FR2863877A1 - Composition for coating keratinic fibers, especially eyelashes, comprises solid particles and has a high solids content - Google Patents

Abstract

Composition for coating keratinic fibers comprises solid particles with a density of at least 0.7 g/cm3> and has a solids content of at least 47%. An independent claim is also included for a composition for coating keratinic fibers, comprising solid particles of glass, silica, silicates, alumina, ceramics, mica, metals, metal oxides, alloys, materials of mineral origin, materials derived from animals secretions and/or polymers and having a solids content of at least 47%.

Description

The present invention relates to a cosmetic composition of

  coating of keratinous fibers comprising specific particles.

  The invention also relates to a cosmetic process for makeup or treatment of keratinous fibers such as eyelashes, eyebrows, hair.

  The composition according to the invention may be a make-up composition, also called mascara, a makeup base for keratinous fibers or a base-coat, a composition to be applied to a make-up, also known as a topcoat, or even a fiber treatment composition. keratin. More specifically, the composition according to the invention is a mascara.

  By mascara is meant a composition intended to be applied to the eyelashes: it may be a makeup composition of the eyelashes, a makeup base of the eyelashes, a composition to be applied to a mascara, also called top coat, or else a composition for cosmetic treatment of the eyelashes. Mascara is especially intended for human eyelashes, but also false eyelashes.

  Preferably, the composition according to the invention is a non-rinsed composition. The makeup compositions of the eyes and in particular eyelashes, such as mascaras, may be in various forms: for example, in the form of oil-in-water or O / W or water-in-oil diphasic emulsions. W / O, aqueous or anhydrous dispersions.

  It is generally through the qualitative and quantitative choice of waxes and polymers that the application specificities sought for makeup compositions, such as, for example, their fluidity, their covering power and / or their curling power, are adjusted. Thus, it is possible to produce various compositions which, applied in particular to the eyelashes, induce various effects such as elongation, bending and / or thickening (loading or volumizing effect).

  It is known from the prior art that the higher the solids content in a composition, the more the deposit of material on the eyelash will be important and therefore the result will be volumizing. It is thus possible to increase the solids content of a composition by incorporating solid particles such as fillers or pigments. Nevertheless, the increase in the solids content in a composition, such as an emulsion or dispersion results in an increase in the consistency of the product obtained and therefore an application to the eyelashes which is difficult and difficult because the product is thick and viscous. difficult to deposit, heterogeneously and in packets. Increasing the solids content is therefore often limited by increasing the consistency.

  The use of solid particles in large amounts therefore does not promote a homogeneous and smooth deposit due not only to the consistency but also the size of the particles introduced which gives a granular and non-smooth appearance to the deposit.

  In addition, the use of fillers to increase the solids content generally results in an adsorption of the liquid medium of the composition on the surface of said fillers, which contributes to the thickening of the composition.

  This is usually the case of so-called volumizing mascaras that are difficult to apply and give a heterogeneous makeup.

  It is therefore difficult to obtain a makeup composition for keratinous fibers, comprising a high solids content and therefore a satisfactory volumizing (or loading) effect, having an easy and homogeneous application.

  The inventors have discovered that such a composition can be obtained by using specific particles.

  Surprisingly, the incorporation of such particles at high levels makes it possible to significantly increase the dry matter content of a composition for coating keratin fibers, while maintaining a consistency that allows easy application and a smooth and homogeneous deposit. on keratinous fibers.

  More specifically, the subject of the invention is a composition for coating keratinous fibers comprising a cosmetically acceptable medium and solid particles having a bulk density (pv) greater than or equal to 0.7 g / cm 3, the said composition having a dry extract greater than or equal to 47%.

  The subject of the invention is also a cosmetic process for makeup or non-therapeutic care of keratinous fibers, in particular eyelashes, comprising the application to the keratinous fibers of a composition as defined above.

  The subject of the invention is also the use of a composition as defined above to obtain a makeup of keratinous fibers, in particular eyelashes, which load and / or lead to a smooth and homogeneous deposition on the keratinous fibers.

  The subject of the invention is also the use of particles of bulk density greater than or equal to 0.7 g / cm 3 in a composition for coating keratinous fibers, in particular eyelashes, to obtain a composition that is easily applied on keratinous fibers and / or leading to a smooth and homogeneous deposition on the keratinous fibers and leading to a charging makeup.

  The term "cosmetically acceptable medium" means a medium compatible with keratinous fibers.

  The dry extract of the composition according to the invention is measured by heating the sample with infrared rays of 2 μm to 3.5 μm wavelength. The substances contained in said compositions which have a high vapor pressure, evaporate under the effect of this radiation. The measurement of the loss of weight of the sample makes it possible to determine the dry extract of the composition. These measurements are made using an LP16 commercial infrared dryer from METTLER. This technique is perfectly described in the documentation of the device supplied by MEULER.

  The measurement protocol is as follows: about 1 g of the composition is spread on a metal cup. This, after introduction into the desiccator, is subjected to a temperature of 120 C for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample, corresponding to the mass after exposure to radiation, are measured using a precision balance.

  The dry matter content is calculated as follows: Dry extract = 100 x (dry mass I wet mass).

  The composition according to the invention is characterized by a dry extract greater than or equal to 47%, better still, greater than or equal to 47.5%, preferably greater than or equal to 48%, better still, greater than or equal to 49%, even better greater than or equal to 50%, up to 60%.

  The particles of the composition according to the invention have a bulk density greater than or equal to 0.7 g / cm 3, better still greater than or equal to 0.8 g / cm 3, more preferably greater than or equal to 0.9 g / cm 3, which can go up to 3 g / cm3.

  The bulk density corresponds to the bulk density of a particle and is measured according to the following protocol: A vessel whose volume Vo (cm) is known with an accuracy of 0.005 cm3 (Vo being of the order of 10 cm), is weighed using a precision scale at 0.00005g. Its mass is noted Mo (g). This container is filled gently with the powder until the overflow of the container. The surface of the container is then leveled with a straight blade to obtain a perfectly flat powder surface. The mass M (g) of the container filled with powder is then measured.

  The unpacked bulk density calculated according to the following relationship: Pv (g / cm 3) = M Mo Vo The particles characterized by such a density have the advantage, compared to the particles of the prior art (such as, for example, for example, porous silica particles, glass powders), to have on their surface an adsorption of the continuous phase of the less important composition and thus a less thickening of the composition.

  Advantageously, the solid particles of the composition according to the invention are solid, non-porous particles.

  Preferably, the solid particles are spherical in shape. By particles of "spherical" shape means particles of spherical or substantially spherical shape (for example of ovoid shape).

  The solid particles used in the compositions according to the invention preferably have a mean size of less than or equal to 50 μm, preferably less than or equal to 40 μm, for example ranging from 0.5 to 30 μm, preferably from 5 to 15 μm. pm and especially about 10 pm. By average size, it is preferably designated the dimension given by the statistical size distribution to half of the population, called D50.

  The solid particles may be of a material chosen from glass, silica, silicates, aluminas, ceramics, mica, a metal such as gold, silver, aluminum, copper, metal oxides such as oxides of titanium, iron, zirconium oxide, cerium oxide, alumina oxides, alloys such as steel, bronze, brass, materials of mineral origin such as quartz, lava or alluvium, or materials derived from animal secretion, such as coral, pearlescent agents, polymers and mixtures thereof.

  The subject of the invention is also a composition for coating keratinous fibers comprising a cosmetically acceptable medium and solid particles made of a material chosen from among glass, silica, silicates, aluminas, ceramics, mica, metals, metal oxides, alloys, materials of mineral origin or materials derived from animal secretion, polymers and mixtures thereof, said composition having a solids content greater than or equal to 47%.

  The particles may be coated or covered in whole or in part by at least one layer of material such as those described above or of other kinds.

  They can be composed of materials of different natures and nonhomogeneous.

  As solid particles that may be used in the present invention, mention may be made in particular of: the glass microspheres sold under the Prizmalite names by Prizmalite, the non-porous silica microspheres marketed under the reference MSS-500 by the company Kobo, and their mixtures.

  Preferably, the solid particles are glass particles.

  This is why the invention also relates to a composition for coating keratinous fibers comprising a cosmetically acceptable medium and glass particles. In particular, the glass particles are glass microbeads. By "glass" is meant any glass composition, the glass generally being, in a nonlimiting manner, composed of a mixture of oxides chosen from oxides of silicon, titanium, barium, aluminum, calcium, magnesium, boron, potassium, sodium, zinc and mixtures thereof.

  In particular, the spherical-shaped glass particles used in the present invention are composed of the following oxides, in the amounts indicated below: SiO 2 in a content ranging from 65 to 76%, Na 2 O in a content ranging from 10 to 16%, CaO in a content ranging from 5 to 15%, MgO in a content ranging from 1 to 6%, Al2O3 in a content ranging from 0.05 to 1%, Fe / Fe2O3 in a content ranging from 0.05 to 0.5% , K2O in a content ranging from 0.05 to 0.5%, and other oxides in the form of traces.

  The solid particles may represent from 0.1 to 40% by weight relative to the total weight of the composition, preferably from 0.5 to 30%, better still from 1 to 20% by weight and more preferably from 5 to 15% by weight. weight.

  Cosmetically acceptable medium This medium may be of the aqueous or non-aqueous type or comprise an aqueous phase and a non-aqueous phase, be non-volatile or comprise at least one volatile compound.

  The cosmetically acceptable medium of the composition may comprise at least one volatile organic solvent or oil defined below.

  For the purposes of the invention, the term "oil or volatile organic solvent" means any nonaqueous medium capable of evaporating on contact with the keratinous fiber in less than one hour, at ambient temperature and atmospheric pressure. The volatile organic solvent (s) and the volatile oils of the invention are organic solvents and volatile cosmetic oils, liquid at ambient temperature, having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, ranging from 0.13 Pa. at 40,000 Pa (10-3 to 300 mmHg), in particular ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa ( 0.01 to 10 mmHg). By "non-volatile oil" is meant an oil remaining on the keratin fiber at ambient temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 10 -3 mmHg (0.13 Pa).

  These oils may be hydrocarbon oils, silicone oils, or mixtures thereof.

  The term "hydrocarbon-based oil" means an oil containing mainly hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur and phosphorus atoms. The volatile hydrocarbon oils may be chosen from hydrocarbon-based oils having from 8 to 16 carbon atoms, and especially branched C 8 -C 16 alkanes such as C 8 -C 16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane. (also known as 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopars' or permetyls, branched esters C8-C16 neopentanoate isohexyl, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell or by Shell, can also be used. Preferably, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.

  As volatile oils, it is also possible to use volatile silicones, for example volatile linear or cyclic silicone oils, in particular those having a viscosity of 6 centistokes (6 × 10 -6 m 2 / s), and having in particular from 2 to 10 carbon atoms. silicon, these silicones optionally containing alkyl or alkoxy groups having from 2 to 22 carbon atoms. As volatile silicone oil that can be used in the invention, there may be mentioned in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethylisiloxane, octamethyltrisiloxane and decamethyl tetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

  The volatile oil may be present in the composition according to the invention in a content ranging from 0.5% to 95% by weight, preferably from 1% to 65% by weight and better still from 5% to 40% by weight, relative to to the total weight of the composition.

  The non-volatile silicone oils that may be used in the composition according to the invention may be non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and / or at the end of the silicone chain, groups each having from 2 to 24 carbon atoms, phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

  The fluorinated oils that can be used in the composition of the invention are in particular fluorosilicone oils, fluorinated polyethers and fluorinated silicones as described in document EP-A-847752.

  The non-volatile oils may be present in the composition according to the invention in a content ranging from 0 to 30% (especially from 0.1 to 30%) by weight, preferably from 0% to 20% by weight (in particular 0, 1 to 20%), relative to the total weight of the composition, and better still from 0% to 10% by weight (especially 0.1% to 10%).

  The oils or organic solvents can in particular form a fatty phase, and in particular a continuous fat phase. The composition may be an anhydrous composition.

  The composition according to the invention may comprise an aqueous medium, constituting an aqueous phase, which can form the continuous phase of the composition.

  The aqueous phase may consist essentially of water; it may also comprise a mixture of water and of a water-miscible solvent (miscibility in water greater than 50% by weight at 25 ° C.), such as lower monoalcohols having from 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 aldehydes; -C4 and mixtures thereof.

  The aqueous phase (water and optionally the water-miscible solvent) may be present in a content ranging from 1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 3% to 80%. by weight, and preferably ranging from 5% to 60% by weight. Wax

  The composition according to the invention may comprise a wax or a mixture of waxes.

  The wax considered in the context of the present invention is generally a lipophilic compound, solid at room temperature (25 ° C.), with reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C. up to 120 ° C. By bringing the wax to the liquid state (melting), it is possible to make it miscible with oils and form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax is obtained in the oils of the mixture.

  In particular, the waxes that are suitable for the invention may have a melting point of greater than about 45, and in particular greater than 55 C.

  The melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name MDSC 2920 by the company TA Instruments.

  The measurement protocol is as follows: A sample of 5 mg of wax placed in a crucible is subjected to a first temperature rise from -20 ° C. to 100 ° C., at a heating rate of 10 ° C./min, and is then cooled. 100 C at -20 C at a cooling rate of 10 C / minute and finally subjected to a second temperature rise ranging from 20 C to 100 C at a heating rate of 5 C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the wax sample as a function of temperature is measured. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature.

  The waxes that may be used in the compositions according to the invention are chosen from waxes, solid and rigid at room temperature, of animal, vegetable, mineral or synthetic origin, and mixtures thereof.

  The waxes that can be used in the compositions according to the invention generally have a hardness ranging from 0.01 MPa to 30 MPa, in particular greater than 0.05 MPa and in particular greater than 0.1 MPa.

  The hardness is determined by the measurement of the compression force measured at 20 C using the texturometer sold under the name TA-TX2i by the company RHEO, equipped with a stainless steel mobile in the form of a cylinder with a diameter of 2 mm by measuring the evolution of the force (compression force or stretching force) (F) as a function of time, during the following operation: The mobile is moved at a speed of 0.1 mm / s and then penetrates in wax to a penetration depth of 0.3 mm. When the mobile penetrated the wax to the depth of 0.3 mm, the mobile is held stationary for 1 second (corresponding to the relaxation time) and is removed at a speed of 0.1 mm / s. During the relaxation time, the force (compression force) decreases sharply until it becomes zero and then when the mobile is removed, the force (stretching force) becomes negative and then increases again to the value 0. The hardness corresponds to the maximum compression force measured between the surface of the mobile and the wax at the time of their contact. The value of this force is expressed in MPa.

  To measure the hardness, the wax is melted at a temperature equal to the melting point of the wax + 20 C. The melted wax is poured into a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C.) for 24 hours and then the wax is kept for at least 1 hour at 20 ° C. before carrying out the hardness measurement.

  In particular, it is possible to use hydrocarbon-based waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Candelilla wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax ; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters.

  Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains.

  Among these, there may be mentioned hydrogenated jojoba oil, isomerized jojoba oil such as trans isomerized partially hydrogenated jojoba oil manufactured or marketed by Desert Whale under the trade reference ISO-JOJOBA-50 , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di (1,1,1-trimethylpropane) tetrastearate sold under the name HEST 2T- 4S by the company HETERENE, di- (trimethylol-1,1,1 propane) tetraprenate sold under the name HEST 2T-4B by the company HETERENE.

  Mention may also be made of silicone waxes and fluorinated waxes.

  It is also possible to use the wax obtained by hydrogenation of olive oil esterified with the stearyl alcohol sold under the name PHYTOWAX Olive 18 L 57 or even the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol. under the name PHYTOWAX ricin 16L64 and 22L73, by the company SOPHIM. Such waxes are described in application FR-A-2792190.

  The composition according to the invention may comprise a content of waxes ranging from 1 to 50% by weight relative to the total weight of the composition, in particular it may contain from 5 to 30%, more particularly from 10 to 30%.

  The wax (es) may be present in the form of an aqueous microdispersion of wax. By aqueous microdispersion of wax is meant an aqueous dispersion of wax particles in which the size of said wax particles is less than or equal to about 1 μm.

  Microdispersions of wax are stable dispersions of colloidal wax particles, and are especially described in "Microemulsions Theory and Practice", L. M. Prince Ed., Academic Press (1977) pages 21-32.

  In particular, these microdispersions of wax can be obtained by melting the wax in the presence of a surfactant, and optionally a portion of the water, and then gradually adding hot water with stirring. The intermediate formation of a water-in-oil type emulsion is observed, followed by a phase inversion with the final obtaining of an oil-in-water type microemulsion. On cooling, a stable microdispersion of solid colloidal particles of wax is obtained.

  The microdispersion of wax can also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high pressure homogenizer, turbines.

  The particles of the microdispersion of wax preferably have average dimensions of less than 1 μm (in particular ranging from 0.02 μm to 0.99 μm), preferably less than 0.5 μm (in particular ranging from 0.06 μm to 0 μm). , 5 pm).

  These particles consist essentially of a wax or a mixture of waxes. However, they may comprise, in a minor proportion, oily and / or pasty fatty additives, a surfactant and / or a usual fat-soluble additive / active agent.

  The composition according to the invention may contain emulsifying surfactants present in particular in a proportion ranging from 2 to 30% by weight relative to the total weight of the composition, and better still from 5% to 15%. These surfactants may be chosen from anionic or nonionic surfactants. Reference can be made to the Encyclopedia of Chemical Technology, KIRK-OTHMER, Volume 22, p.333-43, 3rd edition, 1979, WILEY, for the definition of the properties and functions (emulsifier) of surfactants, in particular p.347 -377 of this reference, for anionic and nonionic surfactants.

  The surfactants preferably used in the composition according to the invention are chosen: from the nonionic surfactants: fatty acids, fatty alcohols, polyethoxylated or polyglycerolated fatty alcohols such as polyethoxylated stearyl or cetylstearyl alcohols, acid esters, fatty and sucrose, alkyl glucose esters, especially polyoxyethylenated C1-C6 alkyl glucose esters, and mixtures thereof.

  - Among the anionic surfactants: C16-C30 fatty acids neutralized with amines, ammonia or alkaline salts, and mixtures thereof.

  Surfactants are preferably used to obtain an oil-in-water or wax-in-water emulsion.

  The composition according to the invention may comprise a film-forming polymer.

  The film-forming polymer may be present in the composition according to the invention in a solids content ranging from 0.1% to 60% by weight relative to the total weight of the composition, preferably from 0.5% to 40%. by weight, and more preferably from 1% to 30% by weight.

  In the present application, the term "film-forming polymer" means a polymer capable of forming, by itself or in the presence of a film-forming auxiliary agent, a continuous and adherent film on a support, in particular on keratin materials such as eyelashes. .

  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.

  By radical-forming film-forming 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 vinyl polymers, or copolymers, especially acrylonitriles.

  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 the monomer bearing an acidic group, α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid may be used. It is preferable to use (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid.

  The acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C 1 -C 30 alkyl, preferably C1-C20, (meth) acrylates of aryl, in particular of C6-C10 aryl, hydroxyalkyl (meth) acrylates, in particular of C2-C6 hydroxyalkyl.

  Among the alkyl (meth) acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl 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. Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.

  According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, that is to say that 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, N-t-octyl acrylamide and N-undecylacrylamide.

  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 and alpha-methyl styrene.

  Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyesters amides, polyamides, and epoxy ester resins, polyureas.

  The polyurethanes may be chosen from anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, poly-urethanespolyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and mixtures thereof.

  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-dimethylglutaric acid , azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2-acid , 6-naphthalenedicarboxylic 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 preferably chosen.

  The diol may be chosen from aliphatic, alicyclic and aromatic diols. A diol chosen from among: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol is preferably 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.

  The polyester may further comprise at least one monomer carrying at least one -SO3M group, with M representing a hydrogen atom, an ammonium NH4 + ion or a metal ion, such as for example an Na +, Li +, K +, Mg2 +, Cal + ion. , Cul +, Fe2 +, Fei +. In particular, it is possible to use a bifunctional aromatic monomer comprising such a group -SO3M.

  The aromatic nucleus of the bifunctional aromatic monomer additionally carrying a group -SO3M as described above may be chosen for example from benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl and methylenediphenyl nuclei. An example of a bifunctional aromatic monomer also bearing an -SO 3 M group is sulfoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid and 4-sulphonaphthalene-2,7-dicarboxylic acid.

  It is preferred to use isophthalate / sulphoisophthalate-based copolymers, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexane di-methanol, isophthalic acid, sulfoisophthalic acid.

  The polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, dammars, elemis, copals, cellulosic polymers, and mixtures thereof.

  According to a first embodiment of the composition according to the invention, the film-forming polymer may be a water-soluble polymer and may be present in an aqueous phase of the composition; the polymer is solubilized in the aqueous phase of the composition. Examples of water-soluble film-forming polymers that may be mentioned include: 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; cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, as well as the quaternized derivatives of cellulose; acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; 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; polymers of natural origin, which may be modified, such as: gum arabic, guar gum, xanthan derivatives, karaya gum; . alginates and carrageenans; glycosaminoglycans, hyaluronic acid and its derivatives; shellac resin, sandaraque gum, dammars, elemis, copals; 15. deoxyribonucleic acid; mucopolysaccharides such as chondroitin sulfate, and mixtures thereof.

  According to another alternative embodiment of the composition according to the invention, the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents such as those described above (it is said that the film-forming polymer is a fat-soluble polymer ). For the purposes of the invention, the term "liquid fatty phase" means a fatty phase that is liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg, ie 105 Pa), composed of one or more fatty substances. liquids at room temperature, such as the oils described above, generally compatible with each other.

  Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil, the oils may be chosen from the oils mentioned above.

  As an example of a fat-soluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and from at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl ester group).

  These copolymers may be crosslinked using crosslinking agents which may be of the vinyl type, or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecanedioate. divinyl.

  Examples of such copolymers include copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyleloctadecene acetate, vinyl acetate / octadecylvinyl ether, propionate vinyl / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, vinyl stearate / allyl acetate, 2,2-dimethyl-vinyl octanoate / vinyl laurate, 2,2-dimethyl-2,2-vinyl allylellaurate pentanoate, vinyl dimethyl propionate / vinyl stearate, allyl dimethyl propionate / vinyl stearate, propionate Vinyl / vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetraallyl oxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / allyl stearate cross-linked with 0 2% divinyl benzene.

  Liposoluble film-forming polymers that may also be mentioned include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 10 to 20 carbon atoms.

  Such liposoluble copolymers may be chosen from copolymers of vinyl polycrystearate, vinyl polystearate crosslinked with divinylbenzene, diallyl ether or diallyl phthalate, copolymers of stearyl poly (meth) acrylate, polyvinylpolate , poly (meth) acrylate lauryl, these poly (meth) acrylates can be crosslinked using dimethacrylate ethylene glycol or tetraethylene glycol.

  The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.

  Liposoluble film-forming polymers that can be used in the invention also include polyalkylenes and especially copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated C such as ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still of C3 to C20 alkene. By way of example of a copolymer of VP which may be used in the invention, mention may be made of the copolymer of VP / vinyl acetate, VP / ethyl methacrylate, polyvinylpyrrolidone (PVP) butylated, VP / ethyl methacrylate / methacrylic acid, VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.

  The film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase or in a non-aqueous solvent phase, generally known under the name of latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

  As the aqueous dispersion of film-forming polymer, it is possible to use the acrylic dispersions sold under the names Neocryl XK-90, Neocryl A-1070, Neocryl A-1090, Neocryl BT-62, Neocryl A1079 and Neocryl A-523 by the company Avecia-Neoresins. Dow Latex 432 by DOW CHEMICAL, Daitosol 5000 AD or Daitosol 5000 SJ by DAITO KASEY KOGYO; Syntran 5760 by the company Interpolymer or the aqueous polyurethane dispersions sold under the trade names Neorez R-981 and Neorez R-974 by the company Avecia-Neoresins, the Avalure UR-405, Avalure UR-410, Avalure UR-425, Avalure UR-450, Sancure 875, Sancure 861, Sancure 878 and Sancure 2060 by the company GOODRICH, Impranil 85 by the company BAYER, Aquamere H-1511 by the company HYDROMER; the sulfopolyesters sold under the brand name Eastman AQ by the company Eastman Chemical Products, vinyl dispersions such as Mexomer PAM and also acrylic dispersions in isododecane, such as Mexomer PAP by the company CHIMEX.

  According to one embodiment, the composition according to the invention advantageously comprises a film-forming linear ethylenic block polymer as described above and particles of film-forming polymer dispersed in an aqueous phase.

  The composition according to the invention may comprise a plasticizer promoting the formation of a film with the film-forming polymer. Such a plasticizer may be chosen from all compounds known to those skilled in the art as being capable of performing the desired function.

  Additives The composition according to the invention may also comprise a dyestuff such as pulverulent dyestuffs, liposoluble dyes and water-soluble dyes.

  This dyestuff may be present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition.

  The pulverulent dyestuffs may be chosen from pigments and nacres.

  The pigments may be white or colored, mineral and / or organic, coated or uncoated. Among the inorganic pigments, titanium dioxide, optionally surface-treated, oxides of zirconium, zinc or cerium, as well as oxides of iron or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue.

  Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.

  The nacres may be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

  Fat-soluble dyes are, for example, Sudan red, D & C Red 17, D & C Green 6, a-carotene, soybean oil, Sudan brown, D & C Yellow 11, D & C Violet 2, D & C orange 5, the yellow quinoline, the annatto. The water-soluble dyes are, for example, beet juice, methylene blue, culinary disodium salt, disodium salt of alizarin green, quinoline yellow, trisodium salt of amaranth, disodium salt of tartrazine, monosodium salt of rhodamine, the disodium salt of fuchsin, xanthophyll.

  The composition according to the invention may further comprise an additional charge, distinct from the particles of the bulk density greater than 0.7 g / cm 3 described above. The fillers may be selected from those well known to those skilled in the art and commonly used in cosmetic compositions. The fillers can be mineral or organic, lamellar or spherical. Mention may be made of talc, mica, silica, kaolin, polyamide powders such as nylon (Orgasol from Atochem), poly-13-alanine and polyethylene, tetrafluoroethylene polymer powders such as Teflon, lauroyllysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as ExpanceL (Nobel Industry), silicone resin microbeads (Toshiba Tospearls for example) particles of polymethyl methacrylate, precipitated calcium carbonate, magnesium carbonate and hydrocyanate, hydroxyapatite, hollow silica microspheres (SILICA BEADS from MAPRECOS), glass or ceramic microcapsules, and derived metal soaps of organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, laurate of zinc, magnesium myristate.

  The fillers can represent from 0.1 to 25%, and better still from 1 to 20% by weight, of the total weight of the composition.

  The composition of the invention may furthermore comprise any additive usually used in cosmetics such as antioxidants, preservatives, perfumes, neutralizers, gelling agents, thickeners, vitamins, and mixtures thereof.

  The gelling agents that may be used in the compositions according to the invention may be lipophilic or hydrophilic gelling agents, they may be organic or inorganic, polymeric or molecular.

  As inorganic lipophilic gelling agents, there may be mentioned optionally modified clays, such as hectorites modified with a C 10 -C 22 fatty acid ammonium chloride, such as hectorite modified with di-stearyl dimethyl ammonium chloride such that for example, that marketed under the name Bentone 38V by the company ELEMENTIS. It is also possible to mention fumed silica optionally treated hydrophobic surface whose particle size is less than 1 dam. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called Silica silylate according to the CTFA (6th edition, 1995). They are for example sold under the references Aerosil R812 by the company Degussa, CAB-O-SIL TS-530 by the company CABOT, dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called Silica dimethyl silylate according to the CTFA (6th edition, 1995). They are for example marketed under the Aerosil R972 references, and Aerosil R974 by the DEGUSSA company, CAB-OSIL TS-610 and CAB-O-SIL TS-720 by CABOT.

  The hydrophobic fumed silica has in particular a particle size that can be nanometric to micrometric, for example ranging from about 5 to 200 nm.

  Polymeric organic lipophilic gelling agents are, for example, partially or fully crosslinked elastomeric organopolysiloxanes of three-dimensional structure, such as those sold under the names KSG6, KSG16 and KSG18 by the company Shin-Etsu, Trefil E-505C and Trefil E-506C. by DOWCORNING, Gransil SR-CYC, SR DMF10, SR-DC556, SR 5CYC gel, SR DMF 10 gel and SR DC 556 gel by GRANT INDUSTRIES, SF 1204 and JK 113 by the company GENERAL ELECTRIC ; ethylcellulose such as that sold under the name Ethocel by Dow Chemical; galactomannans having from one to six, and in particular from two to four, hydroxyl groups per sac, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated with C1-C6 alkyl chains, and in particular with C , C3 and mixtures thereof. Block copolymers of the diblock or triblock type of the polystyrene polyisoprene or polystyrene / polybutadiene type, such as those sold under the name Luvitol HSB by the company BASF, of the polystyrene / polypropylene (ethylenepropylene) type, such as those sold under the name Kraton by Shell Chemical. CO or polystyrene / copoly (ethylene-butylene) type.

  Among the lipophilic gelling agents that can be used in the compositions according to the invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates, in particular such as those sold under the names Rheopearl TL or Rheopearl KL. by the company CHIBA FLOUR.

  As hydrophilic gelling agents, mention may in particular be made of the AMPS / acrylamide copolymers of SEPIGEL or SIMULGEL type sold by the company SEPPIC.

  Of course, those skilled in the art will take care to choose any additional additives and / or their quantity in such a way that the advantageous properties of the composition according to the invention are not or not substantially impaired by the addition envisaged.

  The composition according to the invention can be manufactured by known methods, generally used in the cosmetics field.

  Preferably, the composition according to the invention is a mascara.

  The invention is illustrated in more detail in the following examples. Quantities are given in grams.

  EXAMPLE 1 Emulsion Mascara An emulsion mascara was prepared according to the invention having the following composition: Beeswax 5.4 Candelilla wax 2 Rice bran wax 6.1 Carnauba wax 6.1 Polyolefin wax (Vibar ) 0.1 Hydrogenated jojoba oil 0.5 Cottonseed oil 0.5 Gum arabic 3.4 Ethyl acrylate / methyl methacrylate copolymers 1 crosslinked in a 50% aqueous dispersion (Daitosol 5000AD by DAITO KASEY KOGYO) Polymethacrylate sodium in water at 25% (Darvan 7 1 from VANDERBILT) Hydroxyethyl cellulose quaternized with 2,3 0,1-epoxypropyl trimethylammonium chloride (Polyquaternium 10) Hydroxyethylcellulose 0.9 Glass microspheres from Prizmalite (size: 9 8 microns bulk density: 0.9 g / cm3) 7 Pigments (iron oxides) Stearic acid 5.8 Triethanolamine 2,4 Simethicone 0.1 Polydimethylsiloxane oxyethylenated (20 OE) oxypropylene 0.2 (20 OP) (Resin Q- 2 5220 from Dow Corning) 0.45 Panthenol 0.5 Preservatives Water Qsp 100 Procedure: The waxes are melted in a skillet at a temperature of about 90 ° C. with stearic acid and then the pigments are dispersed with stirring in this waxy phase for about 15 minutes. The aqueous phase, hydroxyethylcellulose) and gum arabic are heated to about 85 C and then gradually incorporated into the above mixture under high shear (Moritz) to form an emulsion. The glass microbeads are then introduced into the mixture with stirring.

  The emulsion obtained is allowed to cool to room temperature (25 ° C.) and then the resin, sodium polymethacrylate, polyquaternium 10, the aqueous dispersion of ethyl acrylate / methyl methacrylate copolymers and dimethicone copolyol are added.

  This mascara has a dry extract, measured by the previously described method, of 49.2% and a satisfactory consistency.

  This mascara has been evaluated by 12 people. It has been judged to have a good loading effect as well as a smooth and homogeneous deposit.

Claims (27)

  1. Composition for coating keratinous fibers comprising a cosmetically acceptable medium and solid particles having a bulk density (pv) greater than or equal to 0.7 g / cm 3, said composition having a solids content greater than or equal to 47%.   2. Composition according to the preceding claim, characterized in that the solid particles have a bulk density greater than or equal to 0.8 g / cm3, better still greater than or equal to 0.9 g / cm3.   3. Composition according to one of the preceding claims, characterized in that the solid particles are of a material selected from glass, silica, silicates, aluminas, ceramics, mica, metals, metal oxides, alloys, materials of mineral origin or materials derived from animal secretion, polymers and their mixtures.   4. Composition for coating keratinous fibers comprising a cosmetically acceptable medium and glass particles.   5. Composition according to claim 1, characterized in that the particles are solid particles.   6. Composition according to one of the preceding claims, characterized in that the particles are spherical.   7. Composition according to one of the preceding claims, characterized in that the solid particles have a mean size less than 50 pm.   8. Composition according to one of the preceding claims, characterized in that the solid particles have a mean size of less than 40 microns.   9. Composition according to one of the preceding claims, characterized in that the solid particles represent from 0.1 to 40% by weight relative to the total weight of the composition, preferably from 0.5 to 30%, better than 1. at 20% by weight and more preferably from 5 to 15% by weight.   10. Composition according to any one of the preceding claims, characterized in that it comprises a volatile oil.   11. Composition according to the preceding claim, characterized in that the volatile oil is selected from hydrocarbon oils, silicone oils, or mixtures thereof.   12. Composition according to claim 10 or 11, characterized in that the volatile oil is present in a content ranging from 0.5% to 95% by weight, preferably from 1 to 65% by weight and better still at 40% by weight.   13. Composition according to any one of the preceding claims, characterized in that it comprises a non-volatile oil.   14. Composition according to the preceding claim, characterized in that the non-volatile oil is present in a content ranging from 0.1% to 30% by weight, preferably from 0.1% to 20% by weight, relative to to the total weight of the composition, and more preferably from 0.1% to 10% by weight.   15. Composition according to any one of the preceding claims, characterized in that it comprises an aqueous phase formed of water or a mixture of water and water-miscible organic solvent.   16. Composition according to the preceding claim, characterized in that the aqueous phase is present in a content ranging from 1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 3% to 80% by weight. weight, and preferably ranging from 5% to 60% by weight.   17. Composition according to any one of the preceding claims, characterized in that it comprises a wax.   18. Composition according to the preceding claim, characterized in that the total wax content of the composition ranges from 1 to 50% by weight relative to the total weight of the composition, in particular from 5 to 30%, more particularly from 10 to 30% by weight. at 30%.   19. Composition according to any one of the preceding claims, characterized in that it comprises a film-forming polymer.   20. Composition according to the preceding claim, characterized in that the film-forming polymer is present in a dry matter content ranging from 0.1% to 60% by weight relative to the total weight of the composition, preferably from 0, 5% to 40% by weight, and preferably ranging from 1% to 30% by weight.   21. Composition according to any one of the preceding claims, characterized in that it comprises a surfactant.   22. Composition according to any one of the preceding claims, characterized in that it comprises an additive chosen from dyestuffs, antioxidants, fillers, pasty fatty substances, preservatives, perfumes, neutralizers, thickeners. , vitamins, coalescing agents, plasticizers, and mixtures thereof.   23. Composition according to one of the preceding claims, characterized in that it has a dry extract greater than or equal to 47.5%, preferably greater than or equal to 48%, better still, greater than or equal to 49%, even better greater than or equal to 50%, up to 60%.   24. Composition for coating keratinous fibers comprising a cosmetically acceptable medium and solid particles made of a material chosen from glass, silica, silicates, aluminas, ceramics, mica, metals, metal oxides, alloys, materials of mineral origin or materials derived from animal secretion, polymers and mixtures thereof, said composition having a solids content greater than or equal to 47%.   25. A cosmetic process for makeup or non-therapeutic care of keratinous fibers comprising applying to the keratin fibers a composition according to any one of claims 1 to 24.   26. Use of a composition according to any one of the preceding claims, for obtaining a makeup of keratinous fibers, in particular eyelashes, loading and / or a smooth and homogeneous deposit on the keratinous fibers.   Use of bulk density particles greater than or equal to 0.7 g / cm 3 in a composition for coating keratinous fibers, in particular eyelashes, to obtain a composition which is easily applied to keratinous fibers and / or leads to a smooth and homogeneous deposit on the keratinous fibers and a makeup loading.