FR2844999A1 - Cosmetic composition comprising an adhesive wax and a filler with a specified surface area, useful for protection or as make-up for keratinic materials - Google Patents

Abstract

Cosmetic composition comprising a wax with an adhesion greater or equal to 0.7 N.s and a hardness less than or equal to 3.5 MPa, and a filler of surface area BET greater or equal to 100 m2/g. Independent claims are also included for the application and use of the composition.

Description

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 The present invention relates to a cosmetic composition combining at least one tacky wax and at least one filler having a specific surface area greater than or equal to 100 m 2 / g. It also relates to a cosmetic process for the care or makeup of keratin materials using said composition.

 The composition according to the invention can be used in particular in the field of makeup or care of keratin materials such as skin, eyelashes, eyebrows, hair and nails of human beings. In this case, it may be in the form of mascara, eyebrow product, eyeliner, eyeshadow, blush, foundation, lip body makeup (semi-permanent tattoo), hair makeup product.

 More particularly, the invention relates to a mascara.

 The mascara composition can be a make-up composition, a composition to be applied on or under a make-up, also called a top-coat or a base-coat, or else an eyelash treatment composition.

 Mascaras are commonly prepared according to two types of formulation: aqueous mascaras, so-called cream mascaras, in the form of emulsion of waxes in water; anhydrous mascaras or low-water mascaras, in the form of dispersions of waxes in organic solvents.

 It is known to use various waxes for the formulation of mascaras such as those described in document WO-A-91/12793, for example beeswax, candelilla wax, carnauba wax, or even wax. of polyethylene.

 However, when the mascaras contain certain waxes in a significant amount, especially beyond 20% by weight of the total weight of the mascara of a wax, such as carnauba wax, rice bran wax or polyethylene wax, the The eyelash makeup deposit obtained has a granular appearance thus conferring a non-smooth and non-homogeneous makeup defects that make the makeup unsightly.

 Recently, the inventors have demonstrated that it is possible to overcome this problem subject to using a particular wax having tacky properties (high tack). Advantageously, this wax makes it possible to obtain a cosmetic composition which is easily applied to keratin materials, having good adhesion to keratin materials and which leads to the formation of a smooth and homogeneous makeup, which does not have a grainy appearance .

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 In addition, such a wax may be incorporated into the composition at a content of up to 50% by weight, relative to the total weight of the composition, without obtaining a build-up of the composition: the composition is stable (especially stability after 24 hours at 25 ° C.), remains of a creamy consistency and is easily applied to keratin materials.

 However, for certain cosmetic applications, it would be advantageous to be able to moderate the natural tights of this type of wax. Thus, in the particular case of mascara-type formulas, this sticky appearance can be troublesome when one seeks to obtain besides a perfect individualisation of the eyelashes.

 Unexpectedly, the inventors have found that it is possible to satisfy this additional requirement provided that said adhesive wax is associated with at least one filler having a BET specific surface area greater than or equal to 100 m 2 / g.

 More specifically, the present invention relates, according to a first aspect, to a cosmetic composition and in particular to the makeup or care of keratinous materials comprising, in a cosmetically acceptable medium, at least one wax having a tack greater than or equal to 0.7 N. s and a hardness less than or equal to 3.5 MPa and at least one filler having a specific surface area greater than or equal to 100 m 2 / g.

 The present invention also relates, according to another of its aspects, to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one C20-C40 alkyl (hydroxystearyloxy) stearate and at least one filler having a BET higher surface area or equal to 100 m2 / g.

 According to a particular variant of the invention, these cosmetic compositions are mascara compositions.

 The subject of the invention is also a cosmetic process for makeup or non-therapeutic care of keratin materials, in particular skin, nails, hair, eyelashes, eyebrows, comprising the application to keratin materials of a composition as defined above.

 The subject of the invention is also, according to another of its aspects, the use of a composition as defined above for producing a makeup of homogeneous and / or smooth keratin materials, and in particular a make-up of the loading and separating eyelashes.

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 According to another of its aspects, the subject of the invention is also the use of at least one filler having a specific surface area greater than or equal to 100 m 2 / g in a cosmetic composition containing in particular at least one wax having a higher tack. or equal to 0.7 N. s and a hardness less than or equal to 3.5 MPa, to obtain a homogeneous and / or smooth makeup of the keratinous materials and in particular an eyelash makeup, loading and separating, and / or obtain a composition stable cosmetic, the wax being present at a content of at least 10%, especially at least 20% by weight, and in particular at least 25% by weight relative to the total weight of the composition.

 Cosmetically acceptable medium is understood to mean a cosmetic medium compatible with keratin materials such as eyelashes, skin including lips, hair, nails, eyebrows.

Sticky wax
As stated above, the wax considered according to the invention has a tack greater than or equal to 0.7 N.s and a hardness less than or equal to 3.5 MPa.

 It has a tack greater than or equal to 0.7 N. s, especially ranging from 0.7 N. s to 30 Ns, in particular greater than or equal to 1 N. s, in particular ranging from 1 N. s to 20 N. s, and in particular greater than or equal to 2 N. s, especially ranging from 2 N.s to 10 Ns, in particular ranging from 2 N.s to 5 Ns

 The tacky wax has a hardness less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, in particular ranging from 0.05 MPa to 3 MPa, or even ranging from 0.1 MPa to 2 MPa. , 5 MPa.

 For the purposes of the present invention, the term "wax" is intended to mean a lipophilic fat compound which is solid at room temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 105 Pa), with a reversible solid / liquid state change. , having a melting temperature of greater than 30 ° C. and better still greater than 55 ° C. and up to 200 ° C., especially up to 120 ° C.

 By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax in the oils of the mixed.

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 The melting point values correspond, according to the invention, to the melting peak measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company METLER, with a temperature rise of 5 or 10 C per minute.

 To measure the stickiness of the wax, the wax is melted at a temperature equal to the melting point of the wax + 10 C. The melted wax is poured into a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C.) for 24 hours so that the surface of the wax is flat and smooth, then the wax is kept for at least 1 hour at 20 ° C. before measuring the adhesive.

The glue of the wax is measured at 20 ° C. using the texturometer sold under the name TA-TX21 # by the company RHEO, equipped with a mobile device made of a cone-shaped acrylic polymer forming an angle of 45, by measuring the evolution of the force (compressive force or stretching force) (F) as a function of time, during the following operation:
The mobile is moved at a speed of 0.5 mm / s and then penetrates into the wax to a depth of penetration of 2 mm. When the mobile penetrated the wax to the depth of 2 mm, the mobile is held stationary for 1 second (corresponding to the relaxation time) and then removed at a speed of 0.5 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 pantyhose corresponds to the integral of the force vs. time curve for the part of the curve corresponding to the negative values of the force (stretching force). The value of the pantyhose is expressed in Ns

 The hardness of the wax is determined by measuring the compressive strength measured at 20 C using the texturometer sold under the name TA-XT2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm moving at the measurement speed of 0.1 mm / s, and penetrating into the wax at a penetration depth of 0.3 mm. To perform the hardness measurement, the wax is melted at a temperature equal to the melting point of the wax + 20 C. The melted wax is cast in 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. The hardness value is the compression force

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 measured maximum divided by the surface of the cylinder of the texturometer in contact with the wax.

dans laquelle n est un entier allant de 18 à 38, ou un mélange de composés de formule (I). As sticky wax, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms), alone or in a mixture, in particular a 12- (12'-hydroxystearyloxy) stearate, may be used. C20-C40 alkyl of formula (I):

wherein n is an integer from 18 to 38, or a mixture of compounds of formula (I).

 Also, the subject of the invention is also a mascara composition comprising, in a physiologically acceptable medium, at least one C20-C40 alkyl (hydroxystearyloxy) stearate, in particular an alkyl 12- (12-hydroxystearyloxy) stearate. in C20-C40, in particular of formula (I) as described above and at least one filler with a specific surface area greater than or equal to 100 m 2 / g.

 Such a wax is especially sold under the names Kester WAX K 82 P # and Kester WAX K 80 P # by the company Koster Keunen.

 The tacky wax, for example a C 20 -C 40 alkyl (hydroxystearyloxy) stearate, may be present in the composition according to the invention in a content ranging from 0.5% to 60% by weight, in particular from 1% to 50% by weight. by weight, especially ranging from 10% to 40% by weight relative to the total weight of the composition.

Specific surface charge
The composition according to the invention comprises at least one filler capable of having a specific surface area greater than or equal to 100 m 2 / g, in particular ranging from 100 to 5000 m 2 / g, in particular from 150 to 1000 m 2 / g, or even from 200 to 800 m 2 m2 / g.

 By charge is meant particles of all forms, insoluble in the medium of the composition, regardless of the temperature at which the composition is manufactured.

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 "Surface-specific charge" means a filler having a specific surface area measured according to the BET method greater than or equal to 100 m 2 / g.

 The BET specific surface is determined according to the BET method (BRUNAUER - EMMET - TELLER) described in The Journal of the American Chemical Society, vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (Appendix D). The BET specific surface area corresponds to the total specific surface area (thus micropores included) of the charge.

 The amount laden in the composition according to the invention is generally adjusted so as to control the stickiness of the associated wax to the desired value.

 Thus, the fillers according to the invention are particularly advantageous for the preparation of cosmetic compositions comprising at least 10%, especially 20%, in particular at least 25% by weight of at least one sticky wax.

 By way of illustration, this filler may be present in the composition according to the invention in an amount ranging from 0.1 to 25%, especially from 0.5 to 20% and in particular from 1 to 15% by weight relative to the weight. total of the composition.

 Advantageously, the tacky wax and the surface-specific filler are present in a content such that the weight ratio of the tacky wax relative to the surface-specific filler varies from 350 to 0.1, especially from 100 to 0.5, in especially from 50 to 0.8 and more preferably from 30 to 1.

 The particles comprising the surface-specific charge may have an average size ranging from 0.01 to 100 m, in particular from 0.1 to 50 m, and better still from 1 to 20 m. By average size, we designate the dimension given by the statistical size distribution to half of the population, called D50.

 The surface-specific filler according to the invention may be chosen in particular from organic and inorganic fillers and / or their mixtures.

 The organic filler may be chosen from polyolefin waxes such as polyethylene waxes and especially those sold under the name Performalen 2000 by the company New Phase Technology or from polymeric fillers such as polymethylmethacrylate (PMMA) such as Jurymer MB1 # sold by Nihon Junyaku or polytetrafluoroethylene (PTFE). As a representative and non-limiting example of the mineral fillers, mention may be made especially of silicas, silicates, aluminas, aluminosilicates, especially those sold under the name

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   Sunsil 130 by the company Sunjin Chemical or Silicabeads SB150 # by the Miyoshi Company.

 The particles composing the surface-specific charge may have various forms. These particles may be in particular globular, lamellar, in particular spherical, hollow or solid. The hollow charges are particularly advantageous.

 Thus, in the particular case of a mineral filler, the hollow silica microspheres are particularly suitable, and in particular such as the Asahi Glass Sunsphere H-51 with a specific surface area of 770 m 2 / g, and the Sunsil 130 of Sunjin Chemical with a surface area of 200-260 m2 / g.

 According to a particular embodiment of the invention, the composition comprises at least one tacky wax and at least one filler having a specific surface greater than or equal to 100 m 2 / g, such as hollow and spherical silica, silica microspheres. hollow, and / or polyethylene wax.

Physiologically acceptable medium
The physiologically acceptable medium of the composition may comprise a volatile solvent, chosen in particular from water, volatile organic solvents and volatile oils defined below, and mixtures thereof.

 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 organic 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-C4 aldehydes .

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

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 The composition according to the invention may comprise an oil or organic solvent, volatile or non-volatile, which may in particular form a fatty phase, and in particular a continuous fat phase. The composition may be an anhydrous composition.

 For the purposes of the invention, the term "oil or volatile organic solvent" means any nonaqueous medium capable of evaporating on contact with the skin 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 which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 0 to 0.1 to 300 mm Hg (1.33 Pa to 40,000 Pa) and preferably greater than 0.3 mm Hg (30 Pa). By "non-volatile oil" is meant an oil remaining on the skin at room temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure of less than 0.01 mmHg (1.33 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-based oils may be chosen from hydrocarbon-based oils containing 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 called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names Isopars' or permetyls, C8-C16 branched esters such as isohexyl neopentanoate, 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 <8 centistokes (8 × 10 -6 m 2 / s), and having in particular from 2 to 7 silicon atoms, these silicones optionally having alkyl or alkoxy groups having from 1 to 10 carbon atoms. As the volatile silicone oil that can be used in the invention, it is possible to

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 mention in particular octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyl disiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

 The volatile oil may be present in the composition according to the invention at a content ranging from 0.1% to 98% by weight, especially from 1% to 65% by weight relative to the total weight of the composition.

 The composition may also comprise at least one non-volatile oil, especially chosen from non-volatile hydrocarbon and / or silicone oils.

Non-volatile hydrocarbon oils that may especially be mentioned include: hydrocarbon-based oils of vegetable origin, such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have various chain lengths of C4 to C24, the latter may be linear or branched, saturated or unsaturated; these oils include wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, avocado, olive, soya, sweet almond oil , palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, pumpkin, rapeseed, blackcurrant, evening primrose, millet, barley quinoa, rye, safflower, bancoulier, passionflower, muscat rose; or alternatively caprylic / capric acid triglycerides, such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810,812 and 818 by the company Dynamit Nobel, synthetic ethers having from 10 to 40 carbon atoms; linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam, squalane, and mixtures thereof; synthetic esters, such as oils of formula R1COOR2 in which R1 represents the residue of a linear or branched fatty acid having from 1 to 40 carbon atoms and R 2 represents a particularly branched hydrocarbon chain containing from 1 to 40 carbon atoms, provided that R 1 + R 2 is # 10, such as for example Purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, C12-C15 alcohol benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate,

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 octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate; and pentaerythritol esters, branched-chain and / or unsaturated carbon-chain liquid fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol , 2-butyloctanol, 2undecylpentadecanol, - higher fatty acids such as oleic acid, linoleic acid, linolenic acid and mixtures thereof.

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 non-volatile oils may be present in the composition according to the invention in a content ranging from 0 to 50% (especially from 0.1 to 50%) by weight, preferably from 0% to 40% by weight (in particular 0, 1 to 40%), relative to the total weight of the composition, and better still from 0% to 30% by weight (especially 0.1% to 30%).

 The composition according to the invention may further comprise an additional wax, different from the sticky wax described above. The additional wax may be chosen from, for example, beeswax, paraffin waxes, hydrogenated castor oil and silicone waxes.

 In particular, the wax may be present in the form of a wax-in-water emulsion.

 The additional wax may be present in the composition according to the invention in a content ranging from 0.1% to 50% by weight, relative to the total weight of the composition, preferably from 0.5% to 30% by weight. and better from 1% to 20% by weight.

 The composition according to the invention may comprise at least one pasty fatty compound at room temperature. For the purposes of the invention, the term "pasty fatty substance" means fatty substances having a melting point ranging from 20 to 55 ° C., preferably 25 to 45 ° C., and / or

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 a viscosity at 40 ° C ranging from 0.1 to 40 Pa · s (1 to 400 poise), preferably 0.5 to 25 Pa · s, measured with Contraves TV or Rhéomat 80, equipped with a mobile rotating at 60 Hz The person skilled in the art can choose the mobile device for measuring the viscosity, among the mobiles MSR3 and MS-R4, on the basis of his general knowledge, so as to be able to measure the pasty compound tested.

 Preferably, these fatty substances are hydrocarbon compounds, optionally of polymeric type; may also be chosen from silicone compounds; may also be in the form of a mixture of hydrocarbon compounds and / or silicone. In the case of a mixture of different pasty fatty substances, use is preferably made of hydrocarbon-based pasty compounds (mainly containing carbon and hydrogen atoms and optionally ester groups), in majority proportion.

 Among the pasty compounds that may be used in the composition according to the invention, mention may be made of lanolins and lanolin derivatives, such as acetylated lanolines, oxypropylenated lanolins or isopropyl lanolate, having a viscosity of 18 to 21 Pa. s, preferably 19 to 20.5 Pa, and / or a melting point of 30 to 55 ° C and mixtures thereof. It is also possible to use esters of fatty acids or alcohols, in particular those having 20 to 65 carbon atoms (melting point of about 20 to 35 ° C. and / or viscosity at 40 ° C. ranging from 0.1 to 40 Pa. S) such as tri-isostearyl citrate or cetyl citrate; arachidyl propionate; vinyl polylaurate; esters of cholesterol such as triglycerides of plant origin such as hydrogenated vegetable oils, viscous polyesters such as poly (12-hydroxystearic acid) and mixtures thereof.

 Mention may also be made of silicone pasty fatty substances such as polydimethylsiloxanes (PDMSs) having pendent chains of the alkyl or alkoxy type having from 8 to 24 carbon atoms, and a melting point of 20-55 ° C., such as, for example, stearyl dimethicones. those sold by Dow Corning under the trade names DC2503 and DC25514, and mixtures thereof.

 The pasty fatty substance may be present in the composition according to the invention in a content ranging from 0.01 to 60% by weight, relative to the total weight of the composition, preferably ranging from 0.5 to 45% by weight. and more preferably from 2% to 30% by weight in the composition.

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 The composition according to the invention and more particularly in the case of mascaras in emulsion form 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 5% to 15%. These surfactants may be chosen from anionic or nonionic surfactants. See Encyclopedia of Chemical Technology, KIRK-OTHMER, Vol. 22, p. 333-432, 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, in particular polyoxyethylenated Ci-Ce alkyl glucose fatty 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 at least one film-forming polymer.

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

 In the present description, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.

 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.

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 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 polymers, or copolymers, vinylic polymers, in particular acrylic polymers.

 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 acid group bearing monomer, unsaturated [alpha], ss-ethylenic 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 (meth) acrylic acid esters (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C 1 -C 30 alkyl, preferably C 1 -C 20, (meth) acrylates of aryl, in particular of 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, 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, ie 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 in particular N-alkyl (meth) acrylamides, in particular alkyl (meth) acrylamides,

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 C2-C12. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, N-tert-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, polyester 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-acid. dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-acid, cyclohexanedicarboxylic acid, 1,4cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5naphthalenedicarboxylic acid, 2,6-acid -naphtalènedicarboxylique. 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.

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 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 bearing at least one -SO 3 M group, with M representing a hydrogen atom, an NH 4 + ammonium ion or a metal ion, for example an Na +, Li +, K +, Mg 2+ or Ca 2+ ion. , Cu2 +, Fe2 +, Fe3. In particular, it is possible to use a bifunctional aromatic monomer comprising such a group -SO 3 M.

 The aromatic nucleus of the bifunctional aromatic monomer additionally carrying a group -SO 3 M 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 a group -SO 3 M: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulphonaphthalene-2,7-dicarboxylic acid.

 It is preferred to use copolymers based on isophthalate / sulphoisophthalate, 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 include:

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 proteins, such as proteins of vegetable origin, such as wheat and 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 quaternized derivatives of cellulose, - acrylic polymers or copolymers, such as polyacrylates or polymethacrylates, - vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, copolymer of acetate vinyl and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl, - polymers of natural origin, optionally modified, such as: - arabic gums, guar gum, xanthan derivatives, karaya gum, - alginates and carrageenans, - glycoaminoglycans, acid hyaluronic acid and its derivatives, shellac resin, sandarac gum, dammars, elemis, copals, deoxyribonucleic acid, muccopolysaccharides such as chondroitin sulphates, 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, also called oils, generally compatible with each other.

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 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: vinyl / allyl stearate copolymers, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinyl ether, vinyl propionate / 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-dimethylvinyl octanoate / vinyl laurate, 2,2-dimethyl-2,2-allyl pentanoate / vinyl laurate, vinyl dimethylpropionate / vinyl stearate, allyl dimethyl propionate / sodium stearate vinyl, vinyl propionate / vinyl stearate, cross-linked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, cross-linked with 0 , 2% tetraallyloxyethane vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 cross-linked 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 homopolymers, and in particular those resulting from homopolymerization.

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 vinyl esters having 9 to 22 carbon atoms or alkyl acrylates or methacrylates, the alkyl radicals having from 10 to 20 carbon atoms.

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

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

 As liposoluble film-forming polymers that can be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, and alkylcelluloses with a linear or branched alkyl radical, whether or not saturated with C 1 to C 8, such as ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and C2 to C40 alkene and better still C3 to C20. 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 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.

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 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.

 Liposoluble dyes are, for example, Sudan Red, D & C Red 17, D & C Green 6, (3-carotene, soybean oil, Sudan Brown, D & C Yellow 11, D & C Violet 2, D & C Orange 5 , quinoline yellow, annatto The water-soluble dyes are for example beet juice, methylene blue, disodium salt of culvert, disodium salt of alizarin green, quinoline yellow, trisodium salt of amaranth , the disodium salt of tartrazine, the monosodium salt of rhodamine, the disodium salt of fuchsin, xanthophyll.

 The composition of the invention may furthermore comprise any additive usually used in cosmetics, such as antioxidants, different charges of fillers having a specific surface area greater than or equal to 100 m 2 / g, preservatives, perfumes, neutralizers, thickeners, vitamins, plasticisers and mixtures thereof.

 According to a particular embodiment of the invention, the composition does not contain a UV filter (organic filter or mineral filter, filter absorbing or reflecting ultraviolet radiation).

 Of course, those skilled in the art will take care to choose the possible additional additives and / or their quantity in such a way that the advantageous properties of the

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 composition according to the invention are not or substantially not, altered by the addition envisaged.

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

 The examples given below are illustrative and not limiting to the field of the invention.

Examples 1 to 3
For the preparation of an anhydrous mascara, the following compounds and their respective amounts were selected: - Sticky wax (Kester Wax K 82 P # from Koster Keunen) 27 g - Bentonite 2.66 g - Propylene carbonate 1, 7 g - Vinyl acetate / allyl stearate copolymer (65/35) (CHIMEX Mexomère PQ #) 2.2 g - Vinyl polylaurate (CHIMEX PPM Mexomer) 0.7 g - Stearate of the oligomer of 12-hydroxystearic acid (SOLSPERSE 21000 # of AVECIA) 0.1g - specific surface charge 15 g - Pigments 4.2 g - Preservatives qs - Isododecane qs 100 g
From this formulation, were prepared three different mascaras according to the invention by incorporating for each of them a specific charge.

 The nature of the three selected fillers, their respective specificities and amounts are indicated in Table 1.

 Sunsil 130 silica is marketed by Sunjin Chemical.

 The polymethyl methacrylate Jurymer MB1 # is marketed by Nihon Junyaku and the silica Sunsphere H-51 is marketed by Asahi Glass.

The tights are appreciated according to the following protocol:
We make up a test tube made of straight hair (60 hair of 15mm

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 of length) by applying the product in 30 successive passages with a brush. After drying for one hour, make-up hair is rubbed back and forth with your finger. The tights are qualitatively assessed according to the degree of hair glued from 1 (not glued at all) to 5 (very glued).

 The three waterproof mascaras thus obtained adhere well to the eyelashes. They give the lashes a smooth and homogeneous makeup, very separating.

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<Tb>

Table <SEP> 1
<tb> Size <SEP> of <SEP> la
<tb> Example <SEP> Name <SEP> Surface <SEP> specific <SEP> Sticky <SEP> after <SEP> friction
<tb> Nature <SEP> Chemical <SEP> Mass <SEP> (g) <SEP> load
<tb> (Formula) <SEP> commercial <SEP> m2 / g <SEP> on <SEP> specimens <SEP>
<tb> m
<tb> N <SEP> 1 <SEP> Silice <SEP> dig <SEP> and <SEP> 1
<tb> sunsil <SEP> 130 # <SEP> 15 <SEP> 6 <SEP> - <SEP> 9 <SEP> 200 <SEP> - <SEP> 260 <SEP>
<tb> spherical
<tb> N <SEP> 2 <SEP> polymethacrylate <SEP> from
<tb> Jurymer <SEP> MB1 # <SEP> 15 <SEP> 8-15 <SEP> 300
<tb> methyl <SEP> 2
<tb> N <SEP> 3 <SEP> Sunsphere <SEP><SEP> Microspheres of <SEP> silica <SEP> 1
<tb> 15 <SEP> 5 <SEP> 770
<tb> H-51 <SEP> digs
<Tb>

Claims (43)

1. Cosmetic composition comprising in a physiologically acceptable medium, at least one wax having a tack greater than or equal to 0.7 N.s and a hardness less than or equal to 3.5 MPa, and at least one filler having a BET specific surface area greater than or equal to 100 m2 / g.  2. Composition according to claim 1, characterized in that the wax has a tack ranging from 0.7 N. s to 30 N.s.  3. Composition according to claim 1 or 2, characterized in that the wax has a tack greater than or equal to 1 N. s, in particular ranging from 1 N. s to 20 N.s.  4. Composition according to any one of the preceding claims, characterized in that the wax has a tack greater than or equal to 2 N. s, in particular ranging from 2 N. s. at 10 N.s  5. Composition according to any one of the preceding claims, characterized in that the wax has a hardness ranging from 0.01 to 3.5 MPa.  6. Composition according to any one of the preceding claims, characterized in that the wax has a hardness ranging from 0.05 MPa to 3 MPa, and in particular ranging from 0.1MPa to 2.5 MPa.  7. Composition according to any one of the preceding claims, characterized in that the wax is a C20-C40 alkyl (hydroxystearoyloxy) stearate alone or in a mixture.  8. Composition according to any one of the preceding claims, characterized in that the wax is present in a content ranging from 0.5% to 60% by weight, especially from 1% to 50% by weight, in particular ranging from % to 40%, relative to the total weight of the composition.  9. Cosmetic composition comprising, in a cosmetically acceptable medium, at least one C20-C40 alkyl (hydroxystearyloxy) stearate and at least one filler having a BET specific surface area greater than or equal to 100 m 2 / g.  10. Composition according to the preceding claim, characterized in that said (C20-C40) alkyl (hydroxystearyloxy) stearate is present in a content ranging from 0.5% to 60% by weight, in particular ranging from 10% to 50% by weight. weight, and in particular ranging from 10% to 40% by weight relative to the total weight of the composition. <Desc / Clms Page number 24>  11. A composition according to claim 9 or 10, characterized in that it comprises at least one C20-C40 alkyl 12- (12'-hydroxystearyloxy) stearate having the following formula (I):

 wherein n is an integer from 18 to 38, or a mixture of compounds of formula (I).  12. Composition according to any one of the preceding claims, characterized in that it comprises at least one filler having a specific surface area ranging from 100 to 5000 m 2 / g in particular from 150 to 1000 m 2 / g, and in particular from 200 to 800 m2 / g.  13. Composition according to any one of the preceding claims, characterized in that the surface-specific filler is chosen from organic and inorganic fillers, and mixtures thereof.  14. Composition according to Claim 13, characterized in that the organic surface-specific filler is chosen from polyolefin waxes and in particular polyethylene waxes and polymer fillers of the polymethyl methacrylate or polytetrafluoroethylene type.  15. The composition of claim 13 or 14, characterized in that the inorganic surface-specific filler is selected from silicas, aluminas, silicates, and aluminosilicates.  16. Composition according to any one of the preceding claims, characterized in that the particles making up the filler have an average size ranging from 0.01 to 100 m, in particular from 0.1 to 50 m and in particular from 1 to 20 m.  17. Composition according to any one of the preceding claims, characterized in that the particles comprising the surface-specific filler are hollow. <Desc / Clms Page number 25>  18. Composition according to any one of the preceding claims, characterized in that the particles comprising the surface-specific filler are microspheres of hollow silica.  19. Composition according to any one of the preceding claims, characterized in that the weight ratio of the tacky wax relative to the surface-specific filler varies from 350 to 0.1, in particular from 100 to 0.5, and in particular from 50 to 0.8 and better from 30 to 1.  20. Composition according to any one of the preceding claims, characterized in that it contains from 0.1 to 25% filler with a specific surface area, in particular from 0.5 to 20%, and in particular from 1 to 15% by weight. weight relative to the total weight of the composition.  21. Composition according to any one of the preceding claims, characterized in that it does not contain a UV filter.  22. Composition according to any one of the preceding claims, characterized in that it comprises an aqueous phase.  23. 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.  24. Composition according to the preceding claim, characterized in that the organic solvent miscible with water is selected from lower monoalcohols having 1 to 5 carbon atoms, glycols having 2 to 8 carbon atoms, C3 ketones -C4, C2-C4 aldehydes.  25. Composition according to one of claims 22, 23 or 24, 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, in particular ranging from 3 % to 80% by weight, and in particular from 5% to 60% by weight.  26. Composition according to any one of the preceding claims, characterized in that it comprises a volatile oil.  27. Composition according to the preceding claim, characterized in that the volatile oil is selected from hydrocarbon oils, silicone oils and mixtures thereof. <Desc / Clms Page number 26>  28. Composition according to one of Claims 26 or 27, characterized in that the volatile oil is present in a content ranging from 0.1% to 98% by weight, in particular ranging from 1% to 65% by weight relative to to the total weight of the composition.  29. Composition according to any one of the preceding claims, characterized in that it comprises a non-volatile oil.  30. Composition according to the preceding claim, characterized in that the non-volatile oil is present at a content ranging from 0.1% to 50% by weight, especially from 0.1% to 40% by weight, in particular from 0% to 50% by weight. , 1% to 30% by weight relative to the total weight of the composition.  31. Composition according to any one of the preceding claims, characterized in that it comprises at least one film-forming polymer.  32. Composition according to claim 31 and one of claims 23 to 25, characterized in that the film-forming polymer is solubilized in the aqueous phase.  33. A composition according to claim 31 and one of claims 26 to 31, characterized in that the film-forming polymer is solubilized in a liquid fatty phase.  34. Composition according to any one of claims 31 to 33, characterized in that the film-forming polymer is present in a dry matter content ranging from 0.1% to 60% by weight, in particular ranging from 0.5% to 40% by weight. % by weight, and in particular ranging from 1% to 30% by weight relative to the total weight of the composition.  35. Composition according to any one of the preceding claims, characterized in that it comprises an additional wax.  36. Composition according to the preceding claim, characterized in that the additional wax is present in a content ranging from 0.1% to 50% by weight, in particular from 0.5% to 30% by weight, in particular from 1% to 20% by weight relative to the total weight of the composition.  37. Composition according to any one of the preceding claims, characterized in that it comprises at least one surfactant.  38. 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, plasticizers, and mixtures thereof. <Desc / Clms Page number 27>  39. Composition according to any one of the preceding claims, characterized in that it is in the form of mascara, product for eyebrows, eyeliner, eyeshadow, blush, background complexion, lip product, body make-up product (semi-permanent tattoo), hair make-up product.  40. Composition according to any one of the preceding claims, characterized in that it is in the form of mascara.  41. A cosmetic process for the makeup or non-therapeutic care of keratin materials, comprising the application to the keratin materials of a composition according to any one of claims 1 to 40.  42. Use of a composition according to any one of claims 1 to 41 to obtain a makeup of keratin materials homogeneous and / or smooth.  43. Use according to claim 42 to obtain makeup loading and separating eyelashes.