FR2848425A1 - Cosmetic composition for make-up or care of the nails, especially nail varnish, comprises nanotubes of a Group IIA, IIIA, IVA, VA, IB, IIB, IIIB, VIB or VIIB element - Google Patents

Abstract

Cosmetic composition for make-up or care of the nails comprises nanotubes of a Group IIA, IIIA, IVA, VA, IB, IIB, IIIB, VIB or VIIB element.

Description

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 The present invention relates to a cosmetic composition for the makeup or care of nails, including a varnish, and more particularly a nail polish.

 In the sense of the invention, it is meant to cover under the term fingernail, both natural nails as artificial nails or false nails.

 More particularly, the composition can be used as a base for varnish, as a nail makeup product, as a finishing composition, also called a top-coat in English terminology, to be applied to the nail makeup product or as a product. cosmetic nail care.

 In general, nail polishes comprise fillers and / or pigments intended either to improve their properties, in particular in terms of mechanics or texture, or to give them hue effects.

 These fillers may be of spherical or particulate form, like talc or more recently fullerene (EP 0 599 687), or in the form of natural or synthetic fibers.

 However, the obtaining of certain properties, particularly in terms of mechanical strength, generally require significant amounts of this type of filler, quantities which can simultaneously adversely affect the visual appearance of the varnish, for example by altering its gloss or by changing its color .

 This problem is particularly exacerbated with nail polish aqueous media where obtaining a subsequent resistance to water requires the use of a latex to film quickly after application. Thus, to reconcile this fast filming at room temperature (25 C) with a satisfactory hardness after drying, it is conventionally added to a low minimum film-forming temperature (MFFT) latex, for example less than 10 C, more than 20% by volume. reinforcing fillers, based on the weight of dry polymer.

 There is therefore a need for a nail polish composition to meet all of the above requirements.

 Surprisingly, the inventors have found that by using nanotubes as filler, it was precisely possible to improve very clearly the mechanical properties of these compositions without altering the visual appearance of the varnish and / or the deposit.

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 The subject of the present invention is therefore, among others, a cosmetic composition for the make-up and / or care of nails comprising in a physiologically acceptable medium at least nanotubes consisting of at least one element belonging to groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, VIB and VIIB of the Periodic Table of Elements.

 The subject of the invention is also the use of nanotubes consisting of at least one element belonging to the groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, VIB and VII of the periodic table of the elements, in particular as a charge and / or pigment, in a cosmetic composition for makeup and / or nail care.

 The invention further relates to a cosmetic process for makeup and / or care of the nails comprising applying at least one composition according to the invention to the nails. This application can be in the form of a single layer or several layers.

 Other objects of the invention will appear on reading the description and examples which follow.

nanotubes
By nanotubes is meant in the sense of the invention any nano-object whose organization of atoms or molecules gives the nano-structure a tube shape.

 More precisely, these nanotubes consist of at least one element belonging to groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, VIB, and VIIB of the periodic table of elements.

 As examples of constituent elements of the nanotubes of the invention, mention may be made of carbon, silicon, tungsten, silver, gold, boron, zinc, platinum, magnesium, iron , cerium and aluminum.

 According to one particular variant of the invention, the nanotubes consist of at least one element belonging to group IVA of the periodic table of elements. More particularly, said element is carbon.

 When one of the constituent elements of the nanotubes is carbon, said nanotubes may consist wholly or partially of organic molecules. Examples of organic molecules that may be mentioned are diacetylenic phospholipids,

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 glutamates, long-chain diamides, glucophospholipids and alkylphenylglucopyranosides.

 Preferably, the backbone of the nanotubes consists solely of carbon atoms.

 These carbon nanotubes are conventionally obtained by condensation of a carbon vapor that can be obtained by sublimation of graphite at a very high temperature by means of an electric arc in the presence or absence of a catalyst such as traces of a metal pulverized (Co, Ni or Fe). The carbon nanotubes can be formed by a single plane of graphene; this case they are called single wall (Single Wall NanoTube, SWNT in English). The winding of graphene planes can be zig-zag, niche or chiral. The nanotubes may also be constituted by several tubes "nested" into each other; in this case they are called multiwall nanotubes (Multi Wall NanoTube, MWNT in English).

 More particularly, the nanotubes are characterized by a form factor.

The form factor is the ratio of the length divided by the diameter (L / d).

 In the context of the present invention, this form factor is at least equal to 1.2, and may vary from 1.5 to 10,000, especially from 2.5 to 5,000, in particular from 5 to 3,000, and better from 10 to 2,000.

 Thus, the diameter (d) of the nanotubes may range from 0.5 to 1000 nm, in particular from 0.8 to 100 nm, and in particular from 1 to 50 nm.

 As for the length (L) of the nanotubes, it can vary from 1 to 100 m, in particular from 2 to 75 m and in particular from 3 to 50 m.

 As specified above, the nanotubes according to the invention and more particularly the carbon nanotubes, are characterized by a strong anisotropy. This high anisotropy associated with a small diameter is particularly advantageous for obtaining a low concentration transparency.

 The nanotubes according to the invention are particularly interesting for their mechanical properties. In this case, according to the single-or multi-sheet nature, the modeling estimates for an elemental carbon nanotube a YOUNG module that may be greater than or equal to 200 GPa and in particular may be between 650 GPa and 1.5 TPa. . In addition, this high module is associated with an elongation capacity

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 significant of said nanotubes, of the order of about 20%, and a satisfactory intrinsic flexibility.

 These mechanical specificities and their strong anisotropy are particularly advantageous in terms of mechanical properties of reinforcement. They make it possible in particular to obtain, at low concentration of nanotubes, in particular of the order of 6% by weight of carbon nanotubes, mechanical properties that are very satisfactory in terms of withstand and which are comparable to those conventionally obtained with at least 20% by volume. of a conventional spherical or particulate filler, that is to say an amount which is otherwise detrimental to the optical properties, in particular the brightness, of the corresponding cosmetic composition. It is customary to express the concentration of a compound in volume percentage when seeking to qualify its mechanical properties vis-à-vis a matrix incorporating it. However, insofar as, in the present case, the density of the carbon nanotube is comparable to that of the matrix consisting essentially of carbonaceous organic matter, it will be considered that this volume concentration is equivalent to the concentration expressed in terms of weight.

 Finally, the nanotubes and in particular the carbon nanotubes advantageously have nonlinear optical properties. In this case, the intensity of their black color is likely to change depending on the received light intensity and thus to confer on the composition incorporating these nanotubes, original and animated optical effects. As such, they also constitute interesting black pigments for the cosmetic compositions according to the invention.

 The nanotubes also have the advantage of being functionalizable in all or part of their surface. This functionalization may be particularly advantageous for imparting properties complementary to the nanotubes. It may in particular be carried out in order to modulate their hydrophobicity and / or to obtain an optimal dispersion of carbon nanotubes in the cosmetic medium and / or a better adhesion to keratin materials.

 Functionalized is meant to characterize in the sense of the invention, the presence of functional groups that can interact physically or chemically with each other or with the external environment.

 In this case, any reaction mechanism can be used to functionalize the graphene planes constituting the carbon nanotubes.

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 By way of example, the functionalization of carbon nanotubes can be carried out by a reaction mechanism of the nucleophilic substitution, electrophilic substitution, radical substitution, addition, elimination, rearrangement, oxidation, reduction, acid-base reaction, electrochemical reaction, or else photochemical reaction.

 The surface of the nanotubes can be functionalized with oxygenated and / or nitrogenous groups.

 Among the functions that can be grafted onto the surface of the graphene planes constituting the carbon nanotube, there may also be mentioned carboxylic groups. An example of such functionalization is described in the article "Solution Properties of Single Walled Carbon Nanotube", J. Chen et al (Science 1998, vol 282, No. 5396, pages 95-98).

 Hydrophobic functions can also be grafted onto the surface of the graphene planes constituting the carbon nanotube. For example, the fluorination of carbon nanotubes described in the article "Fluorinated Single wall nanotubes", K. N. Kudin et al. (Phys Rev B63,45413).

 It is also possible to graft inorganic molecules such as alkoxysilanes (Nano Lett, Vol 2, No. 4, 2002 pages 329 to 332).

 Functionalization of graphene planes can be carried out in several stages, such as, for example, the functionalization of carbon nanotubes with fatty-chain amides, described in the article "Dissolution of Single Wall Carbon Nanotube", M.

A. Hamon et al. (Advance Mater 1999, 11, n 10). To obtain, for example, a single-walled carbon nanotube whose surface is functionalized by the fatty-chain amide function of formula CONH-4-C6H4 (CH2) 13CH3. This functionalization in several steps can also lead to the grafting of glucose (Nano Lett, Vol 2, No. 4, 2002 pages 369 to 373).

 Functionalization of carbon nanotubes can be achieved by simple molecules, but also by oligomers, polymers or dendrimers.

By way of example, mention may be made of the article "A New Purification Method for Single Wall Carbon Nanotubes", by M. Holzinger and Coll (Appl Physics A 70 (2000) 599), which describes the grafting of dendritic structures to the surface of the graphene planes constituting the carbon nanotube.

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 In addition to improving the dispersion of carbon nanotubes in the cosmetic media, the functionalization of the surface can also be carried out in order to increase the affinity of the carbon nanostructures for the surface on which the makeup product is applied, in particular that of the nails. Improving the affinity between the nanotubes and said surface induced by the functionalization of the graphene planes may be the result of the increase in Van der Waals-type interactions and / or the result of the appearance of hydrogen bonds and / or or ionic. Thus, the functional group or groups are capable of creating, with said surface, one or more chemical bonds chosen from the Van der Waals type interactions, the hydrogen bonds, the ionic bonds and the covalent bonds. In this context, mention may be made of the grafting of cationic molecules on the surface of carbon nanotubes, described in the article "Exohedral Sidewall Reactions of Single Walled Carbon Nanotubes in Molecular Nanostructures", M. Holzinger and All (Proceeding of the XIIth International Winterschool on Electronic Properties of Novel Materials: Molecular Nanostructures, Kirchberg, Austria, March 2001). In the context of grafting of cationic molecules, it is also possible to mention the grafting of polyethyleneimine derivatives (Nano Lett., Vol 2, No. 3, 2002 pages 231 to 234).

 In addition to surface chemical functionalization, the dispersion state of the nanotubes in the cosmetic formulations can be optimized using techniques such as the use of ultrasound, the addition of dispersing surfactants, or by shear mixing in the medium. formulation, melted if necessary.

 To increase the affinity of the carbon nanostructures for an application surface and in particular the nail, it is also possible to covalently graft the carbon nanostructure onto this keratin material. To do this, the functionalization of the graphene planes is carried out using groups having a certain reactivity on the amino acids constituting the keratin material.

 Preferably, the functional group (s) capable of creating with the keratin materials one or more covalent chemical bonds are chosen from groups capable of reacting with thiols, disulfides, carboxylic acids, alcohols and / or amines. Preferably, the functional group (s) capable of reacting with thiols, disulfides, carboxylic acids, alcohols and / or amines are chosen from: epoxides,

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 aziridine ring groups, vinyl and vinyl activated groups, such as acrylonitrile, acrylic and methacrylic esters, crotonic acid and ester, cinnamic acids and esters, styrene and derivatives, butadiene, vinyl ethers, vinyl ketone, maleic esters, maleimides, vinyl sulfones, or vinyl cyanoacrylate, carboxylic acids and their derivatives such as anhydride functions, acid chloride, esters, acetals, hemiacetals, aminals, hemi-amines, ketones and alpha-hydroxy ketones, alpha-haloketones, - lactones, thiolactones, - isocyanate, - thiocyanate, - imines, - imides (succinimides, glutimides), such as N-hydroxysuccinimide ester, - imidates, - oxazine and oxazoline, oxazinium and oxazolinium, alkyl or aryl or aralkyl halides, the halogen being selected from iodine, bromine or chlorine, unsaturated ring halides, the cycle being a carbon cycle or a h tereocycle, such as chlorotriazine, chloropyrimidine, chloroquinoxaline, chlorobenzotriazole, - sulfonyl halides of formula RS02X, R being an alkyl group, and X being chosen from fluorine and chlorine, - silicon derivatives such as alkoxysilanes, silanols.

 Suitable nanotubes for the invention include those marketed by MER Corporation and Showa Denko.

 The nanotubes may be present in the cosmetic composition in proportions by weight ranging from 0.05 to 8%, in particular from 0.1 to 6%, and especially from 0.5 to 4% of the total weight of the composition.

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Physiologically acceptable medium
By physiologically acceptable medium is meant a non-toxic medium that can be applied to the dander of human beings.

 The physiologically acceptable medium of the composition comprises at least one volatile solvent. The volatile solvent may especially be chosen from water, volatile organic solvents, and mixtures thereof.

Organic solvents
The composition according to the invention may comprise at least one organic solvent medium constituting an organic phase, composed of at least one volatile organic solvent at ambient temperature.

 As organic solvent which may or may not be volatile at ambient temperature, mention may be made of: ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; alcohols which are liquid at room temperature, such as ethanol, isopropanol, butanol, diacetone alcohol, 2-butoxyethanol or cyclohexanol; glycols that are liquid at room temperature, such as ethylene glycol, propylene glycol, pentylene glycol or glycerol; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, butyl acetate, acetate of aryl, isopentyl acetate; alkanes that are liquid at room temperature, such as decane, heptane, octane, dodecane, cyclohexane or isododecane; - their mixtures.

 The composition according to the invention may also contain one or more silicone oils, generally in a small amount, that is to say may be less than 10% by weight of the solvent phase. It may especially be volatile or non-volatile oils such as dimethicone, phenyldimethicone, alkyldimethicone, dimethicone, dimethicone copolyol or cyclomethicone.

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 The aforementioned organic compounds may be present in a proportion of 0.5 to 99% by weight relative to the total weight of the composition.

 When the physiologically acceptable medium comprises a significant amount of organic phase, it may be present in a proportion of 30 to 99% by weight and in particular 60 to 90% by weight relative to the total weight of the composition.

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

 The aqueous phase may consist essentially of water; 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) can be present in a content ranging from 1 to 95% by weight, especially ranging from 3 to 80% by weight, and in particular ranging from 5 to 60% by weight. by weight, relative to the total weight of the composition.

Surfactants
The composition according to the invention may further contain emulsifying surfactants present in particular in a proportion ranging from 0.1 to 30% by weight, in particular from 2 to 20% by weight, and in particular from 5 to 15% by weight, relative to the total weight of the composition.

 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.333-432, 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.

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 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 acids and sucrose, alkyl glucose esters, in particular polyoxyethylenated fatty acid esters of C1-C6 alkyl glucose, and their mixtures, - among the anionic surfactants: C16-C30 fatty acids neutralized with amines, ammonia or alkaline salts, and mixtures thereof.

Film-forming polymer
The composition according to the invention generally comprises at least one film-forming polymer.

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

 In the composition, it is possible to use a single film-forming polymer or a mixture of film-forming polymers.

 The film-forming polymer may be organic or inorganic.

 In a particular embodiment of the invention, the organic film-forming polymer is at least one polymer chosen from the group comprising: film-forming polymers which are soluble or dispersible in at least one organic solvent class mentioned above, for example: ketones alcohols, glycols and ethers of propylene glycols, short-chain esters, alkanes and their aqueous or non-aqueous mixtures.

Among these film-forming polymers, those which are soluble either in the short-chain esters, in the ketones or in the alcohols, or in their mixtures with one another or in their mixtures with water, are particularly suitable.

 The corresponding polymers may be of any chemical nature, in particular they may result either from the homo- or copolymerization of unsaturated monomers or from polycondensation, or from the modification of natural polymers, in particular polysaccharides. The weight average molecular weights (Mw) of these

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 polymers can vary from 3,000 to 1,000,000, especially from 5,000 to 800,000, and in particular from 10,000 to 500,000.

 Among the polymers soluble or dispersible in the organic solvents mentioned above, the following polymers are particularly suitable: a) homopolymers and copolymers of esters and / or amides of (meth) acrylic acids, in particular polymers resulting from polymerization or copolymerization of methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, ethyl 2-hexyl, heptyl, octyl, isobornyl, norbornyl, adamantyl acrylates and / or methacrylates, or the (meth) acrylamides correspondents. These polymers will preferably comprise from 0 to 20% of a polar comonomer such as (meth) acrylic acid, (meth) acrylamide, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (meth) acrylonitrile. They can also result from the copolymerization with styrene or substituted styrene. b) Homo- and co-polymers, vinyl esters or amides, in particular homo- and co-polymers resulting from the polymerization of vinyl acetate, vinyl propionate, vinyl versatate, with or without the presence of a comonomer polar such as crotonic acids, allyloxyacetic acid, maleic anhydride (or acid), anhydride (or acid) itaconic, vinyl acetamide and vinyl formamide. Likewise, they can result from the copolymerization of at least one of the monomers mentioned with styrene or substituted styrene. c) Nitrocellulose and / or cellulose esters such as cellulose acetates, cellulose propionates, cellulose butyrates, cellulose acetopropionates and cellulose acetobutyrates. d) Soluble or dispersible polycondensates in these solvents. They are generally used as the main film former or as cofilmogen of one of the classes of polymers mentioned above (1-a to 1-c), in particular if they are of low molecular weight (Mw <20,000). They may be chosen from the following polymers or copolymers: polyurethanes, acrylic polyurethanes, polyureas, polyurea polyurethanes, polyester polyurethanes, polyether polyurethanes, polyesters, polyesteramides, fatty-chain polyesters, epoxies, and tosylamide / formaldehyde condensates.

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 Among these polycondensates, in particular if they are used as cofilmogens of one or more nitro-cellulose and / or of a cellulose ester (class 1-c), mention may be made more particularly of: polyesters, in particular polyesters with fatty chain and more particularly the CTFA name copolymers: phthalic anhydride / glycerol / glycidyl decanoate copolymer and adipic acid / neopentyl glycol / trimellitic anhydride copolymer, - tosyl amide / formaldehyde condensates, - polyurethanes and polyurea-urethanes.

 According to a second embodiment, the at least one film-forming polymer may be chosen from aqueous dispersions of polymer particles or film-forming latexes, in this case the composition according to the invention comprises an aqueous phase.

 The aqueous dispersion comprising one or more film-forming polymers may be prepared by a person skilled in the art on the basis of his general knowledge, in particular by emulsion polymerization or by dispersion of the previously formed polymer.

 Among the film-forming polymers of this type that may be used in the composition according to the present invention, mention may be made of synthetic polymers, of the polycondensate type or of a radical type, polymers of natural origin, and their mixtures.

 The polymers (homo- and co-polymers) mentioned in the preceding paragraph (in 1, those which are soluble or dispersible in an organic solvent medium) and more particularly classes 1-a, 1 may be used, but in latex form. -b and 1-c.

 Among the polycondensates, mention may be made of anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethanespolyvinylpyrrolidones, polyester-polyurethanes, polyether polyurethanes, polyureas, polyurea polyurethanes, and mixtures thereof.

 Mention may also be made of polyesters, polyester amides, fatty-chain polyesters, polyamides and epoxy ester resins.

 The polyesters can be obtained, in known manner, by polycondensation of aliphatic or aromatic diacids with aliphatic or aromatic diols or polyols. As aliphatic diacids, it is possible to use succinic acid, glutaric acid,

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 adipic acid, pimelic acid, suberic acid or sebacic acid. As aromatic diacids, it is possible to use terephthalic acid or isophthalic acid, or else a derivative such as phthalic anhydride. As aliphatic diols, it is possible to use ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexane dimethanol, 4,4 '- (1-methylpropylidene) bisphenol. As polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylolpropane.

 The radical-type polymers may in particular be polymers, or copolymers, acrylic and / or vinyl. Anionic radical polymers are preferably used. As anionic group-bearing monomer that can be used during the radical polymerization, mention may be made of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and 2-acrylamido-2-methylpropanesulphonic acid.

 Acrylic polymers may result from the copolymerization of monomers selected from esters and / or amides of acrylic acid or methacrylic acid. As examples of ester monomers, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate and lauryl methacrylate. Examples of amide monomers include N-t-butyl acrylamide and N-t-octyl acrylamide.

 The vinyl polymers may result from the homopolymerization or copolymerization of monomers chosen from vinyl esters, styrene or butadiene. Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate.

 It is also possible to use acrylic / silicone copolymers or else nitrocellulose / acrylic copolymers.

 Mention may also be made of the polymers resulting from the radical polymerization of one or more radical monomers inside and / or partially at the surface of pre-existing particles of at least one polymer chosen from the group consisting of polyurethanes and polyureas. polyesters, polyesteramides and / or alkyds. These polymers are generally called hybrid polymers.

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 When an aqueous dispersion of polymer particles is used, the solids content of said aqueous dispersion may be of the order of 5 to 60% by weight, and in particular of 30 to 50% by weight.

 The size of the polymer particles in aqueous dispersion can be between 10 and 500 nm, and is in particular between 20 and 150 nm, which makes it possible to obtain a film having a remarkable gloss. However, particles up to 1 micron in size can be used.

 In the composition, the content of film-forming polymer (s) belonging to categories 1) or 2) can vary from 5 to 60% by weight, especially from 10 to 50% by weight, and in particular from 15 to 35% by weight. by weight, relative to the total weight of the composition.

Auxiliary filming agent:
The auxiliary film-forming agent may be chosen from all the compounds known to those skilled in the art as being capable of fulfilling the desired function, and may especially be chosen from plasticizers and coalescing agents of the film-forming polymer.

 In particular, mention may be made, alone or as a mixture, of the usual plasticizers or coalescence agents, such as: glycols and their derivatives such as diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether or else diethylene glycol hexyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether; the glycol esters, the propylene glycol derivatives and in particular the propylene glycol phenyl ether, the propylene glycol diacetate, the dipropylene glycol butyl ether, the tripropylene glycol butyl ether, the propylene glycol methyl ether, the dipropylene glycol ethyl ether and the tripropylene glycol methyl ether, diethylene glycol methyl ether, propylene glycol butyl ether, esters of carboxylic acids such as citrates, especially triethyl citrate, tributyl citrate, triethyl acetyl citrate, tributyl acetyl citrate, acetyl citrate, 2-triethylhexyl; phthalates, especially diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dipentyl phthalate, phthalate

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 dimethoxyethyl; phosphates, especially tricresyl phosphate, tributyl phosphate, triphenyl phosphate, tributoxyethyl phosphate; tartrates, especially dibutyl tartrate; adipates; carbonates; sebacates; benzyl benzoate, butyl acetylricinoleate, glyceryl acetylricinoleate, butyl glycolate, camphor, glycerol triacetate, N-ethyl-o, p-toluenesulfonamide, oxyethylenated derivatives such as oxyethylenated oils, especially vegetable oils such as castor oil; silicone oils, - mixtures thereof.

 The plasticizing and / or coalescing agent may be present in the composition in a content ranging from 0.01 to 15% by weight, and preferably ranging from 0.1 to 10% by weight, relative to the total weight of the composition.

Thickening agent
The composition may comprise a thickening agent, in particular to give the composition a consistency allowing a good application of the composition to the nails.

 The thickening agent is more particularly a non-aqueous phase thickener and may be chosen from hydrophobic silicas, such as those mentioned in document EP-A-898960, and for example sold under the references "AEROSIL R812" by the company Degussa , "CAB-O-SIL TS-530 #", "CAB-O-SIL TS-610 #", "CAB-O-SIL TS-720 #" by Cabot, "AEROSIL R972", "AEROSIL R974" by the company Degussa; clays such as montmorillonite, hectorite steralkonium, bentonite steralkonium; polysaccharide alkyl ethers (in particular of which the alkyl group contains from 1 to 24 carbon atoms, preferably from 1 to 10, better still from 1 to 6, and more especially from 1 to 3) such as those described in document EP-A -898,958.

 The thickening agent may be present in the composition according to the invention in a content ranging from 0.05% to 10% by weight, especially from 0.1% to 3% by weight, relative to the total weight of the composition.

 The composition of the invention may, in addition, comprise an additional particulate phase which may be present in a proportion of 0.01 to 25%, in particular 0.01%.

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 at 15%, in particular from 0.02 to 10% and more preferably from 0.05 to 10% by weight relative to the total weight of the composition, and which may comprise at least one pigment and / or at least one mother-of-pearl and / or at least flakes and / or at least one additional filler used in the cosmetic compositions.

 By pigments, it is necessary to include white or colored particles, mineral or organic, insoluble in the cosmetic composition, intended to color and / or opacify the composition. By additional charges, it is necessary to include colorless or white, mineral or synthetic, lamellar or non-lamellar particles. By nacres, it is necessary to understand iridescent particles, in particular produced by some shellfish in their shell or else synthesized. These fillers and nacres serve in particular to modify the texture of the composition.

 The pigments may be present in the composition in a proportion of from 0.01 to 15% by weight, especially from 0.01 to 10% by weight, and in particular from 0.02 to 5% by weight, relative to the total weight of the composition. composition. As inorganic pigments that can be used in the invention, mention may be made of titanium oxide, zirconium oxide or cerium oxide, as well as zinc, iron or chromium oxides, ferric blue, manganese violet, ultramarine blue and the like. chromium hydrate.

 Among the organic pigments that can be used in the invention, mention may be made of carbon black, D & C type pigments, cochineal carmine, barium, strontium, calcium, aluminum or diketo pyrrolopyrrole (DPP) lacquers. ) described in EP-A-542669, EP-A-787730, EP-A-787731 and WO-A-96/08537.

 The quantity and / or the choice of these pigments can, if necessary, be adjusted taking into account the quantity of nanotubes present in the cosmetic composition in question.

 The nacres may be present in the composition in a proportion of 0.01 to 15% by weight, preferably 0.01 to 10% by weight, and more preferably 0.02 to 5% by weight relative to the total weight of the composition. composition. The pearlescent pigments 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 in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

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 The additional fillers may be present in a proportion of 0.01 to 15% by weight, preferably 0.01 to 10% by weight, and more preferably 0.02 to 5% by weight relative to the total weight of the composition. Their quantity is generally adjusted by taking into account the amount of nanotubes.

 Mention may in particular be made of talc, zinc stearate, mica, kaolin, polyamide (nylon) powders (Orgasol from Atochem), polyethylene powders, tetrafluoroethylene polymer powders (Teflon), starch , boron nitride, polymeric microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel (Nobel Industry), acrylic acid copolymers (Polytrap Dow Corning) and silicone resin microbeads (Tospearls Toshiba, for example), elastomeric organopolysiloxanes.

 The composition may also comprise water-soluble or fat-soluble dyes in a content ranging from 0.01 to 6% by weight, especially ranging from 0.01 to 3% by weight relative to the total weight of the composition. The fat-soluble dyes are, for example, Sudan Red, DC Red 17, DC Green 6, 3-carotene, soybean oil, Sudan Brown, DC Yellow 11, Violet DC 2, Orange DC 5, yellow quinoline. The water-soluble dyes are, for example, beet juice, methylene blue.

 The composition according to the invention may also contain ingredients commonly used in cosmetics and more particularly in the field of cosmetics and / or nail care. They may especially be chosen from vitamins, trace elements, softeners, sequestering agents, basifying or acidifying agents, spreading agents, wetting agents, thickening agents, dispersing agents, defoamers, preservatives, UV filters, actives, moisturizers, perfumes, neutralizers, stabilizers, antioxidants and mixtures thereof.

 Thus, when the compositions according to the invention are more particularly intended for the care of natural nails, they may in particular incorporate, as active ingredients, curing agents for keratin materials and / or active agents for treating various conditions localized at the level of the nail, such as onichomycosis.

 The amounts of these various ingredients are those conventionally used in this field and for example from 0.01 to 20% by weight, relative to the total weight of the composition.

<Desc / Clms Page number 18>

 Of course, those skilled in the art will take care to choose this or these optional additional compounds, 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 of the invention can be obtained according to the preparation methods conventionally used in cosmetics or in dermatology.

 The composition may be applied uniformly or non-uniformly, that is to say in a discontinuous manner, in particular in the form of geometric, symmetrical or asymmetrical patterns (for example in the form of dots, squares, rounds, stars) distributed in a random or orderly, with precise or fuzzy outlines on the surface of the nails.

 The following examples of compositions are given for illustrative and non-limiting purposes.

EXAMPLES
Nail polishes comprising nanotubes can be produced with the following formulations, these compositions being prepared according to the preparation methods conventionally used in cosmetics.

The carbon nanotubes used are single-walled and marketed by MER Corporation under the reference MRSW.

<Tb>
<Tb>

Example <SEP> 1 <SEP>: <SEP> varnish <SEP> to <SEP> aqueous nails <SEP>
<tb> Latex <SEP> (PU, <SEP> extract <SEP> sec <SEP> 35 <SEP>%) <SEP> 72.5 <SEP> g
<tb> Nanotubes <SEP> 0.5 <SEP> g
<tb> Pigment (s) <SEP> 1 <SEP> g
<tb> Water <SEP> qsp <SEP> 100 <SEP> g <SEP>
<Tb>
Example 2: nail polish

<Tb>
<tb> Nitrocellulose <SEP> 19 <SEP> g <SEP>
<tb> Sulfonamide <SEP> of <SEP> N-ethyl <SEP> o, <SEP> p- <SEP> toluene <SEP> 6 <SEP> g
<tb> Acetylcitrate <SEP> of <SEP> tributyl <SEP> 6 <SEP> g
<tb> Nanotubes <SEP> 0.5 <SEP> g
<tb> Pigment (s) <SEP> 2 <SEP> g
<Tb>

<Desc / Clms Page number 19>

<Tb>
<tb> Isopropanol <SEP> 8 <SEP> g
<tb> Acetate <SEP> ethyl / acetate <SEP> of <SEP> butyl <SEP> qsp <SEP> 100 <SEP> g
<Tb>

Of course, the invention is not limited to the embodiments which have just been given.

Claims (28)

1. Cosmetic composition for makeup and / or nail care, characterized in that it comprises, in a physiologically acceptable medium, at least nanotubes consisting of at least one element belonging to groups IIA, IIIA, IVA, VA , IB, They, IIIB, VIB and VIIB of the Periodic Table of Elements.  2. Composition according to claim 1, characterized in that the nanotubes consist of at least one element belonging to group IVA of the periodic classification of the elements.  3. Composition according to claim 1 or 2, characterized in that one of the constituent elements of the nanotubes is carbon.  4. Composition according to claim 3, characterized in that the nanotubes consist wholly or partially of organic molecules.  5. Composition according to claim 3, characterized in that the backbone of the nanotubes consists solely of carbon atoms.  6. Composition according to claim 5, characterized in that the carbon nanotubes are single wall nanotubes.  7. Composition according to claim 5, characterized in that the carbon nanotubes are multi-wall nanotubes.  8. Composition according to any one of the preceding claims, characterized in that the nanotubes have a form factor at least equal to 1.2.  9. Composition according to any one of the preceding claims, characterized in that the nanotubes have a form factor ranging from 1.5 to 10,000, in particular from 2.5 to 5000, and in particular from 5 to 3000.  10. Composition according to one of claims 5 to 9, characterized in that the surface of the carbon nanotubes is wholly or partially functionalized.  11. Composition according to claim 10, characterized in that the functionalization of the carbon nanotubes is carried out by a reaction mechanism of the nucleophilic substitution type, electrophilic substitution, radical substitution, addition, elimination, rearrangement, oxidation, reduction, acid-base reaction, electrochemical reaction or photochemical reaction.  12. Composition according to claim 10 or 11, characterized in that the surface of the carbon nanotubes is functionalized by one or more selected groups. <Desc / Clms Page number 21>  among the carboxylic groups, oxygen groups, nitrogen groups, hydrophobic functions, fatty-chain amides, oligomers, polymers and dendrimers.  13. Composition according to Claim 12, characterized in that the functional group or groups are capable of creating, with the application surface, in particular of the nail, one or more chemical bonds chosen from Van der Waals-type interactions. hydrogen, ionic bonds and covalent bonds.  14. A composition according to claim 13, characterized in that the functional group or groups capable of creating with the keratin material or a base makeup layer, one or more covalent chemical bonds are chosen from groups capable of reacting with the thiols, disulfides, carboxylic acids, alcohols and / or amines.  15. Composition according to any one of the preceding claims, characterized in that the diameter of the nanotubes ranges from 0.5 to 1000 nm, and in particular from 0.8 to 100 nm.  16. Composition according to any one of the preceding claims, characterized in that the length of the nanotubes varies from 1 to 100 m, and in particular from 2 to 75 m.  17. Composition according to any one of the preceding claims, characterized in that the nanotubes are present in the cosmetic composition in a proportion of 0.05 to 8% by weight, especially 0.1 to 6% by weight, and in particular of 0.5 to 4% by weight, relative to the total weight of the composition.  18. Composition according to any one of the preceding claims, characterized in that said composition further comprises a particulate phase in a proportion of 0.01 to 25% by weight, in particular of 0.01 to 15%, and in particular of 0 , 02 to 10% by weight relative to the total weight of said composition.  19. Composition according to claim 18, characterized in that said particulate phase comprises at least one pigment and / or at least one nacre and / or flakes and / or at least one additional filler.  20. Composition according to any one of the preceding claims, characterized in that said composition further comprises at least one film-forming polymer.  21. The composition as claimed in claim 20, characterized in that the film-forming polymer is chosen from film-forming polymers that are soluble or dispersible in at least one organic solvent and film-forming or polymeric latexes in aqueous dispersion. <Desc / Clms Page number 22>  22. A composition according to claim 20 or 21, characterized in that the film-forming polymer is present in a proportion of 5 to 60% by weight, especially 10 to 50% by weight, and in particular 15 to 35% by weight relative to to the total weight of the composition.  23. Composition according to any one of the preceding claims, characterized in that it further comprises a plasticizer and / or a coalescing agent.  24. Composition according to any one of the preceding claims, characterized in that it comprises at least one organic solvent medium and / or at least one aqueous medium.  25. Composition according to one of the preceding claims, characterized in that it is in the form of a nail polish.  26. Cosmetic makeup and / or nail care process, characterized in that it comprises the application to the nails of at least one composition according to any one of the preceding claims.  27. Use of nanotubes consisting of at least one element belonging to groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, VIB and VIIB of the periodic table of elements, especially as filler and / or pigment, in a cosmetic composition for makeup and / or nail care.  28. Use according to claim 27, characterized in that the nanotubes are as defined in claims 2 to 17.