T MAA nB + (1- T) MB nB; the theoretical or target average molecular weight of the block copolymer (block A) - (block B) is nA / nT MA + MAA nB / nT • where: - MA is the molar mass of styrene or monomer mixture comprising styrene in step la), - MAA is the molar mass of acrylic acid, - MB is the molar mass of C1-C4 alkyl acrylate or monomer mixture comprising alkyl acrylate C1-C4 implemented in step lb).

By way of reference, the following correspondences are given: nA / nT = 5 corresponds to a theoretical average molecular mass of block A of about 500 g / mol - nA / nT = 5000 corresponds to a theoretical average molecular mass of block A of approximately 500000 g / mol, nB / nT = 5 corresponds to a theoretical average molecular weight of the block B 'of approximately 500 g / mol - nB / nT = 5000 corresponds to a theoretical average molecular weight of the block B' of about 500000 g / mol. - nA / nT MA + MAA nB / nT = 13000 g / mol (respectively 2000, respectively 8000, respectively 20000 or 50000) corresponds to a theoretical average molecular weight of the diblock (block A) - (block B) about 13000 g / mol (respectively 2000, respectively 8000, 20000 or 50000 respectively), considering a total hydrolysis and for the case where the C 1 -C 4 alkyl acrylate is the acrylate 'ethyl.

The ratios by weight between the blocks are defined as the ratios between the theoretical or target total masses (for this descriptor the fiction of a degree of hydrolysis of 1) is not used.

Thus: - MAnA T MAA nB + (1-T) MB nB, indicates that the weight ratio (block B) / (block A)? This is a characteristic of the copolymer used according to the invention,

MAnA / [MAnA + T MAA nB + (1-T) MB nB] indicates the amount by weight of block A in the diblock copolymer (block A) - (block B), that is to say the proportion of block A. - [T MAA nB + (1-T) MB nB] / [MAnA + T MAA nB + (1-T) MB nB] indicates the amount by weight of block B in the diblock copolymer (block A) - (block B), that is to say the proportion of block B. It is mentioned that one would not depart from the scope of the invention by implementing and adapting other methods of preparation leading to diblock copolymers substantially identical. In particular it is conceivable to use transfer agents comprising several transfer groups (for example trithiocarbonates ZS-CS-SZ) leading to telechelic copolymers of type R - [(block B ') - (block A)]. (for example (block A) - (block B ') - R- (block B') - (block A), then to section ("cleave") the telechelic copolymers, to obtain diblock copolymers (block A) - ( Block B '). The section may intervene during the hydrolysis, in which case diblock copolymers (block A) - (block B) are obtained directly. In such cases, those skilled in the art will adapt the conditions of use. to target average molecular weights equivalent to those indicated, for example by multiplying the amounts of monomers introduced by the number of transfer groups included in the transfer agent.

Preferably, the diblock (block A) - (block B) linear copolymers of the type (1) in which the proportion by weight of the block B with respect to the copolymer [T MAA nB + (1-T) MB nB] / [ MAnA + T MAA nB + (1-T) MB nB] is between 50 and 85%, preferably between 50% and 75%, and generally have a theoretical average molecular weight (nA / nT MA + MAA nB / nT) less than or equal to 13000 g / mol, and in particular between 8000 and 13000 g / mol.

Preferably, the diblock linear copolymers (block A) - (block B) of the type (2) in which the proportion by weight of the block B with respect to the copolymer [T MAA nB + (1-T) MB nB] / [ MAnA + T MAA nB + (1-T) MB nB] which is greater than or equal to 85% (BOL 44 and 55 and 64) and generally have a theoretical average molecular weight (nA / nT MA + MAA nB / nT) greater than or equal to 13000 g / mol.

Among these copolymers of the type (2), those particular of the type (2a), in which the proportion by weight of the block B with respect to the copolymer is greater than or equal to 87%, in particular greater than or equal to 87% and less than 94% generally have a theoretical average molecular weight of between 13,000 and 20,000 g / mol. those particular of the type (2b) in which the proportion by weight of the block B with respect to the copolymer is greater than or equal to 94%, in particular ranging from 94% to 97%, generally have a theoretical average molecular mass greater than or equal to 20,000; g / mol and preferably between 20000 and 50000 g / mol.

The amount (of active material) of amphiphilic copolymer based polystyrene can range from 0.5 to 1.5% by weight relative to the total weight of the composition. 4) Polymers derived from polyether

The preferred polyether-derived polymers of the invention are water-soluble polyurethanes, for example: PEG-150 copolymer bearing stearyl ends via urethane linkages, sold under the name Aculyn 46 by Rohm and Haas, the PEG-150 copolymer bearing decyl ends via urethane linkages, sold under the name Aculyn 44 by the company Rohm and Haas; the PEG-136 copolymer bearing stearyl ends via urethane linkages, sold under the name Rheolate FX 1100 by the company Elementis, the PEG-50 copolymer bearing stearyl ends via urethane linkages, sold under the name Borchigel LW 44 by Borchers France.

Polymers derived from polyether may also carry fatty chains without urethane linkages, such as, for example, the Pure Thix HH product sold by Sud Chemie.

5) Polymers of natural origin As polymers of natural origin, mention may be made of: - Cellulose derivatives modified with fatty chains containing from 6 to 30 carbon atoms, such as: cetylhydroxyethylcelluloses such as Natrosol CS Plus 330, 430 and Polysurf 67 CS sold by the company Hercules, hydroxypropylmethylcelluloses modified with stearyloxyhydroxypropyl chains at a molar rate of between 0.3 and 0.6%, sold under the names Sangelose 60L (molar mass in the order of 500 000 g / mol) and Sangelose 90L (molar mass of the order of 900 000 g / mol) by Daido, - hydroxyethylcellulose quaternized with the lauryl di-methyl ammonium epoxide substituted, sold under the name of Quadrisoft LM 200 by Amerchol, - hydroxyethylcellulose quaternized and modified with lauryl or stearyl chains, sold under the name Crodacel QM (C12), QL (C12) and QS (C18) by the company i was Croda. Hydroxyethylcelluloses quaternized with trimethylammonium groups and substituted by dimethyldodecylammonium chains, sold under the name of Soft Cat SL 5, SL 30, SL 60 and SL 100 by the company Amerchol.35 - Guar derivatives modified with fatty chains, comprising: from 6 to 30 carbon atoms, such as the hydroxypropylguar modified with behenic chains, sold under the name Esaflor HM 22 by the company Lamberti. Starch derivatives modified with fatty chains containing from 6 to 30 carbon atoms, such as maize starch esterified with octenylsuccinic anhydride in sodium salt form, sold under the name of N-creamer 46 by the company National Starch, derivatives of gum acacia modified with fatty chains containing from 6 to 30 carbon atoms, such as acacia gum modified by controlled esterification, sold under the name Ticamulsion A-2010 by the company Tic Gums .

These polymers have the advantage of being insensitive to pH variations for values between 4 and 8, which are the usual values of the cosmetic compositions.

In particular, cellulosic derivatives are used in a content (of active material) of polymer ranging from 0.3 to 2% by weight, better still from 0.5 to 2% by weight relative to the total weight of the composition.

emulsifiers

In order to facilitate the emulsification of the oily phase, the composition according to the invention may comprise one or more emulsifiers (distinct from the amphiphilic polymer), also called co-emulsifiers. The amount (of active material) of emulsifier (s) can range, for example, from 0.001% to 5% by weight, preferably from 0.005% to 2% by weight, and more preferably from 0.01% to 1% by weight per relative to the total weight of the composition.

The emulsifier is preferably used at a level of less than 20% by weight relative to the weight of amphiphilic polymer.

The emulsifier can be chosen from alkyl polyglucosides, polyoxyethylene alkyl esters or ethers (POE), alkyl esters or glycerol ethers, alkyl esters or sorbitan ethers which are oxyethylenated or otherwise, dimethicone copolyols, gemini and mono acylglutamates. or disodium.

We can mention in particular:

glycerol esters, such as the mono or polyalkyl esters or glycerol ethers as described in documents EP1010416 and EP1010414, glyceryl monoisostearate, such as the product marketed under the name Peceol Isostaric by the company Gattefosse, polyglycerolated isostearate (4 moles) sold under the name Isolan G134 by Goldschmidt, polyglycerolated diisostearate (3 moles) sold under the name Lameform TGI by Cognis and polyglycerolated distearate (2 moles) sold under the name Emalex PGSA by the company Nihon emulsion.

esters and ethers of polyethylene glycol, such as polyethylene glycol alkyl esters and ethers as described in documents EP1120101 and EP1016453, oleth 50 sold under the name Emalex 550 by the company Nihon Emulsion, oleth 20 sold under the name of Brij 98 by Uniqema, ceteth 2 and 10 sold under the name of Brij 52 and 56 by Uniqema, laureth 23 sold under the name of Brij 35 by Uniqema and PEG 8 stearate sold under the name Myrj 45 by Uniqema, PEG-8 isostearate such as the product marketed under the name Prisorine 3644 by the company Uniquema, PEG 20 stearate and PEG 40 stearate sold under the name Myrj 49 and from Myrj 52 by Uniqema. The following compounds sold by Uniqema may also be mentioned: Trade name INCI name Brij 35 Laureth 23 Brij 30 Laureth 4 Brij 96 Oleth 10 Brij 56 Ceteth 10 Brij 98 Oleth 20 Brij 76 Steareth 10 Brij 72 Steareth 2 Brij 52 Ceteth 2 Brij 78 Steareth 20.

Sorbitan esters or ethers such as oxyethylenated or unoxylated mono- or polyalkyl esters or sorbitan ethers as described in document EP1010415, or the following products sold by Uniqema: Examples: Trade name INCI name 31 Tween 21 Tween 40 Tween 80 Tween 60V Tween 61V Also mentioned is isostearate Polysorbate 21 Polysorbate 40 Polysorbate 80 Polysorbate 60 Polysorbate 61. Sorbitan such as the product sold under the name Arlacel 987 by the company Uniqema, the isosterate of sorbitan and glycerol, such as the product marketed under the name Arlacel 986 by Uniqema, sorbitan sesquioleate such as the product sold under the name Arlacel 83V by Uniqema, sorbitan laurate, sorbitan monopalmitate, sorbitan oleate, trioleate; sorbitan monostearate and sorbitan tristearate such as the products marketed under denomination Span 20, Span 40, Span 80V, Span 85V, Span 60 and Span 65V by Uniqema. Mono or polyalkyl esters or sugar ethers such as mono or polyalkyl esters or sugar ethers as described in patent US 6,689,371. Mention may be made, for example, of methylglucose isostearate such as the Isolan-IS from the company Degussa Goldschmidt or even the sucrose distearate such as Crodesta F50 sold by the company Croda, and the sucrose stearate such as the Ryoto sugar ester S 1570 sold by Mitsubishi Kagaku Foods.

Alkoxylated alkenyl succinates for example as described in document EP1025898. Fatty alcohols, such as fatty alcohols containing from 8 to 26 carbon atoms, for instance cetyl alcohol, stearyl alcohol and their mixture (cetearyl alcohol), octyl dodecanol, 2-butyloctanol and 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol and mixtures thereof. Silicone derivatives, such as dimethicone copolyols, such as the mixture of cyclomethicone and dimethicone copolyol, sold under the name DC 5225 C by Dow Corning, and alkyl dimethicone copolyols such as laurylmethicone copolyol sold under the name Dow Corning 5200 Formulation Aid by Dow Corning and cetyldimethicone copolyol sold under the name Abil EM 90 by the company Goldschmidt, or the 4-polyglyceryl isostearate / cetyl dimethicone copolyol / hexyllaurate mixture sold under the name Abil WE 90 by the company Goldschmidt. Alkoxylated alkenyl succinates such as, for example, those described in document EP1025898. the phosphoric alkyl esters, such as, for example, those described in document EP1013338.

Citrated alkyl ethers, such as, for example, those described in document EP1020219. Lipoamino acids and their salts, such as mono- and di-sodium acylglutamates, for example mono-sodium stearoyl glutamate (Amisoft HS-11PF) and disodium stearoyl glutamate (Amisoft HS-21 P) sold by the company Ajinomoto.

Alkyl phosphates and their salts, such as the alkali metal salts of dicetyl and dimyristyl phosphate, or potassium cetyl phosphate, such as Amphisol K sold by the company DSM Nutritional Products.

Cholesterol derivatives such as the alkaline salts of cholesterol sulfate, the alkaline salts of cholesterol phosphate.

- Ammonium salts of phophatidic acid.

- Phospholipids. Alkyl sulphonic derivatives as described in patent document EP1120101.

According to a preferred embodiment of the invention, the coemulsifier is chosen from glyceryl esters (glyceryl isostearate), sorbitan esters (Polysorbate 60) and polyethylene glycol esters (PEG 8 isostearate).

Aqueous phase

The aqueous phase of the composition according to the invention comprises water and optionally one or more compounds miscible with water or at least partly miscible with water, such as polyols; C2 to C8 lower monoalcohols, such as ethanol and isopropanol. By "room temperature" is meant a temperature of about 25 ° C, at normal atmospheric pressure (760 mmHg).

By "polyol" is meant any organic molecule comprising at least two free hydroxyl groups. Examples of polyols that may be mentioned include glycols such as butylene glycol, propylene glycol, isoprene glycol, glycerol and polyethylene glycols such as PEG-8, sorbitol, sugars such as glucose.

The aqueous phase may also comprise any usual water-soluble or water-dispersible additive as indicated below.

The aqueous phase may represent from 60 to 98% by weight, preferably from 65 to 95% by weight, better still from 70 to 90% by weight, and even more preferably from 70 to 85% by weight relative to the total weight of the composition. . The water-miscible compound (s), such as polyols and lower alcohols, may be present in an amount ranging from 0 to 30% of the total weight of the composition, in particular from 0.1 to 30% and better still in an amount ranging from 1 to 20%.

20 Oily phase

The oily phase is a fatty phase comprising at least one fatty substance chosen from fatty substances that are liquid at room temperature (20-25 ° C.) or volatile or nonvolatile oils of vegetable, mineral or synthetic origin, and mixtures thereof. These oils are physiologically acceptable.

The oily phase of the composition according to the invention contains at least one so-called makeup-removing oil chosen from: - esters resulting from the reaction of at least one fatty acid comprising at least 6 carbon atoms, preferably from 6 to 26 atoms carbon and more preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms and at least one alcohol comprising 1 to 17 carbon atoms and more preferably 3 to 15 carbon atoms. fatty acid ethers comprising from 6 to 20 carbon atoms such as dicaprylyl ether and mixtures thereof.

The esters may especially be chosen from: (1) esters obtained from at least one unsaturated straight chain aliphatic fatty acid having at least 6 carbon atoms, preferably from 6 to 12 carbon atoms and from at least one unsaturated branched chain aliphatic alcohol containing from 2 to 12 carbon atoms, (2) esters obtained from at least one unsaturated straight chain aliphatic fatty acid comprising at least 6 carbon atoms, for example comprising from 8 to 17 carbon atoms. carbon atoms and unsaturated linear chain aliphatic alcohol having 1 to 10 carbon atoms, preferably 2 to 10 carbon atoms, and mixtures thereof.

The esters are preferably mono- or di-esters. In a preferred manner, the esters contain no unsaturation and / or no ether or hydroxyl group. Even more advantageously, it is a saturated ester which contains no ether or hydroxyl group.

Thus, the ester used as makeup-removing oil of the composition in accordance with the invention may be chosen in particular from isopropyl myristate, isopropyl palmitate and ethyl-2-hexyl caprate / caprylate (or octyl caprate / caprylate). ), 2-ethylhexyl palmitate, isostearyl neopentanoate, isononyl isononanoate, hexyl laurate, esters of lactic acid and of fatty alcohols comprising 12 or 13 carbon atoms, dicaprylyl carbonate and mixtures thereof

As ether which can be used in the composition according to the invention, mention may be made in particular of dicaprylyl ether (Cetiol OE from Cognis). According to one embodiment, the composition according to the invention comprises a mixture of at least two cleansing oils mentioned above, in particular the mixture ethylhexyl palmitate and dicaprylyl ether

The amount of makeup-removing oil (s) as defined above may constitute all or part of the oily phase, and for example from 1 to 100%, preferably from 5 to 80% and better from 10 to 70% of the total weight of the oily phase. The makeup-removing oil may represent from 5 to 35% by weight of the composition according to the invention, preferably from 12 to 30% by weight and better still from 15 to 25% by weight. The oily phase may additionally contain all the fatty substances and especially the so-called additional oils, other than those indicated above, conventionally used in the cosmetics field.

As additional oils that may be present in the oily phase, mention may be made, for example, of hydrocarbon-based oils and oils of vegetable origin, such as apricot kernel oil; synthetic oils; volatile or non-volatile silicone oils and fluorinated oils. As examples of additional oils, mention may be made of: hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for example triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn and soybean oils; , squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, coriander, castor oil, avocado, caprylic / capric acid triglycerides, such as those marketed by Stearineries Dubois or those marketed under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; esters and synthetic ethers, in particular of fatty acids, such as the oils of formulas R'COOR2 and R'OR2 in which R 'represents the residue of a fatty acid or of a fatty alcohol containing from 8 to 29 carbon atoms, and R2 represents a hydrocarbon chain, branched or unbranched, containing from 3 to 30 carbon atoms, such as, for example, Purcellin oil, octyl-2-dodecyl stearate, octyl erucate or 2-dodecyl, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythritol tetraisostearate; linear or branched hydrocarbons of mineral or synthetic origin, such as paraffin oils, volatile or not, and their derivatives, petroleum jelly, polydecenes, isohexadecane, isododecane, hydrogenated polyisobutene such as Parleam oil; partially fluorinated hydrocarbon oils and / or silicone oils such as those described in document JP-A-2-295912; silicone oils such as volatile or non-volatile polymethylsiloxanes (PDMS) with a linear or cyclic silicone chain, which are liquid or pasty at room temperature, in particular volatile silicone oils, in particular cyclopolydimethylsiloxanes (cyclomethicones) such as cyclohexadimethylsiloxane and cyclopentadimethylsiloxane; 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 phenyltrimethicones, phenyldimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl-dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyltrimethylsiloxysilicates, and polymethylphenylsiloxanes; - their mixtures. according to one embodiment the additional oil is present in a content less than or equal to 50% relative to the oily phase.

Other fatty substances that may be present in the oily phase may be, for example, fatty acids, pasty compounds, fatty alcohols and waxes.

The amount of oily phase in the composition of the invention is less than 35% of the total weight of the composition, preferably less than or equal to 33% by weight and better still less than or equal to 32% by weight. The amount of oily phase may range, for example, from 2 to 35% by weight, preferably from 5 to 33% by weight, better still from 10 to 33% by weight and even more preferably from 10 to 30% by weight relative to the total weight. of the composition.

As indicated above, this amount of oily phase does not include the amount of emulsifier.

According to one embodiment, the composition according to the invention comprises less than 35% by weight of oils (cleansing and additive oils) relative to the total weight of the composition, preferably less than 30% by weight and better still less than 25% by weight. % by weight of oils.

Additives In known manner, the composition for topical application of the invention may also contain one or more adjuvants usual in the cosmetic or dermatological field. Adjuvants that may be mentioned include gelling agents, active agents, preservatives, antioxidants, perfumes, solvents, salts, fillers, dyestuffs, basic agents (triethanolamine, diethanolamine, sodium hydroxide) or acids ( citric acid), and also lipid vesicles or any other type of vector (nanocapsules, microcapsules, etc.), and mixtures thereof. These adjuvants are used in the usual proportions in the cosmetics 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 of the composition or into the phase oily, or in vesicles or any other type of vector. These adjuvants and their concentrations must be such that they do not modify the property desired for the emulsion of the invention.

Depending on the viscosity desired for the composition according to the invention, one or more hydrophilic gelling agents may be incorporated therein. As hydrophilic gelling agents, mention may be made, for example, of modified or unmodified carboxyvinyl polymers, such as the products sold under the names Carbopol (INCI name: carbomer) by the company Noveon; polyacrylamides; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally crosslinked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) marketed by Clariant under the name Hostacerin AMPS (INCI name: ammonium polyacryldimethyltauramide); crosslinked anionic copolymers of acrylamide and of AMPS, in the form of an W / O emulsion, such as those marketed under the name SEPIGEL 305 (CTFA name: Polyacrylamide / C13-14 Isoparaffin / Laureth-7) and under the name SIMULGEL 600 (CTFA name: Acrylamide / Sodium acryloyldimethyltaurate copolymer / Isohexadecane / Polysorbate 80) by the company SEPPIC; polysaccharide biopolymers such as xanthan gum, guar gum, alginates, modified or unmodified celluloses; and their mixtures. When they are present, these gelling agents must be introduced in such a quantity that they do not modify the properties of the composition according to the invention. As lipophilic gelling agents, mention may in particular be made of modified clays, such as modified magnesium silicate (RHEOX bentonite gel VS38), and hectorite modified with distearyl dimethyl ammonium chloride (INCI name: Disteardimonium hectorite) marketed under the name bentone 38 CE by the company RHEOX.

The gelling agent may be present in an active material content ranging from 0.05% to 10% by weight and preferably from 0.1% to 5% by weight relative to the total weight of the composition.

As fillers which can be used in the composition of the invention, mention may be made, for example, of pigments such as titanium oxide, zinc oxide or iron oxide and organic pigments; kaolin; silica; talcum; boron nitride; organic spherical powders, fibers; and their mixtures. As organic spherical powders, mention may be made, for example, of polyamide powders and in particular nylon powders such as nylon-1 or polyamide 12, sold under the names Orgasol by the company Atochem; polyethylene powders; Teflon; microspheres based on acrylic copolymers, such as those made of ethylene glycol dimethacrylate / lauryl methacrylate copolymer sold by Dow Corning under the name Polytrap; expanded powders such as hollow microspheres and in particular the microspheres sold under the name Expancel by the company Kemanord Plast or under the name Micropearl F 80 ED by the company Matsumoto; silicone resin microbeads such as those sold under the name Tospearl by the company Toshiba Silicone; polymethyl methacrylate microspheres, sold under the name MICROSPHERE M-100 by the company Matsumoto or under the name COVABEAD LH85 by the company Wackherr; ethylene-acrylate copolymer powders, such as those sold under the name FLOBEADS by Sumitomo Seika Chemicals; powders of natural organic materials such as starch powders, especially corn starch, wheat or rice, crosslinked or otherwise, such as starch powders crosslinked with octenylsuccinate anhydride, sold under the name DRY -FLO by the company National Starch. As fibers, mention may be made, for example, of polyamide fibers, such as, in particular, nylon 6 (or polyamide 6) (INCI name: nylon 6), nylon 6,6 (or polyamide 66) fibers (INCI name: nylon 66 ) or such as poly-p-phenylene terephtamide fibers; and their mixtures. These fillers may be present in amounts ranging from 0 to 20% by weight and preferably from 0.5 to 10% by weight relative to the total weight of the composition.

As active agents that may be used in the composition of the invention, mention may be made, for example, of moisturizing agents such as protein hydrolysates; sodium hyaluronate; polyols such as glycerin, glycols such as polyethylene glycols, and sugar derivatives; anti-inflammatories; procyannidol oligomers; vitamins such as vitamin A (retinol), vitamin E (tocopherol), vitamin K, vitamin C (ascorbic acid), vitamin B5 (panthenol), vitamin B3 or PP (niacinamide), derivatives of these vitamins (especially esters) and mixtures thereof; keratolytic and / or desquamating agents such as salicylic acid and its derivatives, alphahydroxyacids such as lactic acid and glycolic acid and their derivatives, ascorbic acid and its derivatives; urea; caffeine; depigmenting agents such as kojic acid, hydroquinone and caffeic acid; salicylic acid and its derivatives; retinoids such as carotenoids and vitamin A derivatives; hydrocortisone; melatonin; extracts of algae, mushrooms, vegetables, yeasts, bacteria; steroids; anti-bacterial active agents such as 2,4,4'-trichloro-2'-hydroxy diphenyl ether (or triclosan), 3,4,4'-trichlorocarbanilide (or triclocarban) and the acids indicated above, and in particular the salicylic acid and its derivatives; enzymes; flavonoids; tensing agents such as synthetic polymers, vegetable proteins, polysaccharides of plant origin in form or not of microgels, starches, wax dispersions, mixed silicates and colloidal particles of inorganic fillers; ceramides; anti-inflammatory agents; soothing agents; mattifying agents; anti-hair loss agents and / or hair regrowth; anti-wrinkle agents; essential oils ; and their mixtures; and any suitable asset for the ultimate purpose of the composition.

The compositions of the invention are advantageously prepared according to a process in which the oily fatty phase, comprising the oils and optionally the other fatty substances, is emulsified in the aqueous phase (into which the amphiphilic polymer has been introduced), with gentle stirring, i.e., under a low degree of shear. Stirring is preferably with a bar magnet or other stirring system giving low agitation and therefore low energy, at a temperature ranging from 20 ° to 45 ° C. By low stirring is meant stirring at a shear rate of less than 1000 microns.

The invention therefore also relates to a process for preparing the compositions as described above in which the oily fatty phase is introduced into the aqueous phase, comprising the amphiphilic polymer, under low shear.

Thus the emulsification process under low shear can be done with any other stirring system giving a low stirring and therefore low energy such as for example: - using a pale or helix, - in the tank equipped with a bottom-bottom turbine, a scraper blade, or a counter-rotating central mixing blade and heating / cooling by the double jacket of the vessel. Examples are the Macef and Maxilab tanks from the OLSA company, the tanks proposed by Pierre Guérin, - using a colloid mill, - using a static foam concentrate, - with a turbine online, from the IKA or KMF brand for example.

This process is critical for obtaining large oil globules according to the invention. One method of preparation may be as follows: the amphiphilic polymer is solubilized in water for 30 minutes with stirring at 25 ° C .; the resulting solution is macroscopically homogeneous. The emulsion is prepared by slow introduction of the oily phase in the aqueous phase with stirring using a Rayneri type homogenizer equipped with a pale under a stirring speed of 250 RPM for 20 minutes.

The compositions according to the invention can be, for example, in all the galenic forms of the O / W emulsions, for example in the form of serum, milk or cream, and they are prepared according to the usual methods. The compositions, objects of the invention, are intended for topical application and may constitute in particular a dermatological or cosmetic composition, for example intended for the treatment (anti-wrinkle, anti-aging, hydration, sun protection, etc.), the treatment, cleaning and makeup keratin materials and in particular the skin, lips, hair, eyelashes, hair and nails of human beings.

According to a preferred embodiment of the invention, the composition constitutes a cosmetic composition and is intended for topical application to the skin.

The invention finally relates to a process for the cosmetic treatment of keratin materials such as the skin, including the scalp, keratinous fibers such as eyelashes, hair, and / or lips, characterized in that applies on said keratin materials, a cosmetic composition as defined above.

The examples which follow will make it possible to better understand the invention, without however being limiting in nature. The quantities indicated are in% by weight, unless otherwise indicated.

EXAMPLES

Example 1: Ethylhexyl glycerin (Sensiva SC 50 from Schulke & Mayr) 0.5% Methylisothiazolinone 0.1% Sorbitol 3% Ethylhexyl palmitate 4% Dicaprylyl ether 16% Copolymer of AMPS and Genapol methacrylate T-080 0.3 % (grafting rate = 7.35%) (Aristoflex SNC from Clariant) Sorbitan monolaurate oxyethylenated 40 EO (Uniqema Tween 21) 0.04% Triethanolamine 0.0004% Water gsp100 Preparation of emulsions: Amphiphilic copolymer, supplied in powder form, is solubilized in water, sorbitol, ethylhexyl glycerin, triethanolamine and the preservative for 30 minutes under stirring under pale (500 rpm) at 25 ° C, the resulting solution is macroscopically homogeneous. The surfactant (Tween 21) is added. The emulsion is prepared by introducing the oily phase comprising the makeup-removing oils in the aqueous phase with stirring using: - an in-line turbine Ika under a stirring speed of 3000 RPM (emulsion 1) - d ' a Moritz-type stirrer under a stirring speed of 2300 RPM for 10 minutes (1 'emulsion).

The average size of the oily globules expressed in apparent average diameter and the viscosity of each composition were measured according to the methods indicated above. Emulsion 1 Emulsion 1 '(according to the invention) D [4.3] (m) 27.4 3.6 Viscosity (Pa. $) 0.136 0.086 Rheomat 180, 25 ° C., 200 RPM, Mobile 2 10 25 then evaluated the cleansing effectiveness of each composition according to the following protocol: The make-up removing tests are carried out on false eyelash specimens (black straight Caucasian hair 19 mm long bangs, mounted between two plates of 30 mm by 30 mm ). 2 test tubes of hair are made up with l'Oréal Paris Lashes Architect Waterproof mascara by making twice 10 brush passages spaced by 2 min of drying with product recovery between each set of 10. The specimens are allowed to dry at room temperature during a drying time of one hour. The first test specimen was then pinched between the fingers for 5 seconds in a cotton pad soaked with 1 g of 1 'emulsion and the second test specimen was pinched between the fingers for 5 seconds in a cotton pad soaked with 1 g of emulsion 1, then the The assembly is inserted into a press and subjected to a pressure equivalent to that of the fingers, holding the cotton and the test piece is extracted with a rapid movement of the cotton. The experiment is repeated for each test piece with a clean cotton impregnated again with 1g of composition 1 or 1 ', and until complete removal of make-up of the hair band made up. The evaluation of the cleansing efficiency consists in counting the number of cottons that are necessary to completely remove the mask of hair made up. Emulsion 1 Emulsion 1 'Number of cottons 11 cottons 20 cottons It can be seen that the effectiveness of emulsion 1 according to the invention, which has an oily globule size of approximately 27 microns, is clearly greater than that of emulsion 1 The size of the oily globules is of the order of 3 μm. Example 2 Cetyl hydroxythylcellulose (Polysurf 67 CS) Ethyl hexyl palmitate Dicaprylyl ether 0.9% 4% 16% 30% Water Conservative 1% Qsp 100 Operating Mode:

The amphiphilic copolymer is solubilized in water and the preservative with stirring under pale (500 rpm) at 25 ° C .; the resulting solution is macroscopically homogeneous. The emulsion is prepared by slow introduction of the oily phase comprising the makeup-removing oils in the aqueous phase with stirring using: - a stirrer to pale (150 rpm) at 25 ° C. (emulsion 2). a stirrer of the Moritz type under a stirring speed of 2300 RPM for 10 minutes (2 'emulsion).

The average size of the oily globules expressed in apparent average diameter of each composition is measured according to the method indicated above. Emulsion 2 Emulsion 2 '(according to the invention) D [4.3] (m) 62 7 Viscosity (Pa. $) 1.15 1.5 Rhéomat 180, 25 ° C., 200 RPM, Mobile 2 It was then evaluated the cleansing efficiency of each composition according to the protocol described in example 1. Emulsion 2 Emulsion 2 'Number of cottons 12 cottons 19 cottons 20 It is found that the cleansing efficiency of the emulsion 2 according to the invention which has a size oily globules of about microns, is significantly higher than that of the emulsion whose size of oily globules is of the order of 7 pm.

Example 3 An emulsion 3 according to the invention and an emulsion 3 'comprising 60% of oils were prepared and prepared according to the method of the examples of FR-2,843,695. Emulsion 3 Emulsion 3 '- (according to the invention) Water Qsp 100 Qsp 100 Copolymer of AMPS and methacrylate 0.4 0.4 of Genapol T-080 12% 24% (grafting rate = 7.35%) ( Aristoflex SNC from Clariant) Isopropyl palmitate Isododecane 18% 36% Glycerin 3% 3% 2% soda in water 0.06% 0.12% Preservative 0.3% 0.3% Amphiphilic copolymer, supplied in form of powder, is solubilized in water and glycerin and the preservative for 30 minutes under stirring under pale (450 rpm) at 25 ° C, the resulting solution is macroscopically homogeneous. The emulsion is prepared by introducing the oily phase comprising the makeup-removing oils in the aqueous phase with stirring using: - a stirrer with pale stirring speed 1500-1800 RPM for 15 minutes (emulsion 3) a Rayneri type stirrer under a stirring speed of 1500-1800 RPM for 15 minutes (3 'emulsion).

The average size of the oily globules expressed in apparent average diameter and the viscosity of each composition were measured according to the methods indicated above. Emulsion 3 Emulsion 3 'D [4.3] (lm) 57 19.5 Viscosity (Pa. $) 2.41 12.5 Rheomat 180, 25 ° C, 200 RPM, Mobile 2 The cleansing efficiency was then evaluated of each composition according to the protocol described in Example 1. Emulsion 3 Emulsion 3 'Number of cottons 8 cottons 8 cottons It is found that emulsion 3 which contains twice as little oil is as effective as emulsion 3'.

EXAMPLE 4 Emulsion 4 Emulsion 4 '- (according to the invention) Water Qsp 100 Qsp 100 Triethanolamine 0.002% 0.002% Polysorbate 60 0.05% 0.05% Copolymer of AMPS and methacrylate 0.3% 0.3 % Genapol T-080 4% - (grafting rate = 7.35%) (Aristoflex SNC from Clariant) Ethylhexyl palmitate Dicaprylyl ether 16% - Cyclohexasiloxane - 8% Parleam - 12% Butylene glycol 5% 5% Preservatives 0.1% 0.1% Each emulsion is prepared as follows: the amphiphilic copolymer is solubilized in water, triethanolamine, glycerine and the preservative for 30 minutes under stirring under pale (500 rpm) at 25 ° C., the solution obtained is macroscopically Homogeneous. The surfactant (Polysorbate 60) is added. The emulsion is prepared by introducing the oily phase comprising the makeup-removing oils in the aqueous phase with stirring using an in-line turbine Ika under a stirring speed of 3000 RPM.

The average size of the oily globules expressed in apparent average diameter and the viscosity of each composition are measured according to the methods indicated above. Emulsion 4 Emulsion 4 'D [4.3] (m) 21.1 19.5 Viscosity (Pa. $) 0.14 0.136 Rheomat 180, 25 ° C, 200 RPM, Mobile 3 The cleansing efficiency was then evaluated of each composition according to the protocol described in example 1. Emulsion 4 Emulsion 4 'Number of cottons 11 cottons After 20 cottons the eyelashes are still very made up The emulsion 4 according to the invention which comprises specific make-up removal oils makes it possible to remove make-up well more effective than the 4 'emulsion comprising conventional oils.

Claims (16)

REVENDICATIONS1. Composition for topical application, in the form of an oil-in-water emulsion comprising an oily phase dispersed in an aqueous phase and at least one non-crosslinked amphiphilic polymer, the globules of said emulsion having an average size ranging from 10 to 500 microns, the oily phase being present in an amount of less than 35% by weight relative to the total weight of the composition and said oily phase comprising at least one cleansing oil chosen from esters resulting from the reaction of at least one fatty acid having at least 6 carbon atoms and at least one alcohol comprising from 1 to 17 carbon atoms, the fatty acid ethers comprising from 6 to 20 carbon atoms and mixtures thereof. 2. Composition according to any one of the preceding claims, characterized in that the amount (of active material) of amphiphilic polymer ranges from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight and more preferably from 0.1 to 3% by weight relative to the total weight of the composition. 3. Composition according to any one of the preceding claims, characterized in that the water-soluble sequence of the amphiphilic polymer is formed of water-soluble monomers (a) chosen from, alone or as a mixture: - (meth) acrylic acid, - vinylsulfonic acid and (meth) allylsulfonic acid, - vinylphosphonic acid, - methyl vinylimidazolium chloride, - (meth) acrylamide, 2-vinylpyridine and 4-vinylpyridine, maleic acid and anhydride; crotonic acid, itaconic acid; the vinyl alcohol of formula CH 2 = CHOH; N-vinyllactams such as N-vinylpyrrolidone, N-vinylcaprolactam and N-butyrolactam; water-soluble derivatives of styrene; dimethyldiallyl ammonium chloride; N-vinylacetamide and N-methyl-N-vinylacetamide, N-vinylformamide and N-methylvinylformamide, the water-soluble vinyl monomers of formula (1): H 2 C = CR (1) CO Xi in which - R is chosen from H, -CH3, -C2H5 or -C3H7-X is chosen from: - alkyl oxides of -OR 'type where R' is a hydrocarbon radical, linear or branched, saturated or unsaturated, having from 1 to 6 carbons, substituted by at least one halogen atom (iodine, bromine, chlorine, fluorine); a sulphonic group (-SO3), sulphate (-SO4), phosphate (-PO4H2); hydroxy (-OH); ether (-O-); primary amine (-NH2); secondary amine (-NHR1), tertiary (-NR, R2) or quaternary (-N + R1R2R3) with R1, R2 and R3 being, independently of one another, a hydrocarbon radical, linear or branched, saturated or unsaturated having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R '+ R, + R2 + R3 does not exceed 7, - the groups -NH2, -NHR' and -NR'R "in which R 'and R "are, independently of each other, linear or branched, saturated or unsaturated hydrocarbon radicals having 1 to 6 carbon atoms, provided that the total number of carbon atoms of R' + R" does not exceed 7, said R 'and / or R "being substituted by a halogen atom (iodine, bromine, chlorine, fluorine); a hydroxy group (-OH); ether (-O-), sulfonic (-SO3); sulfate (-SO4); phosphate (-PO4H2); primary amine (-NH2); secondary amine (-NHR1), tertiary (-NR1R2) and / or quaternary (-N + R1R2R3) with R1, R2 and R3 being, independently of one another, a hydrocarbon radical, linear or branched, saturated or unsaturated having 1 to 6 carbon atoms, provided that the sum of the carbon atoms of R '+ R "+ R, + R2 + R3 does not exceed 7, and mixtures thereof 4. Composition according to any one of preceding claims, characterized in that the water-soluble block of the amphiphilic polymer consists of polycondensates or natural or modified natural polymers selected from: - water-soluble polyurethanes, - polyethyleneimine, polyethers such as polyoxyethylene and polyoxypropylene - xanthan gum, - alginates and their derivatives such as propylene alginate, - iota, kappa and lambda type caraghenans, - pectins of different degrees of modification (HM and LM), - cellulose derivatives and especially the rboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose and quaternized hydroxyethylcellulose; galactomannans and their derivatives, such as Konjac gum, Gellan, Carob, Fennugrec, Karaya, Tragacanth, acacia, guar gum, hydroxypropylguar, hydroxypropylguar modified with sodium methylcarboxylate groups, hydroxypropyl tri-methyl ammonium guar, starch derivatives, and mixtures thereof. 5. Composition according to any one of the preceding claims, characterized in that the hydrophobic block of the amphiphilic polymer comprises a monomer chosen from: - an alkyl radical containing from 6 to 30 carbon atoms, - a fluorinated or alkylfluorinated C6- C30, a cholesteryl radical or a radical derived from cholesterol, one or more aromatic cyclic group (s) such as benzene, naphthalene or pyrene, a silicone or alkylsilicone or alkylfluorosilicone radical, and their mixtures. 6. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is chosen from polymers derived from AMPS, polymers based on (meth) acrylic acid, diblock polymers based on polystyrene, polymers derived from polyether, natural polymers and their mixtures. 7. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is chosen from polymers comprising: (a) from 80 to 99 mol% of 2-acrylamido-2-methylpropanesulphonic acid-CII 2 H unit; Wherein X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion; (b) and from 1 to 20 mol%, and preferably from 1 to 15 mol% of the following unit of formula (3a): ## STR1 ## Wherein n and p, independently of one another, denote a number of moles and ranges from 0 to 30, preferably from 1 to 20 with the proviso that n + p is less than or equal to 30; preferably less than 25 and more preferably less than 20; R denotes a hydrogen atom, a linear or branched C1-C6 alkyl radical (preferably methyl) and R3 denotes a linear or branched alkyl having m carbon atoms ranging from 6 to 30, preferably from 10 to 25 atoms; of carbon. 15 8. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is chosen from polymers prepared from 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its salts. of sodium or ammonium, with a (meth) acrylic acid ester and: - a C, oC alcohol, oxyethylenated with 8 moles of ethylene oxide (Genapol C-20 080 from the company Clariant ), a C 8 oxo-alcohol oxyethylenated with 8 moles of ethylene oxide, - a C 7 oxo-alcohol oxyethylenated with 7 moles of ethylene oxide, - an oxyethylenated C 12 -C 14 alcohol by 7 moles of oxide, of a C 12 -C 14 alcohol oxyethylenated with 9 moles of ethylene oxide, of a C 12 -C 14 alcohol oxyethylenated with 11 moles of oxide, of an alcohol C16-C18 oxyethylenated with 8 moles of ethylene oxide; - a C16-C18 alcohol oxyethylenated with 11 moles of ethylene oxide; - a C16-C18 alcohol oxyethylenated with 15 moles of oxidised e, - a C16-C18 alcohol oxyethylenated with 20 moles of oxide, - a C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide, - a C18-C22 alcohol oxyethylenated by 25 moles of ethylene oxide; - an iso-C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide. 9. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymer is a copolymer of AMPS and C16-C18 alcohol methacrylate having from 6 to 25 oxyethylenated groups, obtained from methacrylic acid. or a salt of methacrylic acid and a C16-C18 alcohol oxyethylenated with 6 to 25 moles of ethylene oxide or a C12-C14 amps and C12-C14 alcohol methacrylate copolymer having from 6 to Oxyethylenated groups, obtained from methacrylic acid or a methacrylic acid salt and a C12-C14 alcohol oxyethylenated with 6 to 25 moles of ethylene oxide. 10. Composition according to any one of the preceding claims, characterized in that the amount of oily phase is less than 33% of the total weight of the composition, preferably less than or equal to 30% by weight. 11. Composition according to any one of the preceding claims, characterized in that the amount of oily phase ranges from 2 to 35% by weight, preferably from 5 to 33% by weight, better still from 10 to 33% by weight and more better from 15 to 30% by weight relative to the total weight of the composition. 12. Composition according to any one of the preceding claims, characterized in that the makeup removal oil is chosen from: - the esters derived from the reaction of at least one fatty acid having from 6 to 26 carbon atoms and better still 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms and at least one unsaturated straight chain aliphatic alcohol comprising 1 to 17 carbon atoms and more preferably 3 to 15 carbon atoms. and their mixtures. 13. Composition according to any one of the preceding claims, characterized in that the cleansing oil is chosen from: (1) esters obtained from at least one unsaturated straight-chain aliphatic fatty acid having at least 6 carbon atoms. carbon, preferably 6 to 12 carbon atoms and at least one unsaturated branched chain aliphatic alcohol having 2 to 12 carbon atoms, (2) esters obtained from at least one straight-chain aliphatic fatty acid unsaturated compound having at least 6 carbon atoms, for example comprising 8 to 17 carbon atoms, and unsaturated linear chain aliphatic alcohol containing 1 to 10 carbon atoms, preferably 2 to 10 carbon atoms, and mixtures thereof. 14. Composition according to any one of the preceding claims, characterized in that the cleansing oil is chosen from isopropyl myristate, isopropyl palmitate and ethyl 2-hexyl caprate / caprylate (or caprate / caprylate). octyl), 2-ethylhexyl palmitate, isostearyl neopentanoate, isononyl isononanoate, hexyl laurate, esters of lactic acid and fatty alcohols comprising 12 or 13 carbon atoms , dicaprylyl carbonate and mixtures thereof 15. Composition according to any one of the preceding claims, characterized in that the cleansing oil represents from 5 to 35% by weight of the composition, preferably from 12 to 30% by weight and better still from 15 to 25% by weight. . 16. Process for the cosmetic treatment of the skin, the hair, and / or the lips, characterized in that a cosmetic composition according to any one of Claims 1 to 10, is applied to the skin, the hair and / or the lips. 15.25