WO2017220742A1

WO2017220742A1 - Composition comprising stabilized polymer particles, a hydrophobic film-forming polymer, an aqueous phase and a surfactant

Info

Publication number: WO2017220742A1
Application number: PCT/EP2017/065450
Authority: WO
Inventors: Philippe Ilekti; Laure DAUBERSIES
Original assignee: L'oreal
Priority date: 2016-06-23
Filing date: 2017-06-22
Publication date: 2017-12-28
Also published as: FR3052976A1

Abstract

The present invention relates to a composition, especially a cosmetic composition, for caring for and/or making up keratin materials, comprising: - particles of at least one polymer surface-stabilized with a stabilizer, - at least one volatile hydrocarbon-based oil, - at least one hydrophobic film-forming polymer, - at least one aqueous phase, and - at least one surfactant chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol.

Description

COMPOSITION COMPRISING STABILIZED POLYMER PARTICLES, A HYDROPHOBIC FILM-FORMING POLYMER, AN AQUEOUS PHASE AND A

SURFACTANT

The present invention relates to the field of caring for and/or making up keratin materials, especially keratin fibers, and is directed toward proposing compositions more particularly intended for making up the eyelashes and the contours of the eyelids and/or the eyes.

The term "keratin materials" preferably means human keratin materials, especially keratin fibers.

The term "keratin fibers" in particular means the eyelashes and/or the eyebrows, and preferably the eyelashes. For the purposes of the present invention, this term "keratin fibers" also extends to synthetic false eyelashes.

The present invention proves to be most particularly advantageous for caring for and/or making up keratin materials.

In general, compositions intended for making up keratin fibers (mascara), for example the eyelashes, or for coating the skin (liner), for example the contour of the eyes or the eyelids (eyeliner) or the lips (lip liner), are of a nature which affords a matt makeup effect. The reason for this is that it is difficult to give them a capacity to afford a glossy film, given the lack of compatibility of the compounds conventionally considered for this purpose, in the field of making up the lips or the nails, and given the implementation imperatives required for making up the eyelashes and the contour of the eyes.

Thus, the glossy appearance is conventionally afforded, in a cosmetic composition of lip gloss type, by the use of oily fatty substances, and in a composition of varnish type, by the use of rigid film-forming polymers.

However, the use of these two types of compound that are efficient for forming a glossy film impairs the drying properties as regards the oils and the comfort as regards the rigid film-forming polymers. Specifically, in the presence of oily fatty substances, the film deposited on the keratin materials does not dry, and the use of rigid film-forming polymers makes the deposit uncomfortable to users due to the perceived rigidity.

The need thus remains for compositions, especially cosmetic compositions, especially mascaras and eyeliners, which have, after application, a long-lasting glossy makeup result, while at the same time remaining capable of presenting good properties in terms of transfer resistance, comfort, residual tack resistance and persistence over time.

The need also remains for compositions, especially cosmetic compositions, especially mascaras and eyeliners, which have an intensified color effect.

Contrary to all expectation, the inventors have found that the combination of at least specific particles of at least one stabilized polymer as defined below, of at least one hydrophobic film-forming polymer, of at least one aqueous phase and of at least one surfactant as defined below, makes it possible precisely to meet this need. Thus, according to a first of its aspects, the present invention relates to a composition, especially a cosmetic composition, for caring for and/or making up keratin materials, comprising:

- particles of at least one polymer that is surface-stabilized with a stabilizer, the polymer of the particles being a C1-C4 alkyl (meth)acrylate polymer; the stabilizer being an isobornyl (meth)acrylate polymer chosen from isobornyl (meth)acrylate homopolymer and statistical copolymers of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate weight ratio of greater than 4,

- at least one volatile hydrocarbon-based oil,

- at least one hydrophobic film- forming polymer,

- at least one aqueous phase, and

- at least one surfactant chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol.

Contrary to all expectation, and as demonstrated in the experimental section below, the inventors have in fact found that the presence of at least specific particles of at least one stabilized polymer as defined below, of at least one hydrocarbon-based volatile oil, of at least one hydrophobic film-forming polymer, of at least one aqueous phase, and of at least one surfactant chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol makes it possible to gain access to a mascara formulation or to a liner formulation which retains expected properties in terms of persistence, and which advantageously makes it possible to obtain a glossy, long-lasting, transfer-resistant deposit which has no residual tack, which is comfortable and which has an intense color effect.

The compositions according to the invention may especially be makeup compositions intended for affording the desired makeup effect solely by using them around the eyes.

In particular, a composition according to the invention proves to be advantageous as a mascara.

According to another of its aspects, a subject of the invention is also a process, especially a cosmetic process, for making up and/or caring for keratin materials, especially the eyelashes, comprising at least one step which consists in applying to said keratin materials a composition in accordance with the invention.

SOLIDS CONTENT

The composition according to the invention advantageously comprises a solids content of greater than or equal to 30%, preferably 35%, in particular 40%>, or even 42%, and preferentially 45%.

For the purposes of the present invention, the "solids content" denotes the content of nonvolatile matter.

The amount of solids content (abbreviated as SC) of a composition according to the invention is measured using a Halogen Moisture Analyzer HR 73 commercial halogen desiccator from Mettler Toledo. The measurement is performed on the basis of the weight loss of a sample dried by halogen heating, and thus represents the percentage of residual matter once the water and the volatile matter have evaporated off.

This technique is fully described in the machine documentation supplied by Mettler Toledo.

The measurement protocol is as follows:

Approximately 2 g of the composition, referred to hereinbelow as the sample, are spread out on a metal crucible, which is placed in the halogen desiccator mentioned above. The sample is then subjected to a temperature of 105°C until a constant weight is obtained. The wet mass of the sample, corresponding to its initial mass, and the dry mass of the sample, corresponding to its mass after halogen heating, are measured using a precision balance. The experimental error associated with the measurement is of the order of more or less 2%.

The solids content is calculated in the following manner:

Solids content (expressed as weight percentage) = 100 x (dry mass/wet mass).

VISCOSITY

The composition according to the invention may be characterized by a viscosity preferably ranging from 0.5 to 50 Pa.s, measured at a room temperature of 25°C using a Rheomat RM100^® machine.

AQUEOUS PHASE

As stated above, a composition according to the invention comprises at least one aqueous phase.

Such an aqueous phase may comprise at least water. The water may be present in a total content ranging from 10% to 50% by weight, relative to the total weight of the composition. Preferably, the water is present in a content ranging from 20% to 50% by weight, relative to the total weight of the composition.

More preferably, the water is present in a content ranging from 25% to 45% by weight, relative to the total weight of the composition.

Preferably, the composition according to the invention comprises at least 10% by weight of water, preferably at least 20% by weight of water and preferably at least 25% by weight of water, relative to the total weight of the composition.

The composition in accordance with the invention may comprise, besides water, at least one water-soluble solvent.

In the present invention, the term "water-soluble solvent" denotes a compound that is liquid at room temperature and water-miscible (miscibility with water of greater than 50%) by weight at 25°C and atmospheric pressure).

The water-soluble solvents that may be used in the compositions according to the invention may also be volatile.

Among the water-soluble solvents that may be used in the compositions in accordance with the invention, mention may be made especially of lower monoalcohols containing from 2 to 5 carbon atoms, such as ethanol and isopropanol, glycols containing from 3 to 8 carbon atoms, such as propylene glycol, 1,3-butylene glycol and dipropylene glycol, C₃ and C₄ ketones and C₂-C₄ aldehydes.

The aqueous phase (water and optionally the water-miscible solvent) may be present in the composition in a content ranging from 10% to 50% by weight and preferably ranging from 20% to 50% by weight relative to the total weight of the composition.

Particularly preferably, the aqueous phase (water and optionally the water- miscible solvent) is present in the composition in a content ranging from 25% to 45% by weight, relative to the total weight of the composition.

The aqueous phase may also contain other additives such as water-soluble active agents, preserving agents, salts, gelling agents, fillers, water-soluble or water- dispersible polymers, water-soluble dyes, film-forming polymers, hydrophilic thickeners, etc. SURFACTANT

The composition of the invention comprises one or more surfactants chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol.

Preferably, the ester of polyhydroxylated fatty acid and of polyoxyalkylene glycol is a fatty acid ester of polyethylene glycol.

The ester of fatty acid and of polyoxyalkylene glycol may be a monoester or a polyester, especially a diester.

The fatty acid may comprise from 12 to 20 carbon atoms, preferably from 14 to 18 carbon atoms.

It may be chosen especially from oleic acid, palmitic acid, stearic acid and hydroxystearic acid, and mixtures thereof.

The polyethylene glycol may comprise from 4 to 50 moles of ethylene oxide and more preferably from 20 to 40 moles of ethylene oxide.

According to one embodiment, use is made of an ester, preferably a diester, of polyethylene glycol comprising from 20 to 40 moles of ethylene oxide and of a polyhydroxylated fatty acid, said polyhydroxylated fatty acid comprising from 14 to 18 carbon atoms, in particular polyhydroxystearic acid. In particular, the ester of fatty acid and of polyoxyalkylene glycol is in the form of a block polymer, preferably of ABA structure, comprising poly(hydroxylated acid ester) blocks A and polyethylene glycol blocks B.

The fatty acid ester of said polymer bears a chain comprising from 12 to 20 carbon atoms and preferably from 14 to 18 carbon atoms.

The polyethylene glycol blocks of said surfactant as defined above preferably comprise from 4 to 50 moles of ethylene oxide and more preferably from 20 to 40 moles of ethylene oxide.

A compound that is particularly suitable for preparing the compositions of the invention is polyethylene glycol dipolyhydroxystearate containing 30 EO, sold under the trade name Cithrol DPHS-SO-(MV) by the company Croda.

According to a particularly preferred embodiment, the surfactant chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol is a fatty acid ester of polyethylene glycol, and is preferably polyethylene glycol dipolyhydroxystearate containing 30 EO.

According to a preferred embodiment of the invention, the composition according to the invention comprises at least 0.5%, preferably at least 1%, even more particularly between 0.5% and 10%, even more particularly between 1% and 8% and better still between 1% and 5% by weight of surfactant(s) chosen from esters of fatty acid and of polyoxyalkylene glycol, relative to the total weight of the composition.

ADDITIONAL SURFACTANT

According to a particular embodiment, the composition according to the invention may comprise, besides the surfactant chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol, an additional surfactant, also known as a coemulsifier.

The additional surfactant may be chosen, for example, from nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof. Reference may be made to Kirk- Othmer's Encyclopedia of Chemical Technology, Volume 22, pages 333-432, 3rd Edition, 1979, Wiley, for the definition of the emulsifying properties and functions of surfactants, in particular pages 347-377 of this reference, for the anionic, amphoteric and nonionic surfactants.

According to a particular embodiment, the composition comprises at least one hydrocarbon-based surfactant as additional surfactant.

According to a particular embodiment, the composition according to the invention comprises at least one nonionic surfactant as additional surfactant.

The nonionic surfactants may be chosen especially from alkyl and polyalkyl esters of poly(ethylene oxide), oxyalkylenated alcohols, alkyl and polyalkyl ethers of poly(ethylene oxide), optionally polyoxyethylenated alkyl and polyalkyl esters of sorbitan, optionally polyoxyethylenated alkyl and polyalkyl ethers of sorbitan, alkyl and polyalkyl glycosides or polyglycosides, in particular alkyl and polyalkyl glucosides or polyglucosides, alkyl and polyalkyl esters of sucrose, optionally polyoxyethylenated alkyl and polyalkyl esters of glycerol, and optionally polyoxyethylenated alkyl and polyalkyl ethers of glycerol, gemini surfactants, cetyl alcohol and stearyl alcohol, and mixtures thereof.

According to a particular embodiment, the composition according to the invention comprises at least one anionic surfactant as additional surfactant.

The anionic surfactants may be chosen from alkyl ether sulfates, carboxylates, amino acid derivatives, sulfonates, isethionates, taurates, sulfosuccinates, alkylsulfoacetates, phosphates and alkyl phosphates, polypeptides, metal salts of C10-C30 and especially C16-C25 fatty acids, in particular metal stearates and behenates, and mixtures thereof.

According to a particular embodiment, the composition according to the invention comprises at least one cationic surfactant as additional surfactant.

The cationic surfactants may be chosen especially from alkylimidazolidiniums such as isostearylethylimidonium ethosulfate, and ammonium salts such as (C 12-30 alkyl)tri(Ci-4 alkyl)ammonium halides, for instance N,N,N-trimethyl-l-docosanaminium chloride (or behentrimonium chloride).

According to a particular embodiment, the compositions according to the invention may also contain as additional surfactant one or more amphoteric surfactants, in particular N-acylamino acids such as N-alkyl aminoacetates and disodium cocoamphodiacetate, and amine oxides such as stearamine oxide, or alternatively silicone surfactants, for instance dimethicone copolyol phosphates such as the product sold under the name Pecosil PS 100^® by the company Phoenix Chemical. According to a particular embodiment, the composition comprises at least one silicone surfactant as additional surfactant. Examples that may be mentioned include:

a) nonionic surfactants with an HLB of greater than or equal to 8 at 25 °C, used alone or as a mixture, in particular dimethicone copolyol, such as the product sold under the name Q2-5220^® by the company Dow Corning, and dimethicone copolyol benzoate such as the product sold under the name Finsolv SLB 101^® and 201^® by the company Fintex;

b) nonionic surfactants with an HLB of less than 8 at 25°C, used alone or as a mixture, in particular the cyclomethicone/dimethicone copolyol mixture sold under the name Q2- 3225C^® by the company Dow Corning. According to one embodiment of the invention, the composition according to the invention comprises at least 0.5%, preferably at least 1%, even more particularly between 0.5%> and 15% and better still between 2% and 5% by weight of additional surfactant(s) other than the esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol, relative to the total weight of the composition.

OILY PHASE

The composition of the invention comprises at least one liquid oily phase, comprising at least one volatile or nonvolatile liquid oil, or a mixture of volatile or nonvolatile liquid oils.

The term "oil" means a water-immiscible non-aqueous compound that is liquid at room temperature (25°C) and at atmospheric pressure (760 mmHg).

The term "liquid oil" means an oil that is capable of flowing under its own weight, at room temperature (20°C) and at atmospheric pressure (760 mmHg), as opposed to "solid" fatty substances.

The oily phase preferably represents from 50% to 85%, preferentially from

50%) to 80%) and advantageously from 50%> to 75% by weight, relative to the total weight of the composition. POLYMER PARTICLES

As mentioned previously, the composition according to the invention comprises particles, which are generally spherical, of at least one surface-stabilized polymer.

The polymer of the particles is a C1-C4 alkyl (meth)acrylate polymer.

The C1-C4 alkyl (meth)acrylate monomers may be chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n- butyl (meth)acrylate, and tert-butyl (meth)acrylate.

A C1-C4 alkyl acrylate monomer is advantageously used.

Preferentially, the polymer of the particles is a methyl (meth)acrylate and/or ethyl (meth)acrylate polymer, more preferentially a methyl acrylate and/or ethyl acrylate polymer.

The polymer of the particles may also comprise an ethylenically unsaturated acid monomer or the anhydride thereof, chosen especially from ethylenically unsaturated acid monomers comprising at least one carboxylic, phosphoric or sulfonic acid function, such as crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid or acrylamidogly colic acid, and salts thereof.

The ethylenically unsaturated acid monomer is preferably chosen from

(meth)acrylic acid, maleic acid and maleic anhydride.

The salts may be chosen from salts of alkali metals, for example sodium or potassium; salts of alkaline-earth metals, for example calcium, magnesium or strontium; metal salts, for example zinc, aluminum, manganese or copper; ammonium salts of formula NH₄ ⁺; quaternary ammonium salts; salts of organic amines, such as, for example, salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2- hydroxyethylamine, bis(2-hydroxyethyl)amine or tris(2-hydroxyethyl)amine; lysine or arginine salts.

The polymer of the particles may thus comprise or consist essentially of from 80% to 100% by weight of C1-C4 alkyl (meth)acrylate and from 0% to 20% by weight of ethylenically unsaturated acid monomer, relative to the total weight of the polymer. According to a first embodiment of the invention, the polymer consists essentially of a polymer of one or more C1-C4 alkyl (meth)acrylate monomers.

According to a second embodiment of the invention, the polymer is essentially constituted of a copolymer of C1-C4 (meth)acrylate and of (meth)acrylic acid or maleic anhydride.

The polymer of the particles may be chosen from:

- methyl acrylate homopolymers,

- ethyl acrylate homopolymers,

- methyl acrylate/ethyl acrylate copolymers,

- methyl acrylate/ethyl acrylate/acrylic acid copolymers,

- methyl acrylate/ethyl acrylate/maleic anhydride copolymers,

- methyl acrylate/acrylic acid copolymers,

- ethyl acrylate/acrylic acid copolymers,

- methyl acrylate/maleic anhydride copolymers, and

- ethyl acrylate/maleic anhydride copolymers.

Advantageously, the polymer of the particles is a non-crosslinked polymer. The polymer of the particles preferably has a number-average molecular weight ranging from 2000 to 10 000 000 and preferably ranging from 150 000 to 500 000.

The stabilizer is an isobornyl (meth)acrylate polymer chosen from isobornyl (meth)acrylate homopolymer and statistical copolymers of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate weight ratio of greater than 4, preferably greater than 4.5 and even more advantageously greater than or equal to 5. Advantageously, said weight ratio ranges from 4.5 to 19, preferably from 5 to 19 and more particularly from 5 to 12.

Thus, according to a particular embodiment, a composition according to the invention comprises one or more stabilizers, said stabilizer(s) being a statistical copolymer of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate weight ratio of greater than or equal to 5.

Advantageously, the stabilizer is chosen from:

- isobornyl acrylate homopolymers, - statistical copolymers of isobornyl acrylate/methyl acrylate,

- statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate, and

- statistical copolymers of isobornyl methacrylate/methyl acrylate,

in the weight ratio described previously.

The stabilizing polymer preferably has a number-average molecular weight ranging from 10 000 to 400 000 and preferably ranging from 20 000 to 200 000.

Preferably, the particles are introduced into the composition in the form of a dispersion of particles, which are generally spherical, of at least one surface-stabilized polymer, in an oily medium, containing at least one hydrocarbon-based oil, especially as defined below, said hydrocarbon-based oil being identical to or different from a nonvolatile oil as described previously, preferably identical. Therefore, the dispersion is preferably prepared separately before it is introduced into the composition.

In the case of a particle dispersion, the polymer(s) of the particles may be present in the dispersion in a content ranging from 21% to 58.5% by weight and preferably ranging from 36% to 42% by weight, relative to the total weight of the dispersion.

The stabilizer is in contact with the surface of the polymer particles and thus makes it possible to stabilize these particles at the surface, in particular in order to keep these particles in dispersion in the oily medium.

Advantageously, the combination of the stabilizer(s) + polymer(s) of the particles present in particular in the dispersion comprises from 10% to 50% by weight of polymerized isobornyl (meth)acrylate and from 50% to 90% by weight of polymerized Ci- C₄ alkyl (meth)acrylate, relative to the total weight of the combination of the stabilizer(s) + polymer(s) of the particles.

Preferentially, the combination of the stabilizer(s) + polymer(s) of the particles present in particular in the dispersion comprises from 15% to 30% by weight of polymerized isobornyl (meth)acrylate and from 70% to 85% by weight of polymerized Ci- C₄ alkyl (meth)acrylate, relative to the total weight of the combination of the stabilizer(s) + polymer(s) of the particles.

Preferably, the stabilizer(s) are soluble in the hydrocarbon-based oil(s), in particular soluble in isododecane. According to a theory which should not limit the scope of the present invention, the inventors put forward the hypothesis that the surface stabilization of the Ci- C₄ alkyl (meth)acrylate polymer particles results from a phenomenon of surface adsorption of the stabilizer onto the C1-C4 alkyl (meth)acrylate polymer particles.

When the polymer particles are provided in the composition in the form of a pre-prepared dispersion, the oily medium of this polymer dispersion comprises a hydrocarbon-based oil, described below.

Hydrocarbon-based volatile oil

As indicated above, the particles are preferably introduced into the composition in the form of a dispersion of particles, which are generally spherical, of at least one surface-stabilized polymer as described above, in an oily medium, containing at least one hydrocarbon-based oil, said hydrocarbon-based oil being identical to or different from a nonvolatile oil as described previously.

This oil may be volatile (vapor pressure greater than or equal to 0.13 Pa measured at 25°C) or nonvolatile (vapor pressure less than 0.13 Pa measured at 25°C).

Preferably, the hydrocarbon-based oil of the dispersion is volatile. The hydrocarbon-based oil of the dispersion may be chosen from hydrocarbon- based oils containing from 8 to 16 carbon atoms, and especially:

- C8-C16 branched alkanes such as Cs-Ci6 isoalkanes of petroleum origin (also known as isoparaffins) such as isododecane (also known as 2,2,4,4, 6-pentamethylheptane), isodecane, isohexadecane and, for example, the oils sold under the trade names Isopar or Permethyl;

- linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, the mixtures of n-undecane (Cn) and of n-tridecane (C13) obtained in Examples 1 and 2 of application WO 2008/155059 from the company Cognis, and mixtures thereof;

- short-chain esters (having from 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate; and

- mixtures thereof. More particularly, the content of hydrocarbon-based volatile oil(s) ranges from 10% to 50% by weight, preferably from 15% to 45% and preferentially from 15% to 40% by weight relative to the total weight of the composition.

This hydrocarbon-based oil may be provided totally or partly with the surface- stabilized polymer particles, in particular when these particles are introduced into the composition in the form of a pre-prepared dispersion of stabilized polymer particles. In this case, the hydrocarbon-based oil present in the composition represents at least the oily medium of the dispersion of polymer particles.

Advantageously, the hydrocarbon-based oil of the dispersion is apolar (thus formed solely from carbon and hydrogen atoms). Preferably, the hydrocarbon-based oil is solely formed from carbon and hydrogen atoms.

The hydrocarbon-based oil of the dispersion is preferably chosen from hydrocarbon-based oils containing from 8 to 16 carbon atoms and better still from 12 to 16 carbon atoms, in particular the apolar oils described previously.

Preferentially, the hydrocarbon-based oil of the dispersion is isododecane.

More particularly, the isododecane content ranges from 10% to 50%, preferably from 15% to 45% and preferentially from 15% to 40% by weight relative to the total weight of the composition.

Thus, according to a particular embodiment, the hydrocarbon-based volatile oil(s) are present in a composition according to the invention in a content ranging from 25% to 65%o, preferably from 30%> to 60%> and preferentially from 35% to 55% by weight relative to the total weight of the composition, the hydrocarbon-based volatile oil(s) preferably being apolar, even more preferentially containing from 8 to 16 carbon atoms, or better still being isododecane.

According to a preferred embodiment, the hydrocarbon-based oil is present in a composition according to the invention in a content ranging from 10% to 50%, preferably from 15% to 45% and preferentially from 15% to 40% by weight relative to the total weight of the composition, the hydrocarbon-based volatile oil(s) preferably being apolar, even more preferentially containing from 8 to 16 carbon atoms, or better still being isododecane. The polymer particles, in particular in the dispersion, preferably have an average size, especially a number-average size, ranging from 50 nm to 500 nm, especially ranging from 75 nm to 400 nm and better still ranging from 100 nm to 250 nm.

In general, a dispersion of polymer particles that is suitable for use in the invention may be prepared in the following manner, which is given as an example.

The polymerization may be performed in dispersion, i.e. by precipitation of the polymer during formation, with protection of the formed particles with a stabilizer.

In a first step, the stabilizing polymer is prepared by mixing the constituent monomer(s) of the stabilizing polymer, with a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers. In a second step, the constituent monomer(s) of the polymer of the particles are added to the stabilizing polymer formed and polymerization of these added monomers is performed in the presence of the free-radical initiator.

When the oily medium is a nonvolatile hydrocarbon-based oil, the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the nonvolatile hydrocarbon-based oil (which should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.

A synthesis solvent which is such that the monomers of the stabilizing polymer and the free-radical initiator are soluble therein, and the polymer particles obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen.

In particular, the synthesis solvent may be chosen from alkanes such as heptane or cyclohexane.

When the oily medium is a volatile hydrocarbon-based oil, the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent. The monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles which is obtained should be insoluble therein.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5%-20% by weight. The total amount of the monomers may be present in the solvent before the start of the reaction, or part of the monomers may be added gradually as the polymerization reaction proceeds.

The free-radical initiator may especially be azobisisobutyronitrile or tert-butyl peroxy-2-ethylhexanoate. The polymerization may be performed at a temperature ranging from 70 to

110°C.

The polymer particles are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer.

The stabilization may be performed by any known means, and in particular by direct addition of the stabilizer, during the polymerization.

The stabilizer is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles. However, it is also possible to add it continuously, especially when the monomers of the polymer of the particles are also added continuously.

From 10% to 30% by weight and preferably from 15% to 25% by weight of stabilizer may be used relative to the total weight of monomers used (stabilizer + polymer of the particles).

The dispersion of polymer particles advantageously comprises from 30%> to 65%o by weight and preferably from 40%> to 60%> by weight of solids, relative to the total weight of the dispersion.

A composition according to the invention may thus comprise from 5% to 25%, preferably from 8% to 25% and more preferentially from 10% to 20% by weight of polymer particles as described previously, relative to the total weight of the composition (content expressed as solids).

A composition according to the invention may thus comprise from 10% to 50%, preferably from 16% to 50% and more preferentially from 20% to 40% by weight of dispersion of polymer particles (particles + hydrocarbon-based oil) as described previously, relative to the total weight of the composition.

HYDROPHOBIC FILM-FORMING POLYMERS

As mentioned previously, a composition according to the invention moreover comprises at least one hydrophobic film-forming polymer, preferably chosen from hydrocarbon-based block copolymers and hydrocarbon-based resins, and mixtures thereof.

In the present patent application, the term "film-forming polymer" means a polymer that is capable, by itself or in the presence of an auxiliary film-forming agent, of forming a macroscopically continuous deposit, and preferably a cohesive deposit, and even better still a deposit whose cohesion and mechanical properties are such that said deposit can be isolated and manipulated individually, for example when said deposit is prepared by pouring onto a non-stick surface such as a Teflon-coated or silicone-coated surface.

The term "hydrophobic" or "water-insoluble" polymer means that the polymer is not soluble in water, according to the definition below.

The term "water-soluble" polymer means that the polymer dissolves in water or in a 50/50 by volume mixture of water and ethanol, or alternatively a mixture of water and isopropanol, without modification of the pH, at a solids content of 5% by weight, at room temperature (25°C, 1 atm.). The polymer is considered to be soluble if it does not form a precipitate or agglomerate that is visible to the naked eye when it is placed in solution, and if it therefore gives a clear solution.

According to the invention, the hydrophobic film-forming polymer(s) are different from the polymers of the particles. Therefore, the compositions according to the invention comprise both polymer particles that are surface-stabilized with a stabilizer and at least one hydrophobic film- forming polymer.

Hydrocarbon-based block copolymers

According to one embodiment, the composition according to the present invention may comprise at least one hydrocarbon-based block copolymer.

The term "block" polymer means a polymer comprising at least two different blocks and preferably at least three different blocks.

The hydrocarbon-based block copolymers that are suitable for use in the invention, also known as block copolymers, are preferably soluble or dispersible in the oily phase.

The hydrocarbon-based block copolymer may especially be a diblock copolymer.

Such hydrocarbon-based block copolymers are described in patent application US-A-2002/005562 and in patent US-A-5 221 534.

The copolymer may contain at least one block whose glass transition temperature is preferably less than 20°C, preferably less than or equal to 0°C, preferably less than or equal to -20°C and more preferably less than or equal to -40°C. The glass transition temperature of said block may be between -150°C and 20°C and especially between -100°C and 0°C.

The hydrocarbon-based block copolymer present in the composition according to the invention may be an amorphous copolymer formed by polymerization of an olefin. The olefin may especially be an elastomeric ethylenically unsaturated monomer.

The term "amorphous polymer" means a polymer that does not have a crystalline form.

Examples of olefins that may be mentioned include ethylenic carbide monomers, especially containing one or two ethylenic unsaturations and containing from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene, isoprene or pentadiene.

Advantageously, the hydrocarbon-based block copolymer is an amorphous block copolymer of styrene and olefin.

Block copolymers comprising at least one styrene block and at least one block comprising units chosen from butadiene, ethylene, propylene, butylene and isoprene or a mixture thereof are especially preferred.

According to one preferred embodiment, the hydrocarbon-based block copolymer is hydrogenated to reduce the residual ethylenic unsaturations after the polymerization of the monomers.

In particular, the hydrocarbon-based block copolymer is an optionally hydrogenated copolymer, containing styrene blocks and ethylene/C3-C4 alkylene blocks.

According to a preferred embodiment, the hydrophobic film-forming polymer is a hydrocarbon-based block copolymer, preferably at least one diblock copolymer, which is preferably hydrogenated, preferably chosen from styrene-ethylene/propylene copolymers, styrene-ethylene/butadiene copolymers and styrene-ethylene/butylene copolymers. Diblock polymers are especially sold under the name Kraton^® G1701E by the company Kraton Polymers.

A diblock copolymer such as those described above, in particular a styrene- ethylene/propylene diblock copolymer, is advantageously used as hydrocarbon-based block copolymer.

The hydrocarbon-based block copolymer(s) may be present in a content ranging from 0.5% to 15% by weight, relative to the total weight of the composition, preferably ranging from 1% to 10% by weight and even more advantageously from 2% to 8% by weight, relative to the total weight of the composition.

Hydrocarbon-based resins

According to one embodiment, the composition according to the present invention may comprise at least one hydrocarbon-based resin.

Preferably, the hydrocarbon-based resin (also known as a tackifying resin) has a number-average molecular weight of less than or equal to 10 000 g/mol, especially ranging from 250 g/mol to 5000 g/mol, better still less than or equal to 2000 g/mol and especially ranging from 250 g/mol to 2000 g/mol.

The number-average molecular weights (Mn) are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

The resin of the composition according to the invention is advantageously a tackifying resin. Such resins are described especially in the Handbook of Pressure Sensitive Adhesives, edited by Donatas Satas, 3rd edition, 1989, pages 609-619.

Preferably, the hydrocarbon-based resin is chosen from low molecular weight polymers that may be classified, according to the type of monomer they comprise, as:

- indene hydrocarbon-based resins, preferably such as resins derived from the polymerization in major proportion of indene monomer and in minor proportion of a monomer chosen from styrene, methylindene and methylstyrene, and mixtures thereof. These resins may optionally be hydrogenated. These resins may have a molecular weight ranging from 290 to 1150 g/mol.

Examples of indene resins that may be mentioned include those sold under the reference Escorez 7105 by the company Exxon Chem., Nevchem 100 and Nevex 100 by the company Neville Chem., Norsolene SI 05 by the company Sartomer, Picco 6100 by the company Hercules and Resinall by the company Resinall Corp., or the hydrogenated indene/methylstyrene/styrene copolymers sold under the name "Regalite" by the company Eastman Chemical, in particular Regalite R 1100, Regalite R 1090, Regalite R-7100, Regalite R1010 Hydrocarbon Resin and Regalite Rl 125 Hydrocarbon Resin; - aliphatic pentanediene resins such as those derived from the majority polymerization of the 1,3-pentanediene (trans- or cis-piperylene) monomer and of minor monomers chosen from isoprene, butene, 2-methyl-2-butene, pentene and 1,4-pentanediene, and mixtures thereof. These resins may have a molecular weight ranging from 1000 g/mol to 2500 g/mol.

Such 1,3-pentanediene resins are sold, for example, under the references Piccotac 95 by the company Eastman Chemical, Escorez 1304 by the company Exxon Chemicals, Nevtac 100 by the company Neville Chem. or Wingtack 95 by the company Goodyear;

- mixed resins of pentanediene and of indene, which are derived from the polymerization of a mixture of pentanediene and indene monomers such as those described above, for instance the resins sold under the reference Escorez 2101 by the company Exxon Chemicals, Nevpene 9500 by the company Neville Chem., Hercotac 1148 by the company Hercules, Norsolene A 100 by the company Sartomer, and Wingtack 86, Wingtack Extra and Wingtack Plus by the company Goodyear;

- diene resins of cyclopentanediene dimers such as those derived from the polymerization of first monomers chosen from indene and styrene, and of second monomers chosen from cyclopentanediene dimers such as dicyclopentanediene, methyldicyclopentanediene and other pentanediene dimers, and mixtures thereof. These resins generally have a molecular weight ranging from 500 g/mol to 800 g/mol, for instance those sold under the reference Betaprene BR 100 by the company Arizona Chemical Co., Neville LX-685-125 and Neville LX-1000 by the company Neville Chem., Piccodiene 2215 by the company Hercules, Petro-Rez 200 by the company Lawter or Resinall 760 by the company Resinall Corp.;

- diene resins of isoprene dimers such as terpenic resins derived from the polymerization of at least one monomer chosen from a-pinene, β-pinene and limonene, and mixtures thereof. These resins may have a molecular weight ranging from 300 g/mol to 2000 g/mol. Such resins are sold, for example, under the names Piccolyte A115 and S125 by the company Hercules or Zonarez 7100 or Zonatac 105 Lite by the company Arizona Chem.

Mention may also be made of certain modified resins such as hydrogenated resins, for instance those sold under the name Eastotac C6-C20 Polyolefm by the company Eastman Chemical Co., under the reference Escorez 5300 by the company Exxon Chemicals, or the resins Nevillac Hard or Nevroz sold by the company Neville Chem., the resins Piccofyn A- 100, Piccotex 100 or Piccovar AP25 sold by the company Hercules or the resin SP-553 sold by the company Schenectady Chemical Co.

According to a preferred embodiment, the hydrocarbon-based resin is chosen from indene hydrocarbon-based resins, aliphatic pentadiene resins, mixed resins of pentanediene and of indene, diene resins of cyclopentanediene dimers and diene resins of isoprene dimers, or mixtures thereof.

Preferably, the composition comprises at least one compound chosen from hydrocarbon-based resins as described previously, especially indene hydrocarbon-based resins and aliphatic pentadiene resins, or mixtures thereof. According to one preferred embodiment, the hydrocarbon-based resin is chosen from indene hydrocarbon-based resins.

According to a preferred embodiment, the hydrophobic film- forming polymer is a hydrocarbon-based resin, preferably an indene hydrocarbon-based resin, which is preferably hydrogenated, preferably derived from the polymerization of an indene monomer and of a monomer chosen from styrene, methylindene and methylstyrene, and mixtures thereof.

According to a preferred embodiment, the hydrocarbon-based resin is an indene resin chosen from hydrogenated indene/methylstyrene/styrene copolymers.

In particular, use may be made of indene/methylstyrene/hydrogenated styrene copolymers, such as those sold under the name Regalite by the company Eastman Chemical, such as Regalite R 1100, Regalite R 1090, Regalite R-7100, Regalite R 1010 Hydrocarbon Resin and Regalite R 1125 Hydrocarbon Resin.

A composition according to the invention may comprise a content of hydrocarbon-based resin(s) ranging from 1% to 20%, advantageously from 2% to 15% and especially from 2% to 10% by weight of active material relative to the total weight of the composition.

Preferably, in a composition according to the invention, the hydrocarbon-based resin(s) are present in a content ranging from 1% to 20%, advantageously from 2% to 15% and especially from 2% to 10% by weight of active material relative to the total weight of the composition.

NONVOLATILE OIL

According to one embodiment, the composition according to the invention may comprise a nonvolatile oil, or a mixture of nonvolatile oils, preferably chosen from optionally fluorinated silicone nonvolatile oils, hydrocarbon-based nonvolatile oils, and mixtures thereof.

According to a particular embodiment, the nonvolatile oil(s) are present in a total content of less than or equal to 10%, preferably less than 5% and especially less than 2% by weight relative to the total weight of said composition.

In a preferred embodiment, the composition contains less than 5% by weight, in particular less than 2% by weight and more particularly less than 1% by weight of nonvolatile oil(s), or even is free of nonvolatile oil(s).

The term "nonvolatile" refers to an oil whose vapor pressure at room temperature and atmospheric pressure is nonzero and is less than 0.02 mmHg (2.66 Pa) and better still less than 10^"3 mmHg (0.13 Pa).

Preferably, the composition according to the invention is liquid.

The term "liquid" refers to a composition that is capable of flowing under its own weight, at room temperature (20°C) and at atmospheric pressure (760 mmHg), as opposed to "solid" compositions.

SILICONE RESIN

The composition according to the invention advantageously comprises at least one silicone resin.

More generally, the term "resin" is understood to mean a compound, the structure of which is three-dimensional. "Silicone resins" are also referred to as "siloxane resins". Thus, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin. The nomenclature of silicone resins (also known as siloxane resins) is known under the name "MDTQ", the resin being described as a function of the various siloxane monomer units it comprises, each of the letters "MDTQ" characterizing a type of unit.

The letter M represents the monofunctional unit of formula RlR2R3SiOi/₂, the silicon atom being bonded to only one oxygen atom in the polymer comprising this unit.

The letter D means a difunctional unit RlR2Si0₂/₂ in which the silicon atom is bonded to two oxygen atoms.

The letter T represents a trifunctional unit of formula RlSi0₃/₂.

Such resins are described, for example, in the Encyclopedia of Polymer Science and Engineering, vol. 15, John Wiley and Sons, New York, (1989), pp. 265-270, and US 2 676 182, US 3 627 851, US 3 772 247, US 5 248 739 or else US 5 082 706, US 5 319 040, US 5 302 685 and US 4 935 484.

In the units M, D and T defined previously, R, namely Rl, R2 and R3, represents a hydrocarbon-based radical (especially alkyl) containing from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group.

Finally, the letter Q means a tetrafunctional unit Si0₄/₂ in which the silicon atom is bonded to four oxygen atoms, which are themselves bonded to the rest of the polymer. Various silicone resins with different properties may be obtained from these different units, the properties of these polymers varying as a function of the type of monomer (or unit), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the pendent chains. As silicone resins that may be used in the compositions according to the invention, use may be made, for example, of silicone resins of MQ type.

MQ resins

As examples of silicone resins of MQ type, mention may be made of the alkyl siloxysilicates of formula[(Rl)₃SiOi/₂]_x(Si0₄/₂)_y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group Rl represents a radical as defined previously, and is preferably an alkyl group containing from 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.

As examples of solid silicone resins of MQ type, mention may be made of the trimethyl siloxysilicate silicone resin, as sold under the reference SRI 000 by the company General Electric, under the reference TMS 803 by the company Wacker, or under the name KF-7312J by the company Shin-Etsu or DC 749 or DC 593 by the company Dow Corning.

Mention may also be made, as silicone resins comprising MQ siloxysilicate units, of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by the company General Electric). The preparation of such resins is described in particular in patent US 5 817 302.

Preferably, the composition comprises trimethyl siloxysilicate silicone resin.

According to a particular embodiment of the invention, the silicone resin is present in the composition in a resin solids content ranging from 2% to 15% by weight relative to the total weight of the composition, preferably ranging from 3% to 10% by weight relative to the weight of the composition.

PIGMENTS

The composition according to the invention may also comprise at least one pigment.

The term "pigments" means a pulverulent material, also known as a particulate material, formed from white or colored, mineral or organic particles, which are insoluble in an aqueous medium, and which are intended to color and/or opacify the resulting composition and/or film. These pigments may be white or colored, and mineral and/or organic.

These pigments are more particularly detailed below.

A composition according to the invention preferably contains from 1% to 30% by weight and preferentially from 5% to 20% by weight of these pigments, relative to the total weight of the composition.

According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments. The term "mineral pigment" means any pigment that satisfies the definition in Ullmann's encyclopaedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, and metal powders, for instance aluminum powder or copper powder. The following mineral pigments may also be used: Ta₂Os, T13O5, Ti₂0₃, TiO, Zr0₂ as a mixture with Ti0₂, Zr0₂, Nb₂0₅, Ce0₂, ZnS.

The size of the pigment that is useful in the context of the present invention is generally between 10 nm and 10 μιη, preferably between 20 nm and 5 μιη and more preferentially between 30 nm and 1 μιη.

In the context of the present invention, the mineral pigments are more particularly metal oxides, for instance iron oxide and titanium dioxide. SURFACE AGENT

The composition according to the invention may also comprise at least one hydrophobic surface agent.

For the purposes of the invention, a surface agent is a molecule that is capable of interacting with the surface of the pigment via a weak interaction, such as adsorption, or via a strong interaction, such as a chemical reaction.

The term "hydrophobic surface agent" means any lipophilic or hydrophobic compound which has interacted or which is interacting with the surface of the pigment(s).

The term "lipophilic compound" means any compound that is soluble or dispersible in an oily phase.

The term "hydrophobic compound" means any compound that is insoluble in water.

Without wishing to be bound to a particular theory, the presence of a hydrophobic surface agent in the composition makes it possible to disperse and stabilize the pigment(s) that may be present within the oily phase of the composition.

Preferably, the composition of the invention comprises at least one pigment as defined above, coated with at least one hydrophobic surface agent as defined below. A pigment coated with a hydrophobic surface agent is particularly advantageous insofar as it shows a predominant affinity for the oily phase of the composition which may then convey it.

For the purposes of the invention, a "coated pigment" according to the invention generally denotes a pigment that is totally or partially surface-treated with a surface agent, absorbed, adsorbed or grafted onto said pigment.

The surface-treated pigments may be prepared according to surface treatment techniques of chemical, electronic, chemical-mechanical or mechanical nature that are well known to those skilled in the art. Commercial products may also be used.

The surface agent may be absorbed, adsorbed or grafted onto the pigments by evaporation of solvent, chemical reaction and creation of a covalent bond.

According to one variant, the surface treatment is constituted of a coating of the pigments.

The coating may represent from 0.1% to 20% by weight and in particular from 0.5%) to 5%> by weight, relative to the total weight of the coated pigment.

A composition according to the invention preferably contains from 1% to 30% by weight and preferentially from 5% to 20% by weight of the combination of pigments and of coating agent, relative to the total weight of the composition. The coating may be performed, for example, by adsorption of a liquid surface agent onto the surface of the solid particles by simple mixing with stirring of the particles and of said surface agent, optionally with heating, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating may be performed, for example, by chemical reaction of a surface agent with the surface of the solid pigment particles and creation of a covalent bond between the surface agent and the particles. This method is especially described in patent US 4 578 266.

The chemical surface treatment may consist in diluting the surface agent in a volatile solvent, dispersing the pigments in this mixture and then slowly evaporating off the volatile solvent, so that the surface agent is deposited at the surface of the pigments. According to a particular embodiment of the invention, the surface agent of the composition of the invention is chosen from silicone surface agents; fluoro surface agents; fluorosilicone surface agents; metal soaps; N-acylamino acids or salts thereof; lecithin and derivatives thereof; isopropyl triisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

According to a more particular embodiment of the invention, the surface agent of the composition of the invention is chosen from silicone surface agents, in particular alkylsilanes and alkoxysilanes, especially triethoxycaprylylsilane; N-acylamino acids or salts thereof, in particular stearoyl glutamate; isopropyl triisostearyl titanate; and mixtures thereof.

Silicone surface agent

According to a particular embodiment, the hydrophobic surface agent is a silicone compound.

The silicone surface agents may be chosen from organopolysiloxanes and silane derivatives, and mixtures thereof.

The term "organopolysiloxane compound" means a compound having a structure comprising an alternance of silicon atoms and oxygen atoms and comprising organic radicals linked to silicon atoms. i) Non-elastomeric organopolysiloxane

Non-elastomeric organopolysiloxanes that may in particular be mentioned include polydimethylsiloxanes, polymethylhydrogenosiloxanes and poly alkoxy dimethy lsilo xanes .

The alkoxy group may be represented by the radical R-O- such that R represents methyl, ethyl, propyl, butyl or octyl, 2-phenylethyl, 2-phenylpropyl or 3,3,3- trifluoropropyl radicals, aryl radicals such as phenyl, tolyl or xylyl radicals, or substituted aryl radicals such as phenylethyl.

One method for surface-treating pigments with a polymethylhydrogenosiloxane consists in dispersing the pigments in an organic solvent and then in adding the silicone compound. On heating the mixture, covalent bonds are created between the silicone compound and the surface of the pigment. According to a preferred embodiment, the silicone surface agent may be a non- elastomeric organopolysiloxane, especially chosen from polydimethylsiloxanes. ii) Alkylsilanes and alkoxysilanes

Silanes bearing alkoxy functionality are especially described by Witucki in "A silane primer, Chemistry and applications of alkoxy silanes, Journal of Coatings Technology, 65, 822, pages 57-60, 1993".

Alkoxysilanes such as the alkyltriethoxysilanes and the alkyltrimethoxysilanes sold under the references Silquest A- 137 (OSI Specialities) and Prosil 9202 (PCR) may be used for coating the pigments.

Mention may also be made of the triethoxycaprylylsilane sold under the reference Unipure AS -EM (Sensient).

The use of alkylpolysiloxanes bearing a reactive end group such as alkoxy, hydroxyl, halogen, amino or imino is described in patent application JP H07- 196946. They are also suitable for treating the pigments.

Fluoro surface agent

According to a particular embodiment, the hydrophobic surface agent is a fluoro compound.

The fluoro surface agents may be chosen from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoropolyethylenes (PTFE), perfluoroalkanes, perfluoroalkyl silazanes, polyhexafluoropropylene oxides, and polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups.

The term "perfluoroalkyl radical" means an alkyl radical in which all of the hydrogen atoms have been replaced with fluorine atoms.

Perfluoropolyethers are described especially in patent application EP 0 486 135, and sold under the trade name Fomblin by the company Montefluos.

Perfluoroalkyl phosphates are in particular described in patent application JP H05-86984. The perfluoroalkyl diethanolamine phosphates sold by Asahi Glass under the reference AsahiGuard AG530 may be used.

Among the linear perfluoroalkanes that may be mentioned are perfluorocycloalkanes, perfluoro(alkylcycloalkanes), perfluoropolycycloalkanes, aromatic perfluoro hydrocarbons (perfluoroarenes) and hydrocarbon-based perfluoro organic compounds comprising at least one heteroatom.

Among the perfluoroalkanes, mention may be made of the linear alkane series such as perfluorooctane, perfluorononane or perfluorodecane.

Among the perfluorocycloalkanes and perfluoro(alkylcycloalkanes), mention may be made of perfluorodecalin sold under the name Flutec PP5 GMP by the company Rhodia, perfluoro(methyldecalin) and perfluoro(C3-C5 alky Icy clohexanes) such as perfluoro(butylcyclohexane).

Among the perfluoropolycycloalkanes, mention may be made of bicyclo[3.3.1]nonane derivatives such as perfluorotrimethylbicyclo[3.3.1]nonane, adamantane derivatives such as perfluorodimethyladamantane, and hydrogenated perfluorophenanthrene derivatives such as tetracosafluorotetradecahydrophenanthrene.

Among the perfluoroarenes, mention may be made of perfluoronaphthalene derivatives, for instance perfluoronaphthalene and perfluoromethyl-1 -naphthalene.

As examples of commercial references of pigments treated with a fluoro compound, mention may be made of:

- yellow iron oxide/perfluoroalkyl phosphate sold under the reference PF 5 Yellow 601 by the company Daito Kasei;

- red iron oxide/perfluoroalkyl phosphate sold under the reference PF 5 Red R 516L by the company Daito Kasei;

- black iron oxide/perfluoroalkyl phosphate sold under the reference PF 5 Black BL 100 by the company Daito Kasei;

- titanium dioxide/perfluoroalkyl phosphate sold under the reference PF 5 Ti0₂ CR 50 by the company Daito Kasei;

- yellow iron oxide/perfluoropolymethyl isopropyl ether sold under the reference

Yellow iron oxide BF-25-3 by the company Toshiki;

- DC Red 7/perfluoropolymethyl isopropyl ether sold under the reference D&C Red 7 FHC by the company Cardre Inc.;

- DC Red 6/PTFE sold under the reference T 9506 by the company Warner- Jenkinson. Fluorosilicone surface agent

According to a particular embodiment, the hydrophobic surface agent is a fluorosilicone compound.

The fluorosilicone compound may be chosen from perfluoroalkyl dimethicones, perfluoroalkyl silanes and perfluoroalkyl trialkoxysilanes.

Perfluoroalkyl silanes that may be mentioned include the products LP-IT and LP-4T sold by Shin-Etsu Silicone.

The perfluoroalkyl dimethicones may be represented by the following formula:

in which:

- R represents a linear or branched divalent alkyl group containing from 1 to 6 carbon atoms, preferably a divalent methyl, ethyl, propyl or butyl group;

- Rf represents a perfluoroalkyl radical containing 1 to 9 carbon atoms and preferably 1 to 4 carbon atoms;

- m is chosen between 0 and 150 and preferably from 20 to 100; and

- n is chosen between 1 and 300 and preferably from 1 to 100.

As examples of commercial references of pigments treated with a fluorosilicone compound, mention may be made of titanium dioxide/fluorosilicone sold under the reference Fluorosil Titanium dioxide 100TA by the company Advanced Dermaceuticals International Inc.

Other hydrophobic surface agents

According to a particular embodiment, the hydrophobic surface agent may also be chosen from:

i) metal soaps such as aluminum dimyristate and the aluminum salt of hydrogenated tallow glutamate;

Metal soaps that may especially be mentioned include metal soaps of fatty acids containing from 12 to 22 carbon atoms and in particular those containing from 12 to 18 carbon atoms. The metal of the metal soap may especially be zinc or magnesium.

Metal soaps that may be used include zinc laurate, magnesium stearate, magnesium myristate and zinc stearate, and mixtures thereof.

ii) fatty acids such as lauric acid, myristic acid, stearic acid and palmitic acid; iii) N-acylamino acids or salts thereof, which may comprise an acyl group containing from 8 to 22 carbon atoms, for instance a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group;

The amino acid may be, for example, lysine, glutamic acid or alanine.

The salts of these compounds can be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts.

Thus, according to a particularly preferred embodiment, an N-acylamino acid derivative may in particular be a glutamic acid derivative and/or a salt thereof, and more particularly a stearoyl glutamate, for instance aluminum stearoyl glutamate.

Examples of coated pigments according to the invention that may be mentioned more particularly include titanium dioxides and iron oxide coated with aluminum stearoyl glutamate, sold, for example, under the reference NAI by Miyoshi Kasei.

iv) lecithin and derivatives thereof;

v) isopropyl triisostearyl titanate;

As examples of isopropyl titanium triisostearate (ITT)-treated pigments, mention may be made of those sold under the commercial references BWBO-I2 (Iron oxide CI77499 and isopropyl titanium triisostearate), BWYO-12 (Iron oxide CI77492 and isopropyl titanium triisostearate) and BWRO-I2 (Iron oxide CI77491 and isopropyl titanium triisostearate) by the company Kobo.

vi) natural plant or animal waxes or polar synthetic waxes;

and mixtures thereof.

The waxes mentioned in the compounds mentioned previously may be those generally used in cosmetics, as defined hereinbelow.

They may especially be hydrocarbon-based, silicone and/or fluoro waxes, optionally comprising ester or hydroxyl functions. They may also be of natural or synthetic origin. A polar wax is especially formed from molecules comprising, besides carbon and hydrogen atoms in their chemical structure, heteroatoms (such as O, N and P).

Non-limiting illustrations of these polar waxes that may especially be mentioned include natural polar waxes, such as beeswax, lanolin wax, orange wax, lemon wax and Chinese insect waxes, rice bran wax, carnauba wax, candelilla wax, ouricury wax, cork fiber wax, sugarcane wax, Japan wax, sumac wax and montan wax.

According to a particular embodiment, the pigments may be coated with at least one compound chosen from silicone surface agents; N-acylamino acids or salts thereof; isopropyl triisostearyl titanate; and mixtures thereof.

According to a preferred embodiment, the pigments may be coated with a silicone surface agent, in particular an alkoxy silane such as triethoxycaprylylsilane.

According to another preferred embodiment, the pigments may be coated with an N-acylamino acid and/or a salt thereof, in particular with a glutamic acid derivative and/or a salt thereof, such as a stearoyl glutamate, for instance aluminum stearoyl glutamate.

According to another preferred embodiment, the pigments may be coated with isopropyl triisostearyl titanate. Needless to say, the compositions according to the invention may in parallel contain pigments not coated with a hydrophobic compound.

These other pigments may be coated with a hydrophilic compound or uncoated. These pigments may be mineral pigments especially as defined previously. These pigments may also be organic pigments, for example carbon black particles.

Thus, according to a preferred embodiment, the composition according to the invention comprises carbon black particles as pigments.

According to a preferred embodiment, a composition of the invention is in the form of a product for the eyelashes, in particular a mascara.

According to another embodiment, a composition of the invention may advantageously be in the form of a product for the eyebrows. Preferably, a composition according to the invention is in the form of a composition for caring for and/or making up keratin fibers, in particular the eyelashes, preferably in the form of a mascara.

According to a preferred embodiment, a composition of the invention is in the form of a product for the contour of the eyes or the eyelids, in particular a liner such as an eyeliner, in particular a makeup composition for the contour of the eyes or the eyelids.

Such compositions are especially prepared according to the general knowledge of a person skilled in the art. Throughout the description, including the claims, the term "comprising a" should be understood as being synonymous with "comprising at least one", unless otherwise specified.

The terms "between... and..." and "ranging from... to..." should be understood as being inclusive of the limits, unless otherwise specified.

In the description and the examples, the percentages are percentages by weight, unless otherwise indicated. The percentages are thus given on a weight basis relative to the total weight of the composition. The ingredients are mixed in the order and under conditions that are readily determined by a person skilled in the art.

EXAMPLES

Example 1 - Preparation of a particle dispersion

In a first step, 1300 g of isododecane, 337 g of isobornyl acrylate, 28 g of methyl acrylate and 3.64 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21 S from Akzo) were placed in a reactor. The isobornyl acrylate/methyl acrylate mass ratio is 92/8. The mixture was heated to 90°C under argon with stirring.

After 2 hours of reaction, 1430 g of isododecane were added to the reactor feedstock and the mixture was heated to 90°C.

In a second step, a mixture of 1376 g of methyl acrylate, 1376 g of isododecane and 13.75 g of Trigonox 21 S were run in over 2 hours 30 minutes, and the mixture was left to react for 7 hours. 3.3 liters of isododecane were then added and part of the isododecane was evaporated off to obtain a solids content of 50% by weight.

A dispersion of methyl acrylate particles stabilized with a statistical copolymer stabilizer containing 92% isobornyl acrylate and 8% methyl acrylate in isododecane was obtained.

The oily dispersion contains in total (stabilizer + particles) 80% methyl acrylate and 20% isobornyl acrylate.

The polymer particles of the dispersion have a number-average size of about 160 run.

The dispersion is stable after storage for 7 days at room temperature (25°C). Example 2 - Preparation of a particle dispersion

A dispersion of polymer in isododecane was prepared according to the preparation method of Example 1, using:

Step 1 : 315.2 g of isobornyl acrylate, 12.5 g of methyl acrylate, 12.5 g of ethyl acrylate, 3.4 g of Trigonox 21, 540 g of isododecane, 360 g of ethyl acetate; followed by addition, after reaction, of 540 g of isododecane and 360 g of ethyl acetate.

Step 2: 145 g of methyl acrylate, 934 g of ethyl acrylate, 157 g of acrylic acid, 12.36 g of Trigonox 21S, 741.6 g of isododecane and 494.4 g of ethyl acetate. After reaction, addition of 3 liters of an isododecane/ethyl acetate mixture (60/40 weight/weight) and total evaporation of the ethyl acetate and partial evaporation of the isododecane to obtain a solids content of 44% by weight.

A dispersion in isododecane of methyl acrylate/ethyl acrylate/acrylic acid (11.7/75.6/12.7) copolymer particles stabilized with an isobornyl acrylate/methyl acrylate/ethyl acrylate (92/4/4) statistical copolymer stabilizer was obtained.

The oily dispersion contains in total (stabilizer + particles) 10% acrylic acid, 10% methyl acrylate, 60% ethyl acrylate and 20% isobornyl acrylate.

The dispersion is stable after storage for 7 days at room temperature (25°C).

Example 3 - Preparation of mascara compositions

The formulations (corresponding to a mascara) in accordance with the invention (compositions 1 and 2) or not in accordance with the invention (compositions 3 to 5) are prepared as described below.

The compositions were prepared in a mini reactor.

The aqueous phase and the hexamethyl diisocyanate/a,co-polyoxyethylene- terminated polyethylene glycol copolymer are first introduced, followed by addition of all the other components, except for the alcohol.

The mixture is heated to 75°C.

It is then dispersed at 4500 rpm at 75°C, for 15 minutes.

The mixture is then cooled to 25°C.

The alcohol is finally added, and the combined mixture is then mixed for 5 minutes.

Formula Formula

Formula Formula Formula 1 2

3 outside 4 outside 5 outside according according

the the the to the to the

invention invention invention invention invention

Isododecane {Isododecane sold by Ineos) 7.50% 6.50% 7.50% 7.50% 7.50%

(Methyl acrylate)-co-(ethyl acrylate)-co-(acrylic acid)-co- (isobornyl acrylate) copolymer (10/60/20/10) at 50% in 30.12% 29.12% 30.12% 30.12% 30.12% isododecane (oily dispersion according to Example 2)

Styrene/ethylene-propylene diblock copolymer (37/63)

3.69% 3.69% 3.69% 3.69% 3.69% (Kraton G1701 EU SQR 1111 sold by Kraton Polymer)

Hydrogenated styrene/methylstyrene/indene copolymer

(Regalite R1100 CH Hydrocarbon Resin sold by Eastman 3.94% 3.94% 3.94% 3.94% 3.94% Chemical)

Black iron oxide (CI 77499) treated with isopropyl

11.40% 11.40% 11.40% 11.40% 11.40% titanium triisostearate (BWBO-I2 sold by Kobo)

Copolymer of polyethylene glycol (30 EO) and of 12- hydroxystearic acid (PEG-1500:30 EO

3% 5%

dipolyhydroxystearate) (Cithrol DPHS-SO-(MV) sold by

Croda)

PEG-20 Glyceryl triisostearate (Shu) (Uniox GT 20IS L

3%

sold by NOF Corporation)

12-Hydroxystearic acid (12 Hydroxy stearic acid Premium

3%

Grade 12H-P sold by Thai Kawaken)

Glyceryl stearate (Tegin M Pellets sold by Evonik

3% Goldschmidt)

Microbiologically clean deionized water 30.50% 30.50% 30.50% 30.50% 30.50%

Hexamethyl diisocyanate/ α,ω-polyoxyethylene- terminated polyethylene glycol copolymer (Rheoluxe 811 4.10% 4.10% 4.10% 4.10% 4.10% sold by Elementis)

1,2-Pentanediol (616751 Hydrolite-5 sold by Symrise) 4% 4% 4% 4% 4%

2-Phenoxyethanol (Sepicide LD sold by SEPPIC) 0.85% 0.85% 0.85% 0.85% 0.85%

Denatured absolute ethyl alcohol (sold by Belgalco) 0.90% 0.90% 0.90% 0.90% 0.90%

Example 3 - Measurements performed and results 1. Gloss measurement protocol

The gloss of compositions 1 to 5 was measured using a Byk spectro-guide sphere gloss glossmeter.

Principle The machine illuminates the sample to be analyzed at a certain incidence and measures the intensity of the specular reflection.

The intensity of the reflected light depends on the material and on the angle of illumination. For non-ferrous materials (paint, plastic), the intensity of reflected light increases with the angle of illumination. The rest of the incident light penetrates the material and, depending on the shade of the color, is either partly absorbed or scattered.

The reflectometer measurement results are not based on the amount of incident light but on a polished black glass standard of defined refractive index.

The measurement is normalized relative to an internal standard and brought to a value out of 100: for this calibration standard, the measurement value is set at 100 gloss units (calibration).

The closer the measured value is to 100, the more glossy the sample. The measurement unit is the Gloss Unit (GU).

The angle of illumination used has a strong influence on the reflectometer value. In order to be able to readily differentiate very glossy and matt surfaces, the standardization has defined 3 geometries or 3 measurement domains.

Test protocol

a- Spread a coat with a wet thickness of 300 μιη of the composition whose mean gloss value it is desired to evaluate onto a Leneta brand contrast card of reference Form 1 A Penopac, using an automatic spreader. The coat covers the white background and the black background of the card.

b - Leave to dry for 24 hours at 37°C.

c- Measure the gloss at 60° or at 20° on the white matt absorbent background (3 measurements) using a Byk Gardner brand glossmeter of reference spectro-guide sphere gloss.

The measured values in GU obtained for the various test compositions should then be compared. The lower the value measured, the more matt the deposit. 2. Black intensity measurement protocol

L * Colorimetric results

The coloring obtained with compositions 1 to 5 is evaluated visually and read on a Minolta spectrocolorimeter (CM3700d, illuminant D65, angle 10°, SCI values) for the L* colorimetric measurements. In an L* a* b* system, the lower the value of L*, the darker the color.

3. Results

The results are collated in the table below.

The gloss performance qualities are largely improved for compositions 1 and 2 in accordance with the invention, unlike the tested comparative compositions 3 to 5.

In addition, the black color intensity is advantageously greater for compositions 1 and 2 according to the invention, compared with compositions 3 to 5.

Examples 4 and 5 (according to the invention) and examples 6 and 7 (outside the invention) - Preparation of particle dispersions

Several oily dispersions of polymethyl acrylate with a stabilizer containing isobornyle and optionally methyl acrylate were prepared, according to the preparation method of Example 1, by varying the mass ratio of isobornyl acrylate and methyl acrylate and observing the stability of the dispersion obtained as a function of the chemical constitution of the stabilizer. All the dispersions comprise in total (stabilizer + particles) 80% methyl acrylate and 20% isobornyl acrylate.

Example 4:

Step 1 : 50g of isobornyle acrylate, 0.5g Trigonox 21, 96g of isododecane; followed by addition, after reaction, of 80g of isododecane.

Step 2: 200g of methyl acrylate, 2g of Trigonox 21S, 200g of isododecane. After reaction, addition of 80g of isododecane and evaporation to obtain a solids content of 31%) by weight.

A dispersion in isododecane of polymethyl acrylate particles stabilized with a polyisobornyl acrylate stabilizer was obtained.

Example 5 :

Step 1 : 48.5g of isobornyle acrylate, 8.5g of methyl acrylate, 0.57g Trigonox 21, 115g of isododecane; followed by addition, after reaction, of 75g of isododecane.

Step 2: 185.5g of methyl acrylate, 1.85g of Trigonox 21S, 185.5g of isododecane. After reaction, addition of 75g of isododecane and evaporation to obtain a solids content of 31% by weight.

A dispersion in isododecane of polymethyl acrylate particles stabilized with an isobornyl acrylate/methyl acrylate (85/15) statistical copolymer stabilizer was obtained.

Example 6 (outside the invention):

Step 1 : 48.5g of isobornyle acrylate, 12g of methyl acrylate, 0.6g Trigonox 21, 115g of isododecane; followed by addition, after reaction, of 60g of isododecane.

Step 2: 182g of methyl acrylate, 1.82g of Trigonox 21S, 182g of isododecane.

After reaction, addition of 60g of isododecane and evaporation to obtain a solids content of 31%) by weight.

A dispersion in isododecane of polymethyl acrylate particles stabilized with an isobornyl acrylate/methyl acrylate (80/20) statistical copolymer stabilizer was obtained. Example 7 (outside the invention):

Step 1 : 48.5g of isobornyle acrylate, 21g of methyl acrylate, 0.7g Trigonox 21, 130g of isododecane; followed by addition, after reaction, of 65g of isododecane.

Step 2: 173g of methyl acrylate, 1.73g of Trigonox 21S, 173g of isododecane. After reaction, addition of 65g of isododecane and evaporation to obtain a solids content of 31% by weight.

A dispersion in isododecane of polymethyl acrylate particles stabilized with an isobornyl acrylate/methyl acrylate (70/30) statistical copolymer stabilizer was obtained.

The stability 12 hours after the end of the synthesis of the oily dispersions of polymethyl acrylate of Examples 1, 4, 5, 6 and 7 was compared, and the following results were obtained.

The results obtained show that the dispersions of polymethyl acrylate in isododecane are stable when the stabilizer is an isobornyl acrylate homopolymer or an isobornyl acrylate/methyl acrylate copolymer with an isobornyle acrylate weight ratio > 80/20.

Claims

1. A composition, especially a cosmetic composition, for caring for and/or making up keratin materials, comprising:

- at least one volatile hydrocarbon-based oil,

- at least one hydrophobic film- forming polymer,

- at least one aqueous phase, and

2. The composition as claimed in claim 1 , in which the surfactant chosen from esters of polyhydroxylated fatty acid and of polyoxyalkylene glycol is a fatty acid ester of polyethylene glycol, and is preferably polyethylene glycol dipolyhydroxystearate containing 30 EO.

3. The composition as claimed in either of claims 1 and 2, comprising at least 0.5%, preferably at least 1%, even more particularly between 0.5% and 10%, even more particularly between 1% and 8% and better still between 1% and 5% by weight of surfactant(s) chosen from esters of fatty acid and of polyoxyalkylene glycol, relative to the total weight of the composition.

4. The composition as claimed in any one of claims 1 to 3, in which the aqueous phase comprises water and a water-soluble solvent.

5. The composition as claimed in any one of claims 1 to 4, in which the aqueous phase is present in a content ranging from 10% to 50% by weight relative to the total weight of the composition, preferably ranging from 20% to 50% by weight and more preferentially in a content ranging from 25% to 45% by weight relative to the total weight of the composition.

6. The composition as claimed in any one of claims 1 to 5, in which the polymer of the particles is a methyl (meth)acrylate and/or ethyl (meth)acrylate polymer, more preferentially a methyl acrylate and/or ethyl acrylate polymer.

7. The composition as claimed in any one of claims 1 to 6, in which the stabilizer is a statistical copolymer of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate weight ratio of greater than or equal to 5.

8. The composition as claimed in any one of claims 1 to 7, in which the stabilizer is chosen from the group formed by:

- isobornyl acrylate homopolymers,

- statistical copolymers of isobornyl acrylate/methyl acrylate,

- statistical copolymers of isobornyl methacrylate/methyl acrylate.

9. The composition as claimed in any one of claims 1 to 8, in which the particles are introduced into the composition in the form of a dispersion of particles of at least one surface-stabilized polymer, in an oily medium, containing at least one hydrocarbon-based oil, said hydrocarbon-based oil being identical to or different from the hydrocarbon-based volatile oil, preferably identical.

10. The composition as claimed in claim 9, in which the hydrocarbon-based oil is present in the composition in a content ranging from 10% to 50%, preferably from 15% to 45% and preferentially from 15% to 40% by weight relative to the total weight of the composition, the hydrocarbon-based volatile oil(s) preferably being apolar, even more preferentially containing from 8 to 16 carbon atoms, or better still being isododecane.

11. The composition as claimed in any one of claims 1 to 10, in which said composition comprises from 5% to 25%, preferably from 8% to 25% and more preferentially from 10% to 20% by weight of polymer particles, relative to the total weight of said composition (content expressed as solids).

12. The composition as claimed in any one of claims 1 to 11, in which the hydrophobic film-forming polymer is chosen from hydrocarbon-based block copolymers and hydrocarbon-based resins, and mixtures thereof.

13. The composition as claimed in any one of claims 1 to 12, in which the hydrophobic film-forming polymer is a hydrocarbon-based block copolymer, preferably a diblock copolymer, which is preferably hydrogenated, preferably chosen from styrene- ethylene/propylene copolymers, styrene-ethylene/butadiene copolymers and styrene- ethylene/butylene copolymers, and is preferably a styrene-ethylene/propylene diblock copolymer.

14. The composition as claimed in claim 12 or 13, characterized in that the hydrocarbon-based block copolymer(s) are present in the composition in a content ranging from 0.5% to 15% by weight relative to the total weight of the composition, preferably ranging from 1% to 10% by weight and even more advantageously from 2% to 8% by weight relative to the total weight of the composition.

15. The composition as claimed in any one of claims 1 to 14, in which the hydrophobic film-forming polymer is a hydrocarbon-based resin, preferably an indene hydrocarbon-based resin, which is preferably hydrogenated, preferably derived from the polymerization of an indene monomer and of a monomer chosen from styrene, methylindene and methylstyrene, and mixtures thereof.

16. The composition as claimed in any one of claims 12 to 15, in which the hydrocarbon-based resin is an indene resin chosen from hydrogenated indene/methy lstyrene/ styrene copolymers .

17. The composition as claimed in any one of claims 12 to 16, in which the hydrocarbon-based resin(s) are present in a content ranging from 1% to 20%, advantageously from 2% to 15%, or even from 2% to 10%, by weight of active material, relative to the total weight of the composition.

18. The composition as claimed in any one of claims 1 to 17, characterized in that it contains less than 5% by weight, in particular less than 2% by weight and more particularly less than 1% by weight of nonvolatile oil(s), or even is free of nonvolatile oil(s).

19. The composition as claimed in any one of claims 1 to 18, characterized in that it has a viscosity at 25°C of between 0.5 and 50 Pa.s, measured at a room temperature of 25°C using a Rheomat RM100^® machine.

20. The composition as claimed in any one of claims 1 to 19, characterized in that it has a solids content of greater than or equal to 30%>, preferably 35%, in particular 40%>, or even 42%, and preferentially 45%.

21. The composition as claimed in any one of claims 1 to 20, characterized in that it is a mascara.

22. A cosmetic process for making up and/or caring for keratin materials, comprising at least one step which consists in applying to said keratin materials a composition as defined according to any one of claims 1 to 21.