FR2968978A1 - Eyeliner composition, useful for make up the lower and/or upper eyelids, comprises a particulate phase comprising coloring agent, solid particles aqueous dispersion of film-forming polymer, and a lipophilic plasticizer - Google Patents

Abstract

Eyeliner composition comprises: a particulate phase comprising: (i) at least one coloring agent; (ii) at least one solid particles aqueous dispersion of at least one film-forming polymer; and a lipophilic plasticizer, where the filmforming polymer is present at >= 20 wt.% of the composition. An independent claim is included for a set for make up of contours skin of eye comprising: an applicator, and the eyeliner composition disposed within a container.

Description

The present invention relates to an eyeliner composition. Such a composition is intended to be applied to the lower and / or upper eyelids in order to emphasize the look. Consumers usually look for eyeliner compositions, gloss, color intensity and good holding properties, especially water. However, the eyeliner compositions formulated in aqueous phase generally have a water resistance defect, and lack shine (satin line). The eyeliner compositions formulated anhydrally generally have a good performance but have the disadvantage of being dull. An object of the invention is therefore to provide an eyeliner composition combining water resistance, color intensity and gloss. The subject of the present invention is therefore, according to a first aspect, an eyeliner composition comprising: a particulate phase comprising: i) at least one coloring agent, ii) at least one aqueous dispersion of solid particles of at least one polymer film-forming, - a lipophilic plasticizer, wherein said film-forming polymer is present at a solids content greater than or equal to 20% by weight relative to the total weight of said composition. Another object of the invention is therefore to provide an assembly for an application of an eyeliner composition allowing a precise and rapid makeup while obtaining a brilliant line, good color intensity and good performance. In particular, the line obtained may have good homogeneity, in particular the color generated is uniform and the makeup obtained uniform, smooth and regular. The subject of the present invention is therefore, according to a second aspect, an assembly intended to condition and apply such a composition, comprising an eyeliner composition as defined above.

The subject of the invention is, according to a third aspect, a process for making up the lower and / or upper eyelids, comprising at least one step of applying to said eyelids a composition as defined above.

Particulate Phase The particulate phase, or pulverulent phase, according to the invention comprises, or even consists mainly of, at least one coloring agent and at least one aqueous dispersion of solid particles of at least one film-forming polymer.

These dyestuffs are preferably chosen from at least one pigment, in order to provide a colored appearance to compositions intended for making up the skin and in particular the eyelids. However, the particulate phase may also comprise other types of particles, for example chosen from fillers.

The particulate phase is preferably present in a composition according to the invention at a content greater than or equal to 21% by weight relative to the total weight of the composition, better still ranging from 25% to 60% by weight, in particular ranging from 30% to 50% by weight, relative to the total weight of the composition.

Staining Agents The coloring agent, or dyestuff, aims in particular to provide a colored appearance to the compositions useful for the makeup of the skin. The coloring agent is preferably chosen from pigments, pearlescent agents, reflective particles and their mixtures, more preferably from the pigments, preferably inorganic pigments. This coloring agent, and preferably the pigments, may represent at least 5% by weight, relative to the total weight of the compounds of the particulate phase, and more particularly, may represent, inclusive limits, between 10 and 50% by weight, relative to the total weight of the compounds of the particulate phase. Pigments By "pigments" it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, mention may be made of carbon black, titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or of chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder, and preferentially carbon black. The organic pigments can be chosen from the following materials and their mixtures: - cochineal carmine, - organic pigments of azo, anthraquinone, indigo, xanthene, pyrenic, quinoline, triphenylmethane, fluorane dyes. Among the organic pigments, mention may be made of the D & C-certified pigments known under the following names: D & C Blue No. 4, D & C Brown No. 1, D & C Green No. 5, D & C Green No. 6, D & C Orange No. 4, D & C Orange # 5, D & C Orange # 10, D & C Orange # 11, D & C Red # 6, D & C Red # 7, D & C Red # 17, D & C Red # 21, D & C Red # 22, D & C Red n ° 27, D & C Red No. 28, D & C Red No. 30, D & C Red No. 31, D & C Red No. 33, D & C Red No. 34, D & C Red No. 36, D & C Violet No. 2, D & C Yellow No. 7 , D & C Yellow No. 8, D & C Yellow No. 10, D & C Yellow No. 11, FD & C Blue No. 1, FD & C Green No. 3, FD & C Red No. 40, FD & C Yellow No. 5, FD & C Yellow No. 6. The The chemical materials corresponding to each of the above-mentioned organic dyestuffs are referred to in International Cosmetic Ingredient Dictionary and Handbook, Edition 1997, pages 371 to 386 and 524 to 528, published by The Cosmetic, Toiletry, and Fragrance Association. whose content is incorporated in the this request by reference. A composition according to the invention may comprise a pigment content ranging from 1% to 20% by weight, relative to the total weight of the composition, preferably ranging from 2% to 18% by weight, and preferably ranging from 3% to 10% by weight relative to the total weight of the composition.

Nacres "Nacres" means colored particles of any shape, iridescent or not, in particular produced by certain shellfish or synthesized and which exhibit a color effect by optical interference.

Examples of pearlescent agents that may be mentioned are pearlescent pigments such as iron oxide-coated titanium mica, bismuth oxychloride-coated mica, chromium oxide-coated titanium mica, pearlescent dye-based pigments. bismuth oxychloride. It may also be mica particles on the surface of which are superimposed at least two successive layers of metal oxides and / or organic dyestuffs. The nacres may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or coppery reflection. As an illustration of the nacres that can be introduced into the composition, mention may be made of gold-colored mother-of-pearl sold by the company Engelhard under the name Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); bronze nacres sold especially by the company Merck under the name Bronze Fine (17384) (Colorona) and Bronze (17353) (Colorona) and by Engelhard under the name Super Bronze (Cloisonne); orange nacres sold especially by the company Engelhard under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the name Passion Orange (Colorona) and Matte Orange (17449) (Microna); brown-colored pearlescent agents marketed by Engelhard under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); nacres with a copper sheen sold especially by Engelhard under the name Copper 340A (Timica); the nacres with a red glint sold especially by MERCK under the name Sienna fine (17386) (Colorona); yellow-colored pearlescent agents marketed by ENGELHARD under the name Yellow (4502) (Chromalite); the red-colored pearlescent agents with a gold glint sold especially by ENGELHARD under the name Sunstone G012 (Gemtone); pink nacres sold especially by Engelhard under the name Tan opal G005 (Gemtone); the black nacres with gold reflection sold by the company Engelhard under the name Nu antique bronze 240 AB (Timica), the blue nacres sold especially by the company Merck under the name Matte Blue (17433) (Microna), the white nacres with reflection silver sold in particular by the company Merck under the name Xirona Silver and the golden-green orange-colored mother-of-pearl marketed by Merck under the name Indian summer (Xirona) and their mixtures. Still as examples of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

Particles with a glass substrate coated with titanium oxide are especially sold under the name METASHINE ™ 1080RY by the company TOYAL. Finally, examples of nacres that may be mentioned include polyethylene terephthalate flakes, especially those marketed by Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes).

The compositions according to the invention are preferably free of nacres. Alternatively, they may comprise from 0.1 to 15%, for example from 0.5 to 10%, better from 1 to 5% by weight of nacres, relative to the total weight of the composition. In particular, they may comprise a content of less than or equal to 15% by weight of nacres relative to the total weight of the composition.

Reflective particles "Reflective particles" means particles whose size, structure, in particular the thickness of the layer or layers constituting it and their physical and chemical natures, and the surface state, enable them to reflect the incident light.

This reflection can, if necessary, have sufficient intensity to create on the surface of the composition or mixture, when it is applied to the support to make up, highlight points visible to the naked eye is ie brighter points that contrast with their surroundings while appearing to shine. The reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them and more particularly to optimize this effect in terms of color rendering. They may more particularly have a color or a yellow, pink, red, bronze, orange, brown, gold and / or coppery reflection. These particles may have various forms, in particular be in the form of platelets or globular, in particular spherical.

The reflective particles, whatever their shape, may have a multilayer structure or not and, in the case of a multilayer structure, for example at least one layer of uniform thickness, especially a reflective material. When the reflective particles do not have a multilayer structure, they may be composed for example of metal oxides, including synthetically obtained titanium or iron oxides. When the reflective particles have a multilayer structure, these may for example comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, in particular at least one metal or metal material. . The substrate may be monomaterial, multimaterial, organic and / or inorganic. More particularly, it may be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and mixtures thereof, this list not being limiting.

The reflective material may include a layer of metal or a metallic material. Reflective particles are described in particular in JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710. Still as an example of reflective particles comprising a mineral substrate coated with a metal layer, there may also be mentioned particles comprising a borosilicate substrate coated with silver. Particles with a silver-coated glass substrate, in the form of platelets, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Particles with a glass substrate coated with a nickel / chromium / molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by the same company.

Particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium steel, bronze, titanium, said substrate being coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, oxide cerium, chromium oxide, silicon oxides and mixtures thereof. By way of example, mention may be made of aluminum, bronze or copper powders coated with SiO 2 sold under the name VISIONAIRE by the company ECKART.

Charges "Charges" means colorless or white, solid particles of all shapes, which are in an insoluble form and dispersed in the medium of the composition. Mineral or organic nature, they allow to confer the composition of softness, dullness and uniformity to make-up. The fillers used in the compositions according to the present invention may be of lamellar, globular, spherical, fiber or any other intermediate form between these defined forms. The fillers according to the invention may or may not be superficially coated, and in particular they may be surface-treated with silicones, amino acids, fluorinated derivatives or any other substance which promotes dispersion and compatibility of the filler in the process. composition. Among the mineral fillers that may be used in the compositions according to the invention, mention may be made of talc, mica, silica, magnesium aluminum silicate, trimethyl siloxysilicate, kaolin, bentone and calcium carbonate. magnesium hydrogen carbonate, hydroxyapatite, boron nitride, hollow silica microspheres (Silica Beads from Maprecos), glass or ceramic microcapsules, silica-based fillers such as Aerosil 200, Aerosil 300; Sunsphere H-33, Sunsphere H-51 marketed by Asahi Glass; Chemicelen marketed by Asahi Chemical; silica and titanium dioxide composites, such as the TSG series marketed by Nippon Sheet Glass, perlite powders, fluorphlogopite, and mixtures thereof.

Among the organic fillers that can be used in the compositions according to the invention, mention may be made of polyamide powders (Nylon Orgasol from Atochem), poly-b-alanine and polyethylene, powders of polytetrafluoroethylene (Teflon), lauroyl-lysine, starch, tetrafluoroethylene polymer powders, hollow microspheres of polymers, for example comprising an (alkyl) acrylate, such as EXPANCEL® (NOBEL INDUSTRIE), metal soaps derived from organic carboxylic acids having from 8 to 22 atoms carbon, preferably from 12 to 18 carbon atoms, for example, zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate, Polypore® L 200 (Chemdal Corporation), microbeads silicone resin (for example Toshiba Tospearl®), polyurethane powders, in particular, cross-linked polyurethane powders comprising a copolymer, said copolymer comprising trimethylol hexylact one, like the polymer of hexamethylene diisocyanate / trimethylol hexyllactone, marketed under the name PLASTIC POWDER D-400® or PLASTIC POWDER D-800® by the company TOSHIKI, the Carnauba microcires, such as that marketed under the name of MicroCare 350® by the company MICRO POWDERS, synthetic wax microwaxes, such as that marketed under the name MicroEase 1145® by the company MICRO POWDERS, the micro-waxes consisting of a mixture of Carnauba wax and polyethylene wax, such as those marketed under the names Micro Care 300® and 310® by the company MICRO POWDERS, the micro-waxes consisting of a mixture of Carnauba wax and synthetic wax, such as that sold under the name Micro Care 325® by the company MICRO POWDERS company, polyethylene microwaxes, such as those marketed under the names Micropoly 200®, 220®, 2 20L® and 2505® by MICRO POWDERS, fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or organized, for example braided, hollow or full. Their shape can be any and in particular of circular or polygonal section (square, hexagonal or octagonal) depending on the specific application envisaged. In particular, their ends are blunt and / or polished to avoid injury. the fibers have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm. Their cross section may be in a circle with a diameter ranging from 2 nm to 500 μm, preferably ranging from 100 nm to 100 μm and better still from 1 μm to 50 μm. As fibers that can be used in the compositions according to the invention, mention may be made of non-rigid fibers such as polyamide (nylon) fibers or rigid fibers such as polyimide-amide fibers, such as those sold under the names KERMEL®, KERMEL TECH® by RHODIA or poly- (p-phenylene-terephthalamide) (or aramid) sold especially under the name Kevlar® by DuPont de Nemours, and mixtures thereof. As representative of such fillers used preferably in the context of the present invention, mention may in particular be made of talc, starch, fluorophlogopite, clays, such as magnesium aluminum silicate, or the like. hollow microspheres of polymer. The compositions according to the invention are preferably free of fillers. Alternatively, the fillers may be present in the composition in a content ranging from 0.1% to 10% by weight, and preferably from 0.5% to 8%, relative to the total weight of the composition.

Film-forming polymers The composition according to the invention comprises at least one aqueous dispersion of solid particles formed of one or more film-forming polymers.

In the present application, the term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous film on a support, at a temperature ranging from 20 ° C. to 150 ° C. C. Such a film-forming polymer present in the form of particles in aqueous dispersion, are generally called (pseudo) latex, that is to say latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

A dispersion suitable for the invention may comprise one or more types of particles, these particles being able to vary in size, structure and / or chemical nature. The eyeliner compositions according to the invention comprise a content of such dispersions greater than or equal to 20% by weight of film-forming polymer solids, relative to the total weight of the composition, preferably a content ranging from 22 to 45% by weight, and in particular from 24 to 40% and better still from 25 to 35% by total weight of film-forming polymer solids, relative to the total weight of the composition.

These dispersions may represent at least 50% by weight of dry matter of film-forming polymer, relative to the total weight of the compounds of the particulate phase, and more particularly, may represent, inclusive limits, between 60 and 95% by weight, relative to total weight of the compounds of the particulate phase.

These solid particles may be of anionic, cationic or neutral nature and may constitute a mixture of solid particles of different natures. In the present invention, the term "aqueous" means a liquid medium based on water and / or hydrophilic solvents. This aqueous liquid medium may consist essentially of water. It may also comprise a mixture of water and organic solvent (s) miscible with water (miscibility in water greater than 50% by weight at 25 ° C) such as lower monoalcohols having 1 to 5 carbon atoms such as ethanol, isopropanol, glycols having 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, C3-C4 ketones, C2-C4 aldehydes.

Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. In general, these polymers may be random polymers, block copolymers of type A-B, multi-block A-B-A or alternatively ABCD ..., or even graft polymers.

Radical Film-forming Polymer By "radical polymer" is meant a polymer obtained by polymerization of unsaturated monomers, especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates).

The radical-type film-forming polymers may in particular be homopolymers or copolymers, acrylic and / or vinylic.

The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acidic group and / or esters of these acidic monomers and / or amides of these acidic monomers. As ethylenically unsaturated monomers having at least one acidic group or monomer carrying an acid group, unsaturated α, β-ethylenic carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, in particular (meth) acrylic acid and crotonic acid, and more particularly (meth) acrylic acid, the acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), especially (meth) acrylates of alkyl, in particular of C1-C20 alkyl, more particularly of C1-C8, aryl (meth) acrylates , especially C 6 -C 10 aryl, hydroxyalkyl (meth) acrylates, in particular C 2 -C 6 hydroxyalkyl, Among the alkyl (meth) acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate. Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate. The esters of (meth) acrylic acid are in particular alkyl (meth) acrylates. According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms. Amides of the acidic monomers include, for example, (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular C 2 -C 12 alkyl. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, N-t-butyl acrylamide and N-t-octyl acrylamide.

The vinyl film-forming polymers can also result from the homopolymerization or copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above. Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. Styrene monomers include styrene of alpha-methyl styrene. The list of monomers given is not limiting and it is possible to use any monomer known to those skilled in the art falling into the categories of acrylic and vinyl monomers (including monomers modified with a silicone chain). As the vinyl polymer, the silicone acrylic polymers can also be used. Mention may also be made of the polymers resulting from the radical polymerization of one or more radical monomers, inside and / or partially on the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes and polyureas. polyesters, polyesteramides and / or alkyds. These polymers are generally called "hybrid polymers".

Polycondensates As polycondensate-type film-forming polymers, mention may be made of anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyureas and polyureas. polyurethanes, silicone polyurethanes, and mixtures thereof. The film-forming polyurethane may be, for example, a polyurethane, polyurea / urethane or polyurea, aliphatic, cycloaliphatic or aromatic copolymer, comprising, alone or as a mixture, at least one sequence chosen from: a sequence of aliphatic polyester origin and / or cycloaliphatic and / or aromatic, and / or - a silicone sequence, branched or unbranched, for example polydimethylsiloxane or polymethylphenylsiloxane, and / or - a sequence comprising fluorinated groups. The film-forming polyurethanes as defined in the invention may also be obtained from branched or unbranched polyesters or from alkyds containing mobile hydrogens which are modified by reaction with a diisocyanate and a bifunctional organic compound (for example dihydro , diamino or hydroxyamino), further comprising either a carboxylic acid or carboxylate group, or a sulfonic acid or sulfonate group, or a tertiary amine neutralizable group or a quaternary ammonium group. Among the film-forming polycondensates, mention may also be made of polyesters, polyester amides, fatty-chain polyesters, polyamides, and epoxy ester resins. The polyesters can be obtained, in known manner, by polycondensation of dicarboxylic acids with polyols, especially diols. The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-acid. dimethylgluratic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-acid, cyclohexanedicarbocylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norborane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid. These dicarboxylic acid monomers may be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are chosen in particular. The diol may be chosen from aliphatic, alicyclic and aromatic diols. In particular, a diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol and 4-butanediol is used. As other polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylolpropane.

The polyester amides can be obtained in a similar manner to the polyesters by polycondensation of diacids with diamines or amino alcohols. As the diamine, there can be used ethylenediamine, hexamethylenediamine, meta or para-phenylenediamine. As aminoalcohol, monoethanolamine can be used.

Polymer of natural origin It is possible to use in the present invention polymers of natural origin, which may be modified, such as shellac resin, sandarac gum, dammars, elemis, copals, water-insoluble cellulosic polymers, for example nitrocellulose, modified cellulose esters including carboxyalkyl cellulose esters such as those described in patent application US 2003/185774, and mixtures thereof. According to a particular embodiment of the invention, said at least one film-forming polymer in the dispersed state is chosen from acrylic polymer dispersions, polyurethane dispersions, sulfopolyesters dispersions, vinyl dispersions, polyvinyl acetate dispersions. vinylpyrrolidone terpolymer dispersions, dimethylaminopropyl methacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride, polyurethane / polyacrylic hybrid polymer dispersions, core-shell particle dispersions and mixtures thereof. The following are various types of aqueous dispersions, especially commercial dispersions, suitable for the preparation of the composition according to the present invention. 1 / Thus, according to a preferred embodiment of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of acrylic polymer. The acrylic polymer may be a styrene / acrylate copolymer, and in particular a polymer chosen from copolymers derived from the polymerization of at least one styrenic monomer and at least one C 1 -C 18 alkyl (meth) acrylate monomer. As styrene monomer usable in the invention include for example styrene or alpha-methylstyrene, and in particular styrene. The monomer of (meth) acrylate C1-C18 is in particular a (meth) acrylate C1-C12 alkyl and more particularly a C1-C10 alkyl (meth) acrylate. The (C 1 -C 18) alkyl (meth) acrylate monomer may be chosen from methyl acrylate, methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylate and the like. butyl, hexyl acrylate, o-octyl acrylate, 2-ethyl hexyl acrylate, lauryl (meth) acrylate and stearyl (meth) acrylate. As acrylic polymer in aqueous dispersion, it is possible to use according to the invention the styrene / acrylate copolymer sold under the name "Joncryl SCX-8211®" by the company BASF, the acrylic polymer marketed under the reference "Acronal® DS-6250" by BASF, the acrylic copolymer "Joncryl® 95" by the company BASF.

2 / according to an alternative embodiment of the invention, the aqueous dispersion of polymer particles is an aqueous dispersion of polyesterpolyurethane particles and / or polyether polyurethane in particular anionic.

The anionic character of the polyester-polyurethanes and polyether polyurethanes used according to the invention is due to the presence in their constituent units of carboxylic acid or sulphonic acid functional groups. The polyester-polyurethane or polyether-polyurethane particles used according to the invention are generally marketed in the form of aqueous dispersions. The particle content of said dispersions currently available on the market ranges from about 20% to about 50% by weight based on the total weight of the dispersion. Among the dispersions of anionic polyester-polyurethane used in the aqueous varnishes according to the invention, mention may in particular be made of the product sold under the name "Avalure UR 405®" by the company Noveon. Among the dispersions of anionic polyether polyurethane particles that can be used according to the invention, mention may be made in particular of those sold under the name "Avalure UR 450®" by the company Noveon, and under the name "Néorez R 970®" by the company DSM. According to one particular embodiment of the invention, it is possible to use a mixture of commercial dispersions consisting of anionic polyester-polyurethane particles as defined above and anionic polyether-polyurethane particles also defined above. For example, it is possible to use a mixture consisting of the dispersion marketed under the name "Sancure 861®" or a mixture of the one marketed under the name "Avalure UR 405®" and that marketed under the name "Avalure UR 450". ®, these dispersions being marketed by the company NOVEON.

3 / According to another particular embodiment of the invention, the aqueous dispersion used comprises a mixture of at least two film-forming polymers in the form of solid particles that are distinct by their respective glass transition temperatures (Tg). In particular, according to one embodiment of the invention, the composition according to the invention may comprise at least one first film-forming polymer in the dispersed state and at least one second film-forming polymer in the dispersed state, said first and second polymers having different Tg and preferably the Tg of the first polymer (Tgl) is greater than the Tg of the second polymer (Tg2). In particular, the difference between Tg1 and Tg2 is in absolute value, at least 10 ° C, preferably at least 20 ° C. More specifically, it comprises in an acceptable aqueous medium: a) solid particles dispersed in the aqueous medium of a first film-forming polymer having at least a glass transition temperature Tgl greater than or equal to 20 ° C, and b) solid particles dispersed in the aqueous medium of a second film-forming polymer having at least a glass transition temperature Tg 2 of less than or equal to 70 ° C. This dispersion generally results from a mixture of two aqueous dispersions of film-forming polymer. The first film-forming polymer has at least one, especially at a glass transition temperature Tgl greater than or equal to 20 ° C, in particular ranging from 20 ° C to 150 ° C, and advantageously greater than or equal to 40 ° C, in particular ranging from 40 ° C to 150 ° C, and in particular greater than or equal to 50 ° C, in particular ranging from 50 ° C to 150 ° C.

The second film-forming polymer has at least one, especially at a glass transition temperature Tg2 of less than or equal to 70 ° C., especially ranging from -120 ° C. to 70 ° C., and in particular lower than 50 ° C., in particular ranging from 60 ° C to +50 ° C, and more particularly ranging from -30 ° C to 30 ° C.

The measurement of the glass transition temperature (Tg) of a polymer is carried out by DMTA (Dynamic and Mechanical Temperature Analysis) as described below. To measure the glass transition temperature (Tg) of a polymer, viscoelasticimetry tests were performed with a DMTA apparatus of "Polymer Laboratories" on a film sample. This film is prepared by casting the aqueous dispersion of film-forming polymer in a Teflon matrix and then dried at 120 ° C. for 24 hours. A film is then obtained in which the specimens are cut (for example by punching). These typically have a thickness of about 150 μm, a width of 5 to 10 mm and a useful length of about 10 to 15 mm. This sample is imposed a tensile stress. The sample is subjected to a static force of 0.01 N superimposed on a sinusoidal displacement of ± 8 μm at the frequency of 1 Hz. This works in the linear domain under low levels of deformation. This tensile stress is performed on the sample at temperatures ranging from -150 ° C to +200 ° C, with a temperature variation of 3 ° C per minute.

The complex modulus E * = E '+ iE "of the tested polymer is then measured as a function of the temperature, from which the dynamic modules E', E" and the damping power are deduced: tg8 = E "/ E '. Then the curve of the values of tg8 is plotted as a function of the temperature, this curve exhibiting at least one peak The glass transition temperature Tg of the polymer corresponds to the temperature at which the peak of this peak is situated. at least 2 peaks (in this case, the polymer has at least 2 Tg), the temperature for which the curve has a peak of greater amplitude (i.e., corresponding to the highest value of tg8 is considered in this case only the "majority" Tg as the Tg value of the tested polymer).

In the present invention, the transition temperature Tg1 corresponds to the "majority" Tg (in the sense defined above) of the first film-forming polymer when the latter exhibits at least 2 Tg; the glass transition temperature Tg2 corresponds to the "majority" Tg of the second film-forming polymer when the latter has at least 2 Tg. The first film-forming polymer and the second film-forming polymer may be chosen, independently of one another, from among the radical polymers, polycondensates and polymers of natural origin as defined above having the characteristics of glass transition temperature defined above. As the first film-forming polymer in aqueous dispersion, it is possible to use the aqueous polymer dispersions sold under the names "NeoRez R-989®" by the company DSM, "Joncryl 95" and "Joncryl® 8211" by the company BASF. As the second film-forming polymer in aqueous dispersion, it is possible to use, for example, the aqueous polymer dispersions sold under the names "Avaluré UR-405", "Avaluré UR-460" by the company NOVEON or "Acrilem IC89RT®" by the company ICAP, Neocryl A-45 by the company DSM. The film-forming polymer of the aqueous dispersion "Avalide UR-460" is a polyurethane obtained by the polycondensation of tetramethylene polyoxide, tetramethylxylylene diisocyanate, isophorone diisocyanate and dimethylol propionic acid.

According to a very particularly preferred embodiment of the invention, the combination of styrene / acrylate polymer dispersion such as the dispersion marketed under the reference "Joncryl 8211®" by BASF is used as the first and second film-forming polymers in aqueous dispersion. acrylic polymer dispersion such as the dispersion marketed under the reference "Neocryl A-45®" by DSM.

According to another preferred embodiment of this particular embodiment of point 3 / above of the invention, a dispersion of acrylic polymer such as the dispersion marketed under the reference "Joncryl 95" is used as the first film-forming polymer in aqueous dispersion. ® by BASF and as a second film-forming polymer an anionic polyurethane polymer dispersion marketed under the reference "Avalure UR405®" by DSM.

In this embodiment of point 3 / above, the total dry matter content of the first film-forming polymer and the second film-forming polymer is generally from 0.1% to 60% by weight, relative to the total weight of the composition. , in particular from 1% to 50%, and more particularly from 5% to 40% by weight. 4 / According to yet another embodiment of the invention, the aqueous dispersion used comprises at least one particular multiphase aqueous dispersion. More specifically, it comprises, in an acceptable aqueous medium, a dispersion of particles, the particles comprising at least one at least partially external flexible phase comprising at least one flexible polymer having at least one glass transition temperature Tg 2 and at least one rigid phase at less in part internally, the rigid phase being an amorphous material having at least a glass transition temperature Tgl, Tgl being greater than Tg2, the flexible polymer being fixed at least partially by chemical grafting on the rigid phase. In particular, the difference between Tg1 and Tg2 is, in absolute value, at least 10 ° C, preferably at least 20 ° C. The particles according to the invention, also called multiphase particles (or composites), are particles comprising at least one flexible phase and at least one rigid phase. The flexible polymer of the particles in dispersion may have at least a glass transition temperature of less than or equal to 70 ° C., in particular ranging from -120 ° C. to 70 ° C., and more particularly lower than or equal to 30 ° C., in particular ranging from -60 ° C to 30 ° C. The flexible polymer may be chosen from block and / or random polymers. By "block and / or random polymers" is meant polymers whose distribution of the monomers on the main chain or the pendent chain members is sequenced (blocks) and / or statistical.

The flexible polymer may be chosen from radical polymers, polycondensates and silicone polymers. The flexible polymer may be chosen from polyacrylics, polymethacrylics, polyamides, polyurethanes, polyolefins, in particular polyisoprenes, polybutadienes, polyisobutylenes (PIB), polyesters, polyvinyl ethers, polyvinylthioethers, polyoxides, polysiloxanes, and especially polydimethyls. siloxanes (PDMS), and their associations. By combinations, we mean the copolymers that can be formed from the monomers leading to the formation of said polymers. In particular, the flexible polymer may be chosen from poly (meth) acrylics, polyurethanes, polyolefins and polysiloxanes. The amorphous material of the rigid phase has a glass transition temperature greater than 20 ° C., in particular ranging from 20 ° C. to 150 ° C., in particular greater than or equal to 30 ° C., in particular ranging from 30 ° C. to 150 ° C. , preferably greater than or equal to 40 ° C, more particularly ranging from 40 ° C to 150 ° C, or even greater than or equal to 50 ° C, in particular ranging from 50 ° C to 150 ° C. The amorphous material of the rigid phase may be a polymer, in particular a block and / or random polymer. It may be a polymer chosen from polyacrylics, polymethacrylics such as, for example, poly (meth) acrylic acid, poly (meth) acrylamides, polyvinyls, polyvinyl esters, polyolefins, polystyrenes, polyvinyl halides such as polyvinyl chloride ( PVC), polyvinyl nitriles, polyurethanes, polyesters, polyamides, polycarbonates, polysulfones, polysulfonamides, polycyclics having a carbon cycle in the main chain such as polyphenylenes, polyoxyphenylenes, and combinations thereof.

Advantageously, the amorphous material of the rigid phase may be a polymer chosen from polyacrylics, polymethacrylics, for example poly (meth) acrylic acid, poly (meth) acrylamides, polyvinyls, polyvinyl esters, polyolefins, polystyrenes, polyvinyl halides such as polyvinyl chloride (PVC), polyvinyl nitriles, polyurethanes, polyamides, polyesters. According to a particular embodiment of the invention, the flexible and rigid phases of the multiphase particles may comprise at least one radical polymer obtained by, or even essentially by, polymerization of monomers chosen from the group formed by: the esters of the acid (meth) acrylic, such as alkyl (meth) acrylates, especially having a C 1 -C 8 alkyl group, vinyl esters of linear or branched carboxylic acids, such as vinyl acetate or vinyl stearate, styrene and its derivatives, such as chloromethyl styrene, alpha methyl styrene, - conjugated dienes, such as butadiene or isoprene, - acrylamide, methacrylamide and acrylonitrile, - vinyl chloride and - (meth) acrylic acid. The monomer selection (nature and content), which can be a single monomer or a mixture of at least two monomers, the flexible polymer and the amorphous material of the rigid phase is determined by the desired glass transition temperature. give each polymer.

The polymers of the rigid and / or flexible phases may be crosslinked using monomers having at least two copolymerizable double bonds, for example chosen from: - conjugated dienes, such as butadiene or isoprene, - allylic esters of alpha beta unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, allyl esters of alpha beta unsaturated dicarboxylic acids such as diallyl maleate, polyacrylics or polymethacrylics generally comprising at least two unsaturations ethylene glycols such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol diacrylate, or pentaneerythritol tetraacrylate; polyvinyls such as divinylbenzene or trivinylbenzene, and polyallylics such as triallyl cyanurate.

Chemical grafting makes it possible, by forming covalent bonds, to bind the rigid phase and the flexible phase of the multiphase particles in a stable manner. The chemical grafting can be done by sequential radical polymerization (also called sequential polymerization) according to the procedures well known to those skilled in the art. The sequenced polymerization consists in polymerizing, in a first step, the monomers of the rigid polymer (polymer forming the rigid phase of the particles) and then, in a second step, continuing the polymerization with the monomers forming the flexible polymer (polymer forming the flexible phase of the particles ). In this way, the polymer chains of the flexible phase are bound at least in part by covalent bonding to the polymer chains of the rigid phase, the covalent bond resulting from the polymerization of a monomer of the flexible polymer with a monomer of the rigid polymer . Advantageously, the monomers of the polymer of the external flexible phase have a greater affinity for the dispersion medium than the monomers of the polymer of the internal rigid phase.

The flexible polymer may be grafted onto the rigid polymer by means of grafting monomer, the latter possibly being a monomer having several double bonds (ethylenic bonds), in particular a monomer having two ethylenic double bonds. The grafting monomer may be a conjugated diene such as those described above or an ester (especially diester) allyl of alpha beta unsaturated dicarboxylic acids such as those described above (such as for example diallyl maleate) which have two polymerizable functions (double bond ethylene) of different reactivities: one of the polymerizable functions (ethylenic double bond) of the grafting monomer is polymerized with the polymer of the amorphous material of the rigid phase (rigid polymer) and the other polymerizable function (ethylenic double bond) of the same monomer graft is polymerized with the flexible polymer. When the flexible polymer or the polymer of the rigid phase is a polycondensate, a polycondensate having at least one ethylenic unsaturation capable of reacting with a monomer also comprising ethylenic unsaturation is used in particular to form a covalent bond with the polycondensate. Polycondensates comprising one or more ethylenic unsaturations are especially obtained by polycondensation of monomers such as allyl alcohol, vinylamine, fumaric acid. For example, vinyl monomers can be polymerized with a polyurethane having vinyl groups in or at the end of the polyurethane chain and thus graft a vinyl polymer onto a polyurethane; a dispersion of particles of such a graft polymer is described in particular in the publications "The structure and properties of acrylic-polyurethane ybride emulsions", Hiroze M., Progress in Organic Coatings, 38 (2000), pages 27-34; "Survey of the applications, properties, and technology of crosslinking emulsions", Bufkin B, Journal of Coatings technology, Vol 50, No. 647, December 1978. The same grafting principle applies to silicones using silicones containing vinyl groups for polymerizing vinyl monomers on silicone and thus grafting vinyl polymer chains onto a silicone. The rigid and flexible phase particles generally have a size ranging from 1 nm to 1 μm, in particular ranging from 10 nm to 1 μm. The flexible phase may be present in the particles in a content of at least 1% by volume, relative to the total volume of the particle, in particular at least 5% by volume, in particular at least 10% by volume , and more particularly at least 25% by volume. The flexible phase may be present in the particles in a content of up to 99.999% by volume, especially up to 99.9% by volume, in particular up to 99% by volume, and more particularly up to 95% by volume. in volume. In particular, the flexible phase may be present in the particles in a content ranging from 1% to 99.999% by volume, in particular ranging from 5% to 99.9% by volume, and more particularly ranging from 10% to 99.9% by volume. % by volume, especially ranging from 25% to 99.9% by volume, and more particularly ranging from 50% to 95% by volume, or even from 50% to 90% by volume.

In all cases, the rigid phase and the flexible phase are incompatible, that is to say they can be distinguished using techniques well known to those skilled in the art, such as for example the observation technique of electron microscopy or measurement of glass transition temperatures of particles by differential calorimetry. The multiphase particles are therefore non-homogeneous particles.

The flexible and rigid phase morphology of the dispersed particles may be, for example, of the core-shell type, with parts of bark completely surrounding the core, but also heart-shell with a multiplicity of cores, or an interpenetrating network of phases. . In the multiphase particles, the flexible phase is at least partly, in particular for the most part, external, and the rigid phase is at least partly, in particular for the most part, internal. The multiphase particles can be prepared by consecutive polymerization series with different types of monomers. The particles of a first family of monomers are generally prepared in a separate step, or formed in situ by polymerization. Then or at the same time, at least one other family of other monomers are polymerized during at least one additional polymerization step. The particles thus formed have at least one structure at least partly internal, or core, and at least one structure at least partly external, or bark. The formation of a heterogeneous "multilayer" structure is thus possible. A great variety of morphologies can result, of the heart-bark type, but also for example with fragmented inclusions of the rigid phase in the flexible phase. According to the invention, it is essential that the flexible phase structure at least partly external is more flexible than the rigid phase structure at least partially internal.

According to a particular embodiment of the invention, the multiphase particles may be dispersed in an aqueous medium, in particular a hydrophilic medium. The aqueous medium may consist mainly of water, and in particular almost completely water. These dispersed particles thus form an aqueous polymer dispersion, generally known as latex or pseudo-latex. By "latex" is meant an aqueous dispersion of polymer particles as can be obtained by emulsion polymerization of at least one monomer. The dispersion of multiphase particles is generally prepared by at least one emulsion polymerization, in an essentially aqueous continuous phase, from reaction initiators, such as photochemical or thermal initiators for radical polymerization, optionally in the presence of additives such as stabilizers, chain transfer agents, and / or catalysts.

As aqueous dispersions of film-forming polymer, it is possible to use: acrylic dispersions sold under the names "Acronal DS-6250®" by the company BASF, "Neocryl A-45®", "Neocryl XK-90®", "Neocryl A" -1070® "," Neocryl A-1090® "," Neocryl BT-62® "," Neocryl A-1079® "and" Neocryl A-523® "by DSM," Joncryl 95® "," Joncryl 8211 " ® by the company BASF, "Daitosol 5000 AD®" or "Daitosol 5000 SJ" by the company DAITO KASEY KOGYO; "Syntran 5760" by the company Interpolymer, - Aqueous dispersions of polyurethane sold under the names "Neorez R-981®" and "Neorez R-974®" by the company DSM, the "Avalure UR-405®", "Avalure UR-410® "," Avalure UR-425® "," Avalure UR-450® "," Sancure 875® "," Avalure UR 445® "," Avalure UR 450® "by NOVEON," Impranil 85® By the company BAYER, the sulfopolyesters sold under the brand name Eastman AQ® by the company Eastman Chemical Products, the vinyl dispersions such as the "Mexomer PAM", the aqueous dispersions of polyvinyl acetate such as "Vinybran®". from the company Nisshin Chemical or those marketed by UNION CARBIDE, aqueous dispersions of terpolymer vinyl pyrrolidone, dimethylaminopropyl methacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride such as "Styleze W ®" - ISP, - aqueous dispersions of hyb polymer polyurethane / polyacrylic wrinkles such as those sold under the references "Hybridur ®" by the company AIR PRODUCTS or "Duromer ®" by NATIONAL STARCH, - dispersions of heart-bark type particles such as those marketed by the company ARKEMA under the reference "Kynar ®" (heart: fluorinated - bark: acrylic) or those described in US 5 188 899 (heart: silica - bark: silicone) and mixtures thereof.

According to a preferred embodiment, a composition in accordance with the invention comprises an aqueous dispersion of solid particles chosen from acrylic aqueous film-forming polymer dispersions and aqueous polyurethane / polyacrylic hybrid polymer dispersions.

Preferably, the particulate phase comprises, or even consists of, thus: i) at least one coloring agent chosen from: organic pigments such as, for example: - Pigments certified D & C by the Food & Drug Administration as listed "CTFA's Color Additives - Batch Certified by the US Food and Drug Administration" section; mention may be made in particular of Blue 1 and 4, Brown 1, Ext.Violet 2, Ext.Yellow 7, Green 3, 5, 6, 8, Orange 4, 5, 10, 11, Red 4, 6, 7 , 17, 21, 22, 27, 28, 30, 36 and 40, Violet 2, Yellow 5, 6, 7, 8, 10 and 11, mineral pigments such as: - carbon black, oxides of iron, titanium, zirconium, cerium, zinc, iron or chromium, - ferric blue, manganese violet, blue, pink or ultramarine violet, chromium hydrate, chromium hydroxide, bismuth oxychloride nacres; reflective particles such as, for example: particles comprising a borosilicate substrate coated with a metal layer; and their mixtures; ii) at least one aqueous dispersion of film-forming polymer (s), preferably chosen from acrylic aqueous film-forming polymer dispersions and aqueous polyurethane / polyacrylic hybrid polymer dispersions; and iii) optionally at least one load.

Lipophilic plasticizer A composition according to the invention also comprises a lipophilic plasticizer, promoting the formation of a film with the film-forming polymer present in the aqueous dispersion.

Such a plasticizer aims in particular to make more flexible said film-forming polymer, and this by decreasing its glass transition temperature (Tg). By lipophilic plasticizer is meant in the present invention a liquid compound at room temperature (25 ° C), preferably having a viscosity of less than 100cPs, preferably less than 50cPs, and having a solubility in water at 25 ° C lower at 10%, preferably below 5%. The plasticizer is in particular chosen from (poly) esters derived from the reaction (s) of at least one carboxylic acid with at least one (poly) ol, glycol ethers, N-ethyl-o, p -toluenesulfonamide, carbonates, ketones, and mixtures thereof.

By (poly) ol is meant a polyol compound or monoalcohol. By polyol is meant an organic compound comprising at least 2 hydroxyl groups, particularly between 2 and 6 hydroxyl groups, said hydroxyl groups being borne by a C1-C6 i) alkyl group optionally interrupted by from 1 to 6 heteroatoms chosen from N, S , O; ii) C5-C20 aryl, iii) heteroaryl comprising between 5 and 20 members with 1 to 3 heteroatoms selected from N, S, O; iv) heterocycloalkyl; and v) cycloalkyl. In particular, as poly (ol), there may be mentioned for example ethylene glycol or glycerol. By monoalcohol is meant an organic compound comprising a single hydroxyl group, said hydroxyl group being carried by a group i) C 1 -C 6 alkyl optionally interrupted by 1 to 6 heteroatoms selected from N, S, O; ii) C5-C20 aryl; iii) heteroaryl comprising between 5 and 20 members with 1 to 3 heteroatoms selected from N, S, O; iv) heterocycloalkyl; and v) cycloalkyl.

The plasticizer may thus be chosen more particularly from:

a) The esters resulting from the reaction, and in particular from the monocondensation or polycondensation, of one or more carboxylic or orthophosphoric acids with one or more (poly) ol, such as a diol. Such esters may be (mono / poly) esters, and preferably polyesters, such as diesters.

Such esters may in general be derived from the reaction of one or more (mono / poly) carboxylic acid of formula R 1 (COOH) n with one or more (poly) ol of formula R 12 (OH) m with: - and R12, identical or different, represent a hydrocarbon chain, preferably comprising from 3 to 15 carbon atoms, linear, branched or cyclic C3-C15 cycloalkyl, saturated or unsaturated, optionally non-aromatic, optionally comprising one or more heteroatoms such as N, O, S such as 0 to 6 heteroatoms, n ranging from 1 to 6, and - m ranging from 6

Preferably, R 11 is a C 2 -C 5 alkyl radical such as ethyl, propyl, butyl, isobutyl and R 12 is a linear saturated or branched hydrocarbon chain comprising from 5 to 10 carbon atoms. As examples of esters, mention may in particular be made of:

esters derived from the reaction of R (COOH) in which R represents a branched alkyl chain of C3 to C10 such as isobutyl or terbutyl, with HOC (R) (R ') - C (OH) - 20 CH ( R ") - R 'where R represents a hydrogen atom or a linear or branched alkyl chain such as methyl and R', R", R "'representing a linear or branched alkyl chain such as methyl. esters derived from the monocondensation or dicondensation of tert-butyl acid and tri-methyl-2,2,4-pentanediol-1,3, in particular a monoester resulting from the reaction of isobutyric acid and octanediol such as 2,2,4-trimethyl-1,3-pentanediol, such as TEXANOL Ester Alcohol sold by the company Eastman Chemical - phosphoric acid esters resulting from the condensation between one or more (poly) ol and one or more orthophosphoric acid of formula (RZ) p = O (O-R ') m with R, R' representing a linear or branched C Wherein n is 1, 2 or 3 and m is 0, 1 or 2, with m + n being 3 and Z is a heteroatom such as oxygen or a sigma bond. By way of example of such esters, mention may be made inter alia of tricresyl phosphate, tributyl phosphate, triphenyl phosphate and tributoxyethyl phosphate; fatty acid esters derived from the (mono / poly) condensation between one or more (poly) ol and one or more fatty acids of formula R (COOH) n with R being a linear linear alkyl chain of C3 to C22 and n being equal to 1 or 2. By way of example of such esters, mention may be made, inter alia, of adipic acid esters, such as diisobutyl adipate, diethyl adipate or stearic acid esters, such as ethyl stearate, or palmitic acid esters, such as 2-ethylhexyl palmitate. esters of citric acid or citrate, such as triethyl citrate, tributyl citrate, triethyl acetyl citrate, tributyl acetyl citrate, triethyl-2 hexyl acetyl citrate; esters of phthalic acid or phthalate, such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dipentyl phthalate, dimethoxyethyl phthalate, butyl phthalate and 2-ethyl hexyl; esters of tartaric acid or tartrates, especially dibutyl tartrate; esters of sebacic acid or sebacates, such as dimethyl sebacate or dibutyl sebacate; propylene glycol diacetate and glycerol triacetate; benzyl benzoate; butyl acetylricinoleate, glyceryl acetylricinoleate; and butyl glycolate. b) Glycol ethers By way of examples of glycol ethers, mention may be made of diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, ethylene glycol ethyl ether and ethylene glycol. butyl ether, ethylene glycol hexyl ether or else propylene glycol phenyl ether, dipropylene glycol butyl ether, tripropylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol ethyl ether, tripropylene glycol methyl ether, diethylene glycol methyl ether and propylene glycol butyl ether, N-ethyl-o, ptoluenesulphonamide and in particular ethyltosylamide, as sold under the reference RESIMPOL 8 by Pan-Americana, can also be used as plasticizer. d) Carbonates; (e) Ketones, including camphor, and their mixtures. Preferably, said lipophilic plasticizer is selected from citric acid esters such as triethyl citrate, and glycol ethers such as propylene glycol butyl ether and mixtures thereof. The plasticizer (s) may be present in a content ranging from 0.1 to 10% by weight relative to the total weight of the composition, preferably from 0.5 to 5%, and better still from 1 to 3% by weight. In general, this plasticizing agent may be present in a quantity by weight greater or equal to, better still, greater than 0.1% relative to the total weight of the composition. Aqueous Phase This aqueous phase, in particular provided by the dispersions of film-forming polymer, is carried out in an amount compatible with the galenical form required according to the invention. The aqueous phase may be deionized water, or floral water such as blueberry water and / or mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water. / or thermal water. The aqueous phase may also comprise a water-miscible polyol at ambient temperature (25 ° C.), chosen in particular from polyols having in particular from 2 to 20 carbon atoms, preferably having from 2 to 10 carbon atoms, and preferentially having from 2 to 6 carbon atoms, such as glycerine, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol; glycol ethers (having in particular from 3 to 16 carbon atoms) such as the mono-, di- or tripropylene glycol (C 1 -C 4) alkyl ethers, the mono (di) or di (C 1 -C 4) alkyl ethers; triethylene glycol; and their mixtures. The composition according to the invention may comprise a polyol which is miscible with water at room temperature. Such polyols may promote the hydration of the skin surface on which the composition is applied. In addition, the composition according to the invention may comprise a monoalcohol having from 2 to 6 carbon atoms such as ethanol and isopropanol. According to a particular embodiment, a composition according to the invention may comprise less than 10% by weight of water relative to the total weight of the composition, or even less than 5% by weight of water.

Dispersing Agents The composition according to the invention may comprise at least one dispersing agent or surfactant. This dispersing agent can promote good dispersion of the pigments and (pseudo) latex in a composition according to the present invention.

These surfactants may be selected from nonionic surfactants of HLB (hydrophilic-lipophilic balance) less than or greater than 8 to 25 ° C in the Griffin sense, anionic, cationic, amphoteric and mixtures thereof. Reference can be made to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER", Vol. 22, p. 333-432, 3rd edition, 1979, WILEY, for the definition of the properties and emulsifying functions of surfactants, in particular p. 347-377 of this reference, for anionic, amphoteric and nonionic surfactants.

The dispersing agent may consist of one or more dispersing agents. The dispersing agent can belong to different chemical families detailed below: 1 / Ionic surfactants such as: - carboxylic salts, - amino acid salts such as glutamic acid, - salts of sulfosuccinic acids, - phosphoric acid salts. By "salts" is meant alkali metal salts such as Na, Li, K of said acids, mono, di or triethanolamine salts or basic amino acids such as lysine or arginine, said acids, and mixtures thereof. . the oxyethylenated derivatives of phosphoric acid and in particular: the esters resulting from the reaction of phosphoric acid and of at least one alcohol comprising a linear or branched alkyl chain, saturated or unsaturated, having from 8 to 22 atoms of carbon, - the esters resulting from the reaction of phosphoric acid and at least one ethoxylated alcohol, comprising a linear or branched, saturated or unsaturated alkyl chain having from 8 to 22 carbon atoms and having from 2 to 40 groups oxyethylenes, - their salts - and their mixtures. These esters may in particular be chosen from esters of phosphoric acid and of C 9 -C 15 alcohols or their salts, such as the potassium salt of (C 9-15) alkylphosphate sold under the name Arlatone MAP by the company UNIQEMA, esters of phosphoric acid and of stearyl and / or isostearyl alcohols, such as stearyl alcohol / isostearyl alcohol phosphate (CTFA name: Octyldecylphosphate), sold under the name Hostaphat CG120 by the company Hoechst Celanese, esters of phosphoric acid and cetyl alcohol, and their oxyethylenated derivatives such as the product sold under the name Crodafos CES (mixture of cetearyl alcohol, dicetyl phosphate and ceteth-phosphate) by the company Croda, the acid esters phosphoric acid and tridecyl alcohol, and their oxyethylenated derivatives such as the product marketed under the name Crodafos T10 (CTFA name: Trideceth-10 Phosphate) by the company Croda. the alkyl sulphates, the alkyl benzene sulphonates, the alkyl ether citrates which may be chosen in particular from the group comprising monoesters, diesters or triesters resulting from the reaction of citric acid and at least one oxyethylenated fatty alcohol comprising a linear or branched alkyl chain, saturated or unsaturated, having from 8 to 22 carbon atoms, and comprising from 3 to 9 oxyethylenated groups, and mixtures thereof. Mention may be made, for example, of mono-, di- and tri-esters of citric acid and ethoxylated lauric alcohol, comprising from 3 to 9 oxyethylenated groups, sold by Witco under the name Witconol EC, in particular Witconol EC. 2129 which is predominantly a dilaureth-9 citrate, and Witconol EC 3129 which is predominantly a trilaureth-5 9 citrate. The alkyl ether citrates can advantageously be used in neutralized form at a pH of about 7, the neutralization agent being chosen from inorganic bases such as sodium hydroxide, potassium hydroxide, ammonia, and organic bases such as mono-, di- and tri-ethanolamine, aminomethylpropanediol-1,3, N-methylglucamine, basic amino acids such as arginine and lysine, and mixtures thereof. 2 / nonionic surfactants such as: - ethers of C10-C30 fatty alcohols and of polyethylene glycol (also called alkyl polyoxyethylene ethers) comprising from 2 to 100 oxyethylenated groups, such as those sold under the name BRIJ by the company UNIQEMA or else lauryl alcohol oxyethylenated (OE), in particular at 21 or 23 OE groups, - fatty acid esters (especially C8-C24, and preferably C16-C22 acid) and polyethylene glycol (Also called alkyl polyoxyethylene esters) comprising from 2 to 100 oxyethylenated groups, such as those sold under the name MYRJ by the company UNIQEMA, alkyl sorbitan esters such as those sold under the name SPAN by the company UNIQEMA, alkyl esters polyoxyethylene sorbitan comprising from 4 to 100 oxyethylenated groups (such as those sold under the name TWEEN by the company UNIQEMA), - C8-C24 fatty acid esters and polyglycerol (in particular tetraglycerol, hexaglycerol or decaglycerol) comprising from 2 to 10 oxyethylenated groups (as those sold under the name Tetraglyn, Hexaglyc, Decaglyn by the company NIKKOL), polyhydroxystearic acid esters (such as for example 1 '). ARLACEL 165 from the company Uniquema), alkyl glucosides, for example compounds derived from the reaction of coconut alcohol and glucose (my INCI: coco-glucosides), such as those marketed under the reference APG by COGNIS company) and alkyl maltosides.

Mention may also be made of silicone surfactants, in particular oxyalkylenated silicones also called dimethicone copolyols.

The copolyol dimethicones according to the invention are more preferably chosen from the compounds of general formula (I): ## STR5 ## wherein R 1 is SiO 2 SiO 3 In which: R 1, R 2, R 3, independently of each other, represent an alkyl, aryl, aralkyl group, containing not more than 10 carbon atoms, or a radical - (R 5) CH 2) x - (OCH 2 CH 2) y (OCH 2 CH 2 CH 2) z - OR 4, at least one radical R 1, R 2 or R 3 not being an alkyl radical; R4 being a hydrogen, an alkyl radical or an acyl radical; some of the radicals R 1, R 2, and R 3 may also additionally contain an ethylcyclohexylenemonoxide group and are in a small proportion in the polysiloxane chain. The radicals R5, which may be identical or different, represent an alkyl, aryl or aralkyl group containing not more than 10 carbon atoms and preferably chosen from C1-C4 lower alkyls such as methyl, ethyl or butyl or chosen from 25 phenyl and benzyl groups and even more preferentially all denote methyl groups; some of the R5 radicals may also contain an ethylcyclohexylenemonoxide group and are in a small proportion in the polysiloxane chain.

A is an integer ranging from 0 to 200; B is an integer from 0 to 50; provided that A and B are not equal to zero at the same time; x is an integer from 1 to 8; y is an integer from 1 to 30; z is an integer ranging from 0.5 to 5.

According to a preferred embodiment of the invention, in the compound of formula (I), the alkyl radical is a methyl radical, x is an integer ranging from 2 to 6 and y is an integer ranging from 4 to 30. By way of example of silicone surfactants of formula (I), mention may be made of the compounds of formula (II): in which A is an integer ranging from 20 to 105, B is an integer ranging from 2 to 10 and y is an integer ranging from 10 to 20. Mention may also be made, by way of example of silicone surfactants of formula (I), of the compounds of formula (III): ## STR2 ## in which A 'and y are integers ranging from 10 to 20. It is possible to use as compounds of the invention those sold by Dow Corning under the names DC 5329, DC 7439-146, DC 2. -5695 and Q43667. Compounds DC 5329, DC 7439-146, DC 2-5695 are compounds of formula (II) wherein A is 22, B is 2 and Y is 12, respectively; A is 103, B is 10 and y is 12; A is 27, B is 3 and y is 12. Compound Q4-3667 is a compound of formula (III) where A is and y is 13. According to another preferred embodiment of the invention, by way of example of silicone surfactants of formula (I), the following formulas (IV) and (V): R5 Si-O R5 R5 Si-R5 R5 R5 R5 R5 E-Si-O Si-O Si In which: u is 5 to 59, preferably 10 to 50 and more preferably 12 to 25; - v is 3 to 12, preferably 4 to 10 and more preferably 5 to 8; E denotes a group - (CH 2) x - (OCH 2 CH 2) y (OCH 2 CH 2 CH 2) z - OR 4 in which: x is 1 to 8, preferably 2 to 4 and more preferably 3; - y> 0 and z> 0; y and z are chosen so that the total molar mass of the radical E varies from 200 to 10,000 g / mol and more preferably from 350 to 3000; preferably, the number z is equal to zero. In formula E, when z is positive, the oxyethylene and oxypropylene units may be randomly distributed in the polyether chain E and / or in block form. The water-soluble silicones according to the invention are known and in particular described in US Pat. No. 5,338,352 and their method of preparation is described in particular in US Pat. No. 4,847,398. Such silicones are for example sold by OSI under the trade names Silwet L-720®, Silwet L-7002®, Silwet L-7600®, Silwet L-7604®, Silwet L-7605®, Silwet L-7607® Silwet 1614, Silwet L-7657®, Silwet L-7200®, Silwet L7230, Silsoft 305, Silsoft 820, Silsoft 880 or by Goldschmidt under the trade names Tegowet 260, Tegowet 500, Tegowet 505 and Tegowet 510.

3 / Ionic polymers such as: - polyacrylic acids and their salts, - styrene / acrylic acid copolymers and their salts, - vinylnaphthalene / acrylic acid copolymers and their salts, - styrene / maleic acid copolymers and their salts, vinylnaphthalene / maleic acid copolymers and their salts, copolymers of maleic anhydride and of diisobutylene and their salts and more particularly that marketed under the name Orotan 731DP® by the company Rhodia, acrylic acid copolymers and their salts maleic anhydride copolymers and their salts, in particular copolymers obtained by copolymerization of one or more maleic anhydride co-monomers and of one or more comonomers chosen from vinyl acetate and vinyl alcohol; , vinylpyrrolidone, olefins having from 2 to 20 carbon atoms such as octadecene, ethylene, isobutylene, diisobutylene, isooctyl not, and styrene, and mixtures thereof, maleic anhydride co-monomers which can be optionally hydrolysed, partially or totally. Mention may be made, for example, of styrene / maleic anhydride copolymer (50/50) in the form of the 30% ammonium salt in water sold under the reference SMA1000H® by Arkema or the styrene / maleic anhydride copolymer ( 50/50), in the form of 40% sodium salt in water sold under the reference SMA1000HNâ by the company Arkema. the non-crosslinked N-vinylimidazole polymers or copolymers (by non-crosslinked is meant any polymer comprising N-vinylimidazole units, and not comprising a crosslinking agent), in particular the copolymers associating N-vinylimidazole subunits with subunits; N-vinylpyrrolidone and / or vinylcaprolactam units. It is possible to use for this purpose the vinylpyrrolidone / vinylimidazole copolymer (50/50) having a weight average molecular weight of 1 200 000 sold under the reference LUVITEC VPI 55K72W by BASF or the vinylpyrrolidone / vinylimidazole copolymer (50/50). having a weight average molecular weight of 10,000 sold under the reference LUVITEC VPI 55K18P by the company BASF. polymers obtained by copolymerization or grafting of hydrophobic groups with the ionic monomers mentioned above, polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid (AMPS), such as for example Aristoflex marketed by Clariant, water-dispersible polymers of isophthalic acid or of sulphoisophthalic acid, and in particular the phthalate / sulfoisophthalate / glycol copolymers (for example diethylene glycol / phthalate / isophthalate / 1,4-cyclohexanedimethanol) sold under the names "Eastman AQ polymer" (in particular AQ35S, AQ38S, AQ55S, AQ48 Ultra) by the company Eastman Chemical, and their mixtures. 4 / Nonionic polymers such as: polyvinyl alcohols, homopolymers of vinylpyrrolidone, such as Luviskol K 17 Powder, Kollidon 17 PF, Kollidon 12 PF BASF, Kollidon 30, Kollidon 90 of the company BASF, polyvinylpyrrolidone K 60 solution from FLUKA, - polyalkylene glycols, preferably chosen from those whose alkylene group contains from 1 to 4 carbon atoms, in particular polyethylene glycols, polypropylene glycols and polybutylene glycols, - block copolymers. ethylene oxide and propylene oxide, which can be chosen in particular from block copolymers of formula (VI):

HO (C2H4O) o (C3H6O) p (C2H4O) gH (VI)

in which o, p and q are integers such that o + q is from 2 to 100 and p is from 14 to 60, and mixtures thereof, and more particularly from block copolymers of formula (VI) having an HLB ranging from from 2 to 16. These block copolymers can be chosen especially from poloxamers (INCI name) and in particular from Poloxamer 231 such as the product sold by BASF under the name Pluronic L81 of formula (VI) with o = q = 6 , p = 39 (HLB 2); Poloxamer 282 such as the product sold by BASF under the name Pluronic L92 of formula (VI) with o = q = 10, p = 47 (HLB 6); and Poloxamer 124, such as the product sold by BASF under the name Pluronic L44 of formula (VI) with o = q = 11, p = 21 (HLB 16).

The citric acid, alpha hydroxy acids and mixtures thereof may also be mentioned as dispersing agents.

Among all the dispersing agents mentioned above, those chosen from anionic polymers such as polyacrylic acid salts, styrene / acrylic acid copolymer salts, vinylnaphthalene / acrylic acid copolymer salts, copolymer salts are preferred. styrene / maleic acid, the vinylnaphthalene / maleic acid copolymer salts, the copolymers of maleic anhydride and of diisobutylene and their salts, and more generally all the salts of copolymers of acrylic acid, or of maleic anhydride, or else, and preferably, those chosen from nonionic surfactants and in particular ethers of C 10 -C 30 fatty alcohols and of polyethylene glycol, such as lauryl alcohol which is oxyethylenated for example with 21 or 23 OE groups.

According to a particularly preferred embodiment, said at least one dispersing agent comprises a nonionic surfactant chosen from a C 10 -C 30 fatty alcohol ether and polyethylene glycol comprising from 2 to 100 oxyethylenated groups. The dispersing agent may be present in a content ranging from 0.01 to 10% by weight, in particular ranging from 0.1 to 7.5% by weight, or even from 0.1 to 5% by weight relative to the total weight. of the composition according to the invention.

According to a particular embodiment, a composition according to the present invention may comprise at least two distinct dispersing agents. According to a particular embodiment, a composition according to the present invention may comprise at least one dispersing agent disposed on the surface of the pigment particles. To do this, the pigment particles can advantageously be surface-treated. For example, they may be treated to include organic functions capable of promoting the adsorption of the dispersing agent. According to one particular embodiment, the pigment particles comprise, after such a treatment, polar functions. Gelling agents A composition in accordance with the invention may further comprise at least one hydrophilic or water-soluble gelling agent. As hydrophilic or water-soluble gelling agents, mention may be made of: the homo- or copolymers of acrylic or methacrylic acids or their salts and their esters and in particular the products sold under the names "VERSICOL F" or "VERSICOL K" by the company ALLIED COLLOID, "UTRAHOLD 8" by CIBA-GEIGY, polyacrylic acids of SYNTHALEN K type, copolymers of acrylic acid and acrylamide sold in the form of their sodium salt under the names "RETEN" by the company HERCULES, the sodium polymethacrylate sold under the name "DARVAN No. 7" by the company Vanderbilt, the sodium salts of polyhydroxycarboxylic acids sold under the name "HYDAGEN F" by Henkel, polyacrylic acid / acrylate copolymers, PEMULEN-type alkyl, - AMPS (polyacrylamidomethyl propane sulfonic acid partially neutralized with ammonia and highly crosslinked) marketed by the company CLARIANT - the AMPS / acrylamide copolymers of SEPIGEL or SIMULGEL type sold by the company SEPPIC, and - polyoxyethylenated AMPS / alkyl methacrylate copolymers (crosslinked or otherwise) and their mixtures. As other examples of water-soluble gelling polymers, mention may be made of: proteins, such as proteins of vegetable origin, such as wheat or soy proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and keratin sulfonates; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers; cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, as well as the quaternized derivatives of cellulose; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and of malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and of vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol; associative polyurethanes such as the C16-OE120-C16 polymer from the company Servo Delden (marketed under the name Ser AD FX1100, urethane functional molecule and average molecular weight by weight of 1300), EO being an oxyethylenated unit, the rheolate 205 with a urea function sold by RHEOX or else Rheolate 208 or 204 (these polymers being sold in pure form) or DW 1206B from RHOM & HAAS with a C20 alkyl chain and a urethane bond, sold at 20% by dry matter in water. It is also possible to use solutions or dispersions of these associative polyurethanes, especially in water or in a hydroalcoholic medium. As examples of such polymers, mention may be made of SER AD fx1010, SER AD FX1035 and SER AD 1070 from Servo Delden, Rheolate 255, Rheolate 278 and Rheolate 244 sold by Rheox. It is also possible to use the product DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from Rhom & Haas or Borchigel LW 44 from Borchers, the original polymers. natural, optionally modified, such as: - Arabic gums, guar gum, xanthan derivatives, karaya gum; alginates and carrageenans; glycoaminoglycans, hyaluronic acid and its derivatives; - shellac resin, sandaraque gum, dammars, elemis, copals; Deoxyribonucleic acid; - Muccopolysaccharides such as hyaluronic acid, chondroitin sulfate, and mixtures thereof. Some of the film-forming polymers mentioned above may also act as water-soluble gelling agents. The hydrophilic gelling agents may be present in the compositions according to the invention in a content ranging from 0.05 to 10% by weight relative to the total weight of the composition, preferably from 0.1 to 5% and better still from 0, 2 to 3% by weight.

Viscosity According to a preferred embodiment, the compositions according to the present invention are liquid. Such compositions advantageously have a relatively low viscosity. In particular, the viscosity is advantageously less than or equal to 1000 cps. Typically, the viscosity of the composition can range from 2 to 800 cps, particularly from 5 to 500 cps, and more preferably from 10 to 200 cps. The viscosity measurement is for example measured using a Brookfield RV type apparatus. The protocol for measuring the viscosity is as follows. The mobile used is No. 5. The rotational speed of the mobile is 100 rpm. The measurement is made after 10 minutes of rotation. The liquid is placed in a 30 ml bottle. The measurement is carried out at a temperature of the water bath of 25 ° C.

Adjuvants The composition may comprise other ingredients (adjuvants) usually used in cosmetics such as preservatives, cosmetic active agents, moisturizing agents, UV filters, thickeners, metal salts, perfumes. Of course, one skilled in the art will take care to choose the optional adjuvant (s) added to the composition according to the invention in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or substantially not , altered by the envisaged addition. The content of these various ingredients can for example range from 0.01 to 20%, and especially from 0.01 to 10%, by weight, relative to the total weight of the composition.

In another aspect, the invention also relates to a make-up assembly comprising: i) an applicator, ii) an eyeliner composition according to the invention disposed inside a container.

The container may delimit one or more compartment (s). The container may for example be in the form of a tube.

Such an applicator may be secured to a cover mounted reversibly on said container between a closed position of said container and a makeup position. Alternatively, such an applicator may be irreversibly mounted on said container. In addition, a hood can be attached to this applicator.

EXAMPLES Two examples of eyeliner composition according to the invention were made and compared to a composition outside the invention, in particular from the point of view of: - Coverage, - Intensity of the black, - Gloss, and - General holding of the deposit.

Protocols - Measurement of Coverage The coverage of the eyeliner compositions is measured at a finite thickness of 50 μm. The composition is spread on matt black and matt white contrast cards, for example LENETA Form WP1 for the matte black card and Leneta 1A for the matte white card. The application can be performed with an automatic spreader. The measurements are carried out on the compositions thus spread. Reflectance spectra are acquired using a MINOLTA 2002 spectrocolorimeter (diffuse / 8 ° measurement geometry and observation D65 / 10 °, specular component mode included, small aperture (CRIIMM) on the black and white backgrounds, Contrast cards are optionally coated with BLENDERM® as indicated above The spectra are expressed in colorimetric coordinates in the space CIELab76 within the meaning of the International Commission on Illumination according to recommendation 15: 2004. coverage, is calculated by averaging Y on a black background, divided by the average value of Y on a white background, multiplied by 100. - Intensity of black Colorimetric results: L * The coloring obtained with said compositions is evaluated visually and read to the Minolta spectrocolorimeter (CM3700d, illuminant D65, 10 ° angle, SCI values) for L * colorimetric measurements In a L * a * b * system, the L * value is low, the darker the color.

Chromaticity Result: C * The chromaticity in the CIE L *, a *, b * system is calculated according to the following equation: The higher the value of C *, the more saturated the coloration obtained.

Brightness On a LENETA brand contrast card and PENOPAC FORM 1A reference card, a 50 μm thick layer of the composition of which the average gloss is to be evaluated is spread with the aid of an automatic spreader. . The layer covers the white background and the black background of the map. It is allowed to dry for 1 hour at room temperature and then the gloss is measured at 20 °, 60 ° and 85 ° on the white matt absorbent base (3 measurements) using a branded glossmeter. BYK GARDNER and microTRl-GLOSS reference.

- General holding of the deposit Preparation of the zones 25 Clean the inside of the forearms with a classic EFFACIL-type make-up remover Rinse with water and allow to dry for 10 minutes Apply the eyeliners compositions in 2 transverse lines Dry 10 min in the air ambient. In order to evaluate the general behavior of the deposit a score is then awarded corresponding to the average rating of three criteria, the "resistance to water", the "resistance to 44 sebum" and the "resistance to friction". This rating can range from 0 to 8; 0 being the score obtained when the line remains intact, and 8 the score obtained when the line has completely disappeared.

By "water resistance" is meant according to the present application the resistance to water in vitro evaluated according to the following protocol: - Pass the first forearm 1 min under running water at 25 ° C, evaluate the state of the line (intensity of the color, degradation of the line, presence of traces ...) - Rub slightly the line with the finger in 1 go / return, evaluate the state of the 1st line (intensity of the color, degradation of the line, presence of traces ...). The resulting traces are assigned a visually evaluated score of between 0 and 8; 0 being the score obtained when the line remains intact, and 8 the score obtained when the line has totally disappeared

By "resistance to sebum" is meant according to the present application the resistance to vegetable squalene (squalene is present at 18% in the composition of sebum) in vitro evaluated according to the following protocol: - On the second forearm, rub slightly in 1 return, the first trait with a cotton soaked in vegetable squalene (1.5 mL), evaluate the condition of the trait with the same evaluation scale as previously mentioned.

By "resistance to friction" is meant according to the present application the in vitro friction resistance evaluated according to the following protocol: - On the second forearm, gently rub back and forth, the second line with the finger, evaluate the state of the line with the same rating scale as previously cited.

EXAMPLES AND RESULTS COMPOUNDS COMPOSITION COMPOSITION COMPOSITION 2 1 according to the invention according to the invention invention the invention COPOLYMER 70.75 70.75 STYRENE / ACRYLATE / A METHONRY METHACRYLATE (AND) SODIUM LAURETH-12 SULPHATE WITH 38% COPOLYMER (SYNTRAN 5760 of INTERPOLYMER) WATER 70.75 16.20 PPG-2 BUTYL ETHER 2.00 2.00 2.00 (DOWANOL DPNB from DOW CHEMICAL) DISPERSION BLACK OF 24.00 24.00 CARBON AND LAURETH 21 IN WATER AT 25 % Carbon Black (WD-CB2 from DAITO KASEI KOGYO) IRON OXIDES 6.00 LAURETH-23 1.80 (BRIJ L23 PA from CRODA) PRESERVATIVES 5.55 5.55 5.55 HEC 0.40 0.40 0.40 (CELLOSIZE QP of 4400 H) Homogenous characterization, homogeneous deposition, deposit deposit smooth, glossy and migration, homogeneous, (Eyeliner applied on covering covering and moderately matte skin) covering, satin HOMOGENEITY OF Deposit very Deposit Deposit DEPOT DEPOT homogeneous inhomogeneous homogeneous Couvrance (CR) 100 92 66 Intensity of black L * 26.03 33.25 31.08 (dry film) 0.28 2.89 0.61 Gloss 20 ° 7.2 0.2 0.9 60 ° 43.0 2.4 10.1 85 ° 69.2 39.0 43.7 General holding of deposit 0 5 0 Preparation procedure - In a beaker, disperse the conservative system, deflocculated at 50 ° C in the pigment paste (carbon black or iron oxides); - Cool to room temperature, disperse, still under deflocculating, the lipophilic plasticizer (PPG-2 BUTYL ETHER). Homogenize until a smooth, glossy paste is obtained; - Add the aqueous dispersion of polymer (Syntran 5760) and / or demineralized water. Stir until a fluid and homogeneous formula is obtained; Add the hydrophilic or water-soluble gelling agent (HEC, or hydroxyethylcellulose), always under deflocculating agent. Homogenize until a smooth, fluid and glossy gel is obtained. For "Composition 2 According to the Invention": Disperse LAURETH-23 in the first step at 50 ° C under deflocculator.

Result The compositions 1 and 2 according to the invention lead to a covering film, an intense and brilliant black, which has excellent performance. The resulting film is flexible and provides comfort. In particular it should be noted that the composition 1 according to the invention using carbon black as a pigment gives rise to a particularly advantageous film of good coverage, excellent performance and an intense and brilliant black. It is understood that in the context of the present invention, the weight percentages given for a compound or a family of compounds are always expressed as the dry weight of the compound in question. Throughout the application, the expression "includes one" or "includes one" must be understood to mean "containing at least one" or "comprising at least one," unless the contrary is specified.

Claims (12)

REVENDICATIONS1. An eyeliner composition comprising: - a particulate phase comprising: i) at least one coloring agent, ii) at least one aqueous dispersion of solid particles of at least one film-forming polymer, - a lipophilic plasticizer, wherein said at least one film-forming polymer is present at a solids content greater than or equal to 20% by weight relative to the total weight of said composition. 2. Composition according to claim 1, in which the particulate phase is present at a content greater than or equal to 21% by weight relative to the total weight of the composition, better still ranging from 25% to 60% by weight, in particular ranging from 30% to 30% by weight. 50% by weight relative to the total weight of the composition. The composition of claim 1 or 2, wherein said at least one aqueous dispersion of solid particles of at least one film-forming polymer is selected from acrylic polymer dispersions, polyurethane dispersions, sulfopolyester dispersions, vinyl dispersions, polyvinyl acetate dispersions, vinyl pyrrolidone terpolymer, dimethylaminopropyl methacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride dispersions, polyurethane / polyacrylic hybrid polymer dispersions, core-shell particle dispersions and mixtures thereof. The composition of claim 1, 2 or 3, wherein said at least one aqueous dispersion of solid particles of at least one film-forming polymer is selected from acrylic polymer dispersions. 5. A composition according to any one of the preceding claims, wherein said at least one coloring agent comprises at least one pigment. The composition of claim 5, wherein said at least one pigment is selected from organic pigments, inorganic pigments, and mixtures thereof. 7. Composition according to claim 5 or 6, wherein said at least one pigment is selected from inorganic pigments selected from carbon black, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, as well as oxides of zinc, iron or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder and copper powder, and preferably being black of carbon. 8. Composition according to any one of the preceding claims, comprising at least one dispersing agent. 9. Composition according to any one of claims 5 to 8, comprising 10 at least one dispersing agent disposed on the surface of said at least one pigment. 10. Composition according to the preceding claim 8 or 9, wherein said at least one dispersing agent is chosen from: - ionic surfactants such as carboxylic salts, amino acid salts, sulfosuccinic acid salts, sodium salts; phosphoric acid, oxyethylenated phosphoric acid derivatives, alkyl sulfates, alkyl benzene sulfonates, alkyl ether citrates, nonionic surfactants such as C 10 -C 30 fatty alcohol ethers, and polyethylene glycol ethers including from 2 to 100 oxyethylenated groups, polyethylene glycol fatty acid esters comprising from 2 to 100 oxyethylene groups, alkyl sorbitan esters, polyoxyethylene alkyl sorbitan esters comprising from 4 to 100 oxyethylenated groups, fatty acid esters, C8-C24 and polyglycerol comprising from 2 to 10 oxyethylenated groups, polyhydroxystearic acid esters, alkyl glucosides, silicone surfactants such as oxyalkylenated silicones; ionic polymers such as polyacrylic acids and their salts, styrene / acrylic acid copolymers and their salts, vinylnaphthalene / acrylic acid copolymers and their salts, styrene / maleic acid copolymers and their salts, vinylnaphthalene / maleic acid copolymers and their salts, copolymers of maleic anhydride and diisobutylene and their salts, acrylic acid copolymers and their salts, maleic anhydride copolymers and their salts, non-crosslinked N-vinylimidazole polymers or copolymers, polymers obtained by copolymerization or grafting of hydrophobic groups, polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, water-dispersible polymers of isophthalic acid or sulfoisophthalic acid; nonionic polymers such as polyvinyl alcohols, homopolymers of vinylpyrrolidone, polyalkylene glycols, block copolymers of ethylene oxide and propylene oxide; citric acid or alpha hydroxy acids and; - their mixtures. 11. Composition according to any one of claims 8 to 10, wherein said at least one dispersing agent comprises a nonionic surfactant chosen from a C 10 -C 30 fatty alcohol ether and polyethylene glycol comprising from 2 to 100 oxyethylenated groups. . 12. Composition according to any one of the preceding claims, in which the said lipophilic plasticizer is chosen from: the (poly) esters resulting from the reaction (s) of at least one carboxylic acid with at least one (poly) ol, glycol ethers, N-ethyl-o, p-toluenesulfonamide, carbonates, ketones, and mixtures thereof. 18. Composition according to the preceding claim, wherein said lipophilic plasticizer is selected from citric acid esters such as triethyl citrate, and glycol ethers, such as propylene glycol butyl ether, and mixtures thereof. 19. A composition according to any one of the preceding claims, further comprising a hydrophilic or water-soluble gelling agent. 20. The eye contour skin makeup kit comprising: - an applicator, and - an eyeliner composition according to any one of the preceding claims disposed within a container. 16. A process for making up the lower and / or upper eyelids comprising at least one step of applying to said eyelids the eyeliner composition according to any one of claims 1 to 14.