WO2006097351A1

WO2006097351A1 - Anhydrous cosmetic composition comprising nitrogen monoxide in a microporous solid crystalline material

Info

Publication number: WO2006097351A1
Application number: PCT/EP2006/002662
Authority: WO
Inventors: Marie-Madeleine Cals-Grierson; Xavier Blin; Nathalie Jager Lezer
Original assignee: L'oreal
Priority date: 2005-03-15
Filing date: 2006-03-03
Publication date: 2006-09-21

Abstract

The invention relates to an anhydrous cosmetic composition comprising nitrogen monoxide adsorbed in a microporous solid crystalline material. This composition can be a composition for making up or caring for keratinous substances, such as the lips or skin, and can be provided in the form of a lipstick, lip gloss or lip balm.

Description

ANHYDROUS COSMETIC COMPOSITION COMPRISING NITROGEN MONOXIDE IN A MICROPOROUS SOLID CRYSTALLINE MATERIAL

The present invention relates to a cosmetic composition comprising nitrogen monoxide adsorbed by a porous solid crystalline material which is intended to be applied to keratinous substances of human beings, such as the skin, lips, eyelashes, eyebrows, nails or hair. The composition is more particularly intended to be applied to the skin or lips. More especially, this composition is provided in the form of a homogeneous anhydrous gel, cream or stick including this active agent. The composition of the invention can in particular constitute a product for making up the skin of the face or of the body, lips or superficial body growths of human beings having in particular nontherapeutic treatment and/or care properties. The composition of the invention can in particular constitute a product for coating keratinous fibres, such as the eyelashes, eyebrows and hair and more particularly eyelashes.

The composition according to the invention can be provided in the form of a mascara, of a product for the eyebrows, of an eye liner or of a product for making up the hair. The composition can be a free or compact powder, a foundation, a face powder, an eyeshadow, a blusher, a lipstick, a lip balm, a lip gloss, a lip or eye pencil, a mascara, an eye liner, a nail varnish, a product for the artificial tanning of the skin, a product for colouring or caring for the hair, or a product for making up the body or colouring the skin.

Application WO 05/003032 provides for the use of zeolites as nitrogen monoxide adsorbent and shows that the active agent is released in water and in blood. The document furthermore discloses certain known uses of nitrogen monoxide in cosmetics and suggests the use in cosmetics of nitrogen monoxide adsorbed in zeolites. However, this document does not provide a dosage form which is suitable both for retaining the stability of the nitrogen monoxide in the composition and for conferring good cosmetic properties on the composition, such as good consistency, good homogeneity and good deposition during application. The inventors have found that it is possible to formulate nitrogen monoxide in a stable fashion in a cosmetic composition. This is because it is possible to trap zeolites in an anhydrous fatty matrix without initiating the release of the nitrogen monoxide. According to the present invention, zeolites begin to release nitrogen monoxide during the application of the cosmetic composition to keratinous substances. More specifically, a subject-matter of the invention is an anhydrous cosmetic composition comprising nitrogen monoxide adsorbed in a microporous solid crystalline material. An other subject-matter of the invention is a process for making up or caring for the skin or lips, which consist in applying said composition.

An other object of the invention is the cosmetic use of said composition for caring or making up the skin, lips or nails.

The term "anhydrous composition" is understood to mean a composition comprising less than 10% by weight of water, preferably less than 5% by weight of water, more preferably less than 2% by weight of water. According to one embodiment, the water which may be present in the composition is not added to the ingredients during its preparation. This water may be bound in the form of traces in the ingredients used to prepare the said composition. The composition according to the invention is intended in particular to improve keratinous tissues, such as the skin, hair, lips, nails, eyelashes and eyebrows .

In particular, the composition can be a composition for caring for and/or making up the eyelashes of human beings or for the preparation of a composition for caring for and/or treating the eyelashes of human beings.

The composition is intended in particular to restore fullness to the lips and/or to promote their naturally pink colouring, to improve the appearance of the complexion (good look effect) and/or to reduce periocular lines.

The composition can also be used to improve the appearance of the lips or the contour of the lips, in particular in order to increase the volume of the lips and/or to model them and/or to render them smoother. The composition can also be used to modify the colour of the lips, to render them pinker or more living, indeed even to obtain a bitten lip effect.

In particular, the composition is intended to: restore fullness to the lips, that is to say to increase their size, their volume and/or their thickness and/or to give them a more swollen or fleshy appearance and/or to model them and/or to render them smoother and/or to stimulate the naturally pink colouring of the lips; stimulate the naturally pink colouring of the skin and/or to confer a good natural look effect on the skin; - homogenize the complexion and/or to promote its lustre and/or its radiance and/or to reduce the muddy or waxy complexion effect; reduce bags and/or to lighten lines around the eyes and/or to render the complexion of the area of the lines around the eyes uniform with the remainder of the face. In one embodiment or application, the compositions of the present invention are of use for slowing down, minimizing, erasing and/or preventing signs of cutaneous ageing, in particular visible and/or tactile discontinuities in the texture of the skin associated with ageing, thus improving the appearance and/or the feel of the skin, for example a smoother or more uniform appearance and/or feel.

The term "signs of cutaneous ageing" is understood to mean the development of discontinuities in texture, such as wrinkles, comprising fine surface wrinkles and coarse deep wrinkles, lines of the skin, cracks, bumps, wide pores, a scaly appearance, flakiness and/or other forms of unevenness or of roughness of the skin, loss of elasticity of the skin, sagging (including distensions in the area of the eyes and cheeks) , loss of firmness of the skin, loss of tightness of the skin or loss of recovery of the skin after deformation.

For example, the length, the depth and/or other dimensions of the lines and/or wrinkles can be reduced, the apparent diameter of the pores can decrease or the apparent height of the tissue in the immediate proximity of the pore openings can decrease. The compositions of the present invention can also be used to stabilize or remodel hypodermal or deeper fat. The stabilization of fat, in particular in human beings, is generally associated with the appearance of the ageing attributed to fat atrophy and to fat regression in the skin. The methods and the compositions described in this text may contribute to the prevention of the formation of wrinkles and may promote the improvement in the appearance of deep wrinkles by supporting the vascularity of the skin.

Microporous solid crystalline material

The composition according to the invention comprises at least one organic, inorganic or hybrid solid crystalline material. The material is solid at atmospheric pressure and at a temperature of less than approximately 40⁰C.

The solid crystalline material is microporous. The size of the pores is less or equal than 1 micron, preferably less than or equal to

1000 angstroms, more preferably less than or equal to

50 angstroms, more preferably less than or equal to

30 angstroms.

The pores can form a repeating three- dimensional network capable of trapping the nitrogen monoxide or a complex of nitrogen monoxide with at least one organic or inorganic cation. According to one embodiment, the microporous solid crystalline material is a zeolite. The composition of the present invention can comprise nitrogen monoxide adsorbed in a zeolite material. Zeolite materials constitute a class of aluminosilicate materials which are known and used in various applications, for example ion exchange, gas separation and catalysis (A. Dyer, An Introduction to Zeolite Molecular Sieves, J. Wiley and Sons, 1988). Zeolites can be of natural origin or can be prepared synthetically. Zeolites are nanoporous crystalline aluminosilicate structures composed of AlO₄- and SiO₄- tetrahedra connected to one another via oxygen vertices. Assembling the tetrahedra in space forms polyhedra which delimit a network of 1-, 2- or 3- dimensional channels, cages and cavities in which cations are positioned at points where they balance the negative charges carried by the AIO₄- tetrahedra. The size and the arrangement of the tetrahedra differentiate the zeolites.

The zeolite can be represented by the general formula Al_ySii__yO₄ ^Y". For each aluminium atom in the zeolite structure, one negative charge is balanced by an extraframework cation. These cations can be inorganic or organic in nature and can be exchanged using standard ion exchange processes (M. E. Davis, Ordered Porous Materials for Emerging Applications, Nature, 417, 813, 2002).

Zeolites can comprise transition element cations as extraframework entity, for example iron, copper or ruthenium, and nitrogen monoxide forms complexes inside the cavities of the zeolite material.

Cations of other elements, for example sodium and potassium, bind nitrogen monoxide less strongly. A person skilled in the art can use standard ion exchange processes to introduce the required metal ions into a zeolite structure as extraframework cations (Plank et al., US Patent No. 3 140 249; Preparation, Characterisation and Performance of Fe-ZSM-5 Catalysts, R. Joyner and M. Stockenhuber, J. Phys . Chem. B., 1999, 103, 5963-5976) . By using such techniques, it is possible to incorporate mixtures of cations in zeolite structures .

Zeolites can be in the dehydrated state. The amount of nitrogen monoxide charged to the zeolites can be controlled by varying the relative amounts of the extraframework cations, by controlling their chemical nature and/or the total number of cations present. For example, the number of extraframework cations present in the zeolite structure can depend on the amount of aluminium present in the framework. More aluminium ions require more extraframework cations to balance the negative charge. The chemical nature of the extraframework cations can also be modified (for example, monovalent cations, for example Na⁺ and Ag⁺, can be exchanged by divalent cations, for example Fe²⁺ and Cu²⁺, or trivalent cations, for example Ru³⁺ and Fe³⁺) . Each different cation can have a different affinity for NO and changing the cations present in the zeolite framework can be used to control the release of NO. Such an adjustment of the zeolite composition can affect the kinetics under which the nitrogen monoxide is released. For example, a sodium-loaded zeolite can bind nitrogen monoxide less strongly than an iron-loaded zeolite and can release the nitrogen monoxide more rapidly. A sodium/iron mixed zeolite can release the nitrogen monoxide at a different rate from a sodium-loaded zeolite or from an iron-loaded zeolite and such a release of nitrogen monoxide can exhibit a different rate profile.

The zeolite framework can also be chosen in order to vary the rate of release of nitrogen monoxide. Zeolite frameworks are available in the form of synthetic materials having different structures (Atlas of Zeolite Framework Types, Fifth Revised Edition, Ch. Baerlocher, W. M. Meier, D. H. Olson, 2001, Elsevier) . For example, the size of the pores and of the channels of the zeolite framework can be varied. For example, the zeolite having the LTA structure has openings defined by 8 pore tetrahedral units (that is to say, a ring of 8 Si/Al atoms and 8 oxygen atoms) . Zeolite MFI has a bigger ring opening defined by 10 tetrahedral units and FAU by an even bigger pore opening of 12 tetrahedral units. The configuration of the pores in space can also differ from one zeolite to another. For example, some zeolites have channels which extend in only one direction (one-dimensional channel systems) , while others have systems of channels which interact in two or three dimensions (2-dimensional or 3-dimensional channel systems) . The size, the shape and the configuration in space of zeolites can affect the rates of diffusion and of adsorption/desorption of the nitrogen monoxide (NO) and can be used to control the rate of release of NO. Consequently, the composition of the zeolite material can be adjusted so as to control the amount of nitrogen monoxide charged to the zeolite structure and/or the rate at which the nitrogen monoxide is released from the zeolite. Such zeolite structures can be chosen, without being limited thereto, from the frameworks having the following three-letter codes: LTA, FAU, MFI, MOR, FER, BEA, PEI and SAS (see the website of the International Zeolite Association, www. iza-online . orq, for further details on the correspondence between the codes and the framework structures of the zeolites) . These three-letter codes describe the framework architecture of the zeolites, that is to say their structure, but they do not describe the composition of the zeolite, which can vary greatly. The three-letter codes are used as nomenclature systems for zeolites. The zeolites used in the present invention can have the following general formula (I) :

[ (Miⁿ⁺)_x/n (M₂ ^P+) _y/p ...(M_n ^q+)_v/q] [Al₂Si₁^O₄] (I) in which Mi and M₂ to M_n are chosen independently from - extraframework metal cations chosen independently from the group consisting of Li, Na, K, Mn, Ca, Mg, Fe, Cu, Ru, Rh, Co, Ni, Zn and Ag, and organic cations, such as N (R₁) _a (R₂) _b ⁺ _f where R₁ and R₂ are chosen independently from H, -CH₃, -CH₂CH₃ or -CH₂CH₂CH₃ and a and b are independently 0, 1, 2, 3 or 4 so that a + b = 4, such as NH₄ ⁺, for example, x ranges from zero to nz, y ranges from zero to pz and v ranges from zero to qz, provided that x/n + y/p + ... + v/q = z, z is the number of silicon atoms replaced by aluminium atoms in the zeolite framework, n+, p+ and q+ are independently integers 1+, 2+ or 3+ when the associated cation is a metal cation or equal to 1+ when the associated cation is an organic cation.

The zeolites used in the present invention can have the following general formula (II): [(M₁ ⁿ⁺)_x/n(M₂ ^p+)_y/p] [Al_zSii__zO₄] (II) in which Mi and M₂ are as defined above, x ranges from zero to nz, and y ranges from zero to pz, provided that x/n + y/p = z.

Preferably, the extraframework metal cations Mi and M₂ are cations of elements Zn or Mn, more preferably of Zn.

Zeolites can be prepared by ion exchange according to the method described in the work Verified Synthesis of Zeolitic Materials, Robson H. and Lillerud K. P., Verified Synthesis of Zeolitic Materials, 2nd Revised Edition, International Zeolite Association, 2001, www. iza-synthesis . org. Reference may also be made to the examples of

Application WO 05/003032, the content of which is incorporated in the present application by reference. Before charging with nitrogen monoxide, the zeolites can be completely or partially dehydrated, for example under vacuum, to remove water from the zeolite channels. The resulting zeolite can subsequently be exposed to nitrogen monoxide. Typically, charging with nitrogen monoxide is carried out at a temperature of -100⁰C to 50⁰C. Charging with nitrogen monoxide can be carried out with pure NO or with a mixture of NO and of a carrier gas, such as an inert gas, for example helium, argon or another inert gas, including mixtures of these. Charging is typically carried out at a pressure between atmospheric pressure and a pressure of 10 bar.

Nitrogen monoxide begins to be released when the cosmetic composition is deposited on keratinous substances .

The zeolite charged with nitric oxide can be prepared in the powder or monolith form. The monoliths can be formed by compressing a zeolite powder or by mixing a pulverulent zeolite with an appropriate binder. Appropriate binders comprise, without being limited thereto, ceramic binders, for example silica or alumina, and polymeric binders, for example polysulphone, polyethylene, PET, polystyrene, polytetrafluoroethylene (PTFE) and other polymers.

According to another embodiment, the microporous solid crystalline material is a zeotype. The term "zeotypes" is understood to mean crystalline structures of zeolite type in which all or part of the silicon and/or aluminium atoms are replaced by one or more atoms of the elements from Groups 2 to 13 of the Periodic Table, in particular by boron (III), gallium(III) , iron (III), chromium (III, IV or V), germanium (IV) , titanium (IV) , vanadium (IV or V), cobalt (II) or cobalt (III) atoms. The zeotype can be silicalite (see the article by C. Lamberti, S. Bordiga and A. Zecchina which appeared in the review Rassegna Scientifica, Vol. 4, No. 2, December 1999, the content of which is incorporated in the present application by- reference) .

Processes for the preparation of titanium and iron zeotypes are disclosed respectively in Patent Applications US 4 480 135 and US 5 110 995. In particular, Patent Application US 4 480 135 discloses the preparation of a titanium silicalite (TS-I) from a reaction mixture comprising a silicon oxide, a titanium oxide, optionally an alkali metal oxide, a nitrogenous organic base and water. Patent Application US 5 110 995 discloses the preparation of an iron zeotype from a mixture comprising a source of silica, a source of iron and, if necessary, a source of Elⁿ⁺ (where El is an element from Periods 2, 3, 4 or 5 of the Periodic Table of the Elements) , a base, an organic surfactant and optionally a crystallization seed.

The zeolite comprising adsorbed nitrogen monoxide can be present in the composition in an amount sufficient to improve keratinous tissues, such as the skin, hair, lips, nails, eyelashes and eyebrows. In particular, the zeolite comprising adsorbed nitrogen monoxide is in an amount sufficient to improve the appearance of the lips or the contour of the lips, in particular to increase the volume of the lips and/or to model them and/or to render them smoother. The zeolite comprising adsorbed nitrogen monoxide can also be in an amount sufficient to modify the colour of the lips, to render them pinker or more living, indeed even to obtain a bitten lip effect.

In one embodiment, the zeolite comprising adsorbed nitrogen monoxide is in an amount sufficient to slow down, minimize, erase and/or prevent signs of cutaneous ageing, in particular visible and/or tactile discontinuities in the texture of the skin associated with ageing, thus improving the appearance and/or feel of the skin, for example a smoother and more uniform appearance and/or feel.

In one embodiment, the zeolite comprising adsorbed nitrogen monoxide is in an amount sufficient to stabilize or remodel the hypodermal or deeper fat. The composition can comprise at least one fatty substance chosen from oils, waxes and pasty fatty substances .

Oil

According to one embodiment of the invention, the composition comprises at least one oil. This oil preferably represents at least 5% by weight, with respect to the total weight of the composition, preferably at least 10% by weight.

The composition can comprise a polar or nonpolar oil or a mixture of the two. The term "polar oil" is understood to mean an oil composed of chemical compounds comprising at least one polar group. Polar groups are well known to a person skilled in the art: they can in particular be groups of alcohol, ester or carboxylic acid type.

Nonpolar oils can comprise oils which have a mean solubility parameter at 25°C δ_a = 0 (J/cm³)^1/2.

Weakly polar oils comprise oils which have a mean solubility parameter at 25⁰C of: 0 < δ_a < 5.0 (J/cm³) ^1/2, in particular of less than or equal to 4.9, better still of less than or equal to 4.5 and better still of less than or equal to 4.0 (J/cm³)^1/2.

Highly polar oils have a mean solubility parameter δ_a according to the Hansen solubility space at 25°C of: δ_a > 5.0 (J/cm³)^1/2, in particular of greater than or equal to 5.3, indeed even of greater than or equal to 5.5 and better still of greater than or equal to 6.0 (J/cm³) ^1/2, indeed even of greater than or equal to 7.0 (J/cm³)¹⁷².

The definition and the calculation of the solubility parameters in the Hansen three-dimensional solubility space are described in the paper by CM. Hansen: "The Three-dimensional Solubility Parameters", J. Paint Technol., 39, 105 (1967). According to this Hansen space: δ_D characterizes the London dispersion forces resulting from the formation of dipoles induced during molecular impact; δ_p characterizes the forces of Debye interactions between permanent dipoles and the forces of Keesom interactions between induced dipoles and permanent dipoles; δ_n characterizes the forces of specific interactions (such as hydrogen bonds, acid/base, donor/acceptor, and the like) ; δ_a is determined by the equation:

The parameters δ_p, δh, δ_D and δ_a are expressed in (J/cm³)¹⁷².

When the oily phase is a mixture of different oils, the solubility parameters of the mixture are determined from those of the components taken separately, according to the following relationships: δ_Dmi_X = Σ xi - δ_Di; δ_pmi_X = Σ xi * δ_pi and δ_hmi_X = Σ xi - δ_h± i i i

where xi represents the fraction by volume of the compound i in the mixture . It is within the scope of a person skilled in the art to determine the amounts of each oil in order to obtain an oily phase which meets the desired criteria.

The nonpolar or weakly polar oil can be a hydrocarbon oil.

The term "hydrocarbon oil" is understood to mean an oil formed essentially, indeed even composed, of carbon and hydrogen atoms and optionally of oxygen or nitrogen atoms which does not comprise a silicon or fluorine atom. It can comprise alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

The nonpolar or weakly polar oil can be nonvolatile.

The term "nonvolatile oil" is understood to mean any oil having a nonzero vapour pressure at ambient temperature and atmospheric pressure which is less than 0.02 mmHg and better still less than 10^"3 mmHg.

The composition advantageously comprises a nonpolar oil or a weakly polar oil or a mixture of the two. The oil or the mixture of oils advantageously represents at least 5% by weight of the total weight of the composition. The nonpolar oil and/or the weakly polar oil advantageously represent 5% to 99% by weight of the total weight of the composition, for example from 10% to 85% by weight or even from 15% to 80% by weight . According to one embodiment, the oil is chosen from nonvolatile nonpolar hydrocarbon oils, for example from saturated and linear or branched alkanes. According to one embodiment, the oil is chosen from linear or branched hydrocarbons, such as liquid paraffin, liquid petrolatum and liquid naphthalene, hydrogenated polyisobutene, isoeicosane, squalane, decene/butene copolymers and their mixtures. According to one embodiment, the fatty phase comprises from 30 to 70% by weight of nonvolatile nonpolar hydrocarbon oil(s), with respect to the weight of the fatty phase, preferably from 40 to 60% by weight, with respect to the weight of the fatty phase.

The composition advantageously comprises a sufficient amount of nonvolatile highly polar oil to disperse the solid crystalline material including the nitrogen monoxide. These nonvolatile highly polar oils can represent from 0.1 to 30% of the total weight of the composition, for example from 1 to 20%, in particular of the order of 10% by weight, with respect to the total weight of the composition. The composition can thus comprise an oily phase comprising one or more oils which can themselves be polar or nonpolar and volatile or nonvolatile. These oils can be chosen, alone or as a mixture, from volatile or nonvolatile oils of animal, vegetable, mineral or synthetic origin.

Mention may in particular be made of: - animal or vegetable oils formed by esters of fatty acid and of polyols, in particular liquid triglycerides, for example sunflower, maize, soybean, cucumber, grapeseed, sesame, hazelnut, apricot, almond or avocado oils; fish oils, glyceryl tricaprate/ caprylate, or vegetable or animal oils of formula RiCOOR₂ in which Ri represents the residue of a higher fatty acid comprising from 7 to 19 carbon atoms and R₂ represents a branched hydrocarbon chain comprising from 3 to 20 carbon atoms, for example purcellin oil; liquid paraffin, liquid petrolatum or calophyllum, macadamia, rapeseed, coconut, groundnut, palm, castor, jojoba, olive or cereal germ oils; shea butter oil; or perhydrosqualene;

- synthetic esters and ethers, in particular of fatty acids, such as oils of formula RiCOOR₂ in which

Ri represents the residue of a higher fatty acid comprising from 7 to 29 carbon atoms and R₂ represents a hydrocarbon chain comprising from 3 to 30 carbon atoms, such as, for example, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isononyl isononanoate or isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxy- stearate, diisostearyl malate, triisocetyl citrate or heptanoates, octanoates or decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate or diethylene glycol diisononanoate; pentaerythritol esters, such as pentaerythrityl tetraisostearate; or esters of the tridecyl trimellitate type;

- fatty alcohols having from 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol or oleyl alcohol;

- linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and their derivatives, liquid petrolatum, polydecenes, hydrogenated polyisobutene, such as parleam, or isoparaffins, such as isohexadecane and isodecane;

- glycerides and in particular acetyl- glycerides or triglycerides of fatty acids having 4 to 10 carbon atoms, such as triglycerides of heptanoic, octanoic and capric/caprylic acids.

Mention may be made, among the polar oils which are particularly preferred, of octyldodecanol, hexyldecanol, octyldecanol, oleyl alcohol, castor oil, diisostearyl malate, glyceryl triheptanoate, glyceryl trioctanoate, the triglyceride of capric/caprylic acids, triisononanoin, tridecyl trimellitate and their mixtures .

Mention may be made, among the nonpolar oils which are particularly preferred, of aliphatic hydrocarbons, in particular C₆-C₄₀ aliphatic hydrocarbons, such as liquid paraffins, which are volatile, such as isohexadecane or isododecane, or nonvolatile, and their derivatives; liquid petrolatum, hydrogenated or nonhydrogenated polydecenes, hydrogenated polyisobutene, such as parleam oil, squalane, polybutylenes or isononyl isononanoate; fluorinated oils, in particular perfluorinated oils, and their mixtures.

Mention may in particular be made of the following oils:

In addition, the composition can comprise nonvolatile silicone oils, such as polyalkylmethyl- siloxanes substituted by functional groups, such as hydroxyl, thiol and/or amine groups; or polysiloxanes modified by fatty acids, fatty alcohols or polyoxy- alkylenes . Volatile oil of the fatty phase

One or more volatile oils can be included in the fatty phase of the composition according to the invention. These oils can be hydrocarbon oils or silicone oils optionally comprising pendant alkyl or alkoxy groups or alkyl or alkoxy groups at the end of the silicone chain.

The term "volatile oil" is understood to mean any oil having a vapour pressure at ambient temperature and atmospheric pressure of greater than 0.02 πtmHg.

Mention may be made, as volatile silicone oil which can be used in the invention, of linear or cyclic silicones having a viscosity at ambient temperature of less than 8 cSt and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. Mention may in particular be made, as volatile silicone oil which can be used in the invention, of octamethylcyclotetrasiloxane, decamethylcyclopenta- siloxane, dodecamethylcyclohexasiloxane, heptamethyl- hexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and their mixtures.

Preference is in particular given, as volatile oil which can be used in the invention, to C₈-Ci₆ isoalkane oils (also known as isoparaffins) , such as isododecane, isodecane or isohexadecane, for example the oils sold under the trade names of Isopar or Permethyl and in particular isododecane (Permethyl 99 A) .

Preferably, the fatty phase of the composition comprises less than 10% of one or more volatile oils. Preferably, the fatty phase comprises less than 5%, less than 3%, indeed even less than 1%, of one or more volatile oils. The composition of the invention can be provided in the solid, pasty or more or less fluid liquid form. It can be a solid or soft anhydrous gel, a liquid oily phase or a foam. It can be provided in the form of a solid composition and more especially in the form of a stick.

This phase is capable of forming a continuous phase and comprises, as its name indicates, at least one nonaqueous organic solvent which is preferably a water-insoluble compound which is liquid at ambient temperature and atmospheric pressure.

The composition according to the invention can also comprise one or more cosmetically acceptable (acceptable tolerance, acceptable toxicology and acceptable feel) organic solvents.

These solvents can generally be present in a content ranging from 0.1 to 90%, more preferably from 10 to 90% by weight, with respect to the total weight of the composition, and better still from 30 to 90%. Mention may be made, as solvents which can be used in the composition of the invention, in addition to the hydrophilic organic solvents mentioned above, of ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono (n-butyl) ether; short-chain esters (having a total of 3 to 8 carbon atoms) , such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate or isopentyl acetate; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at ambient temperature, such as decane, heptane, dodecane, isododecane or cyclohexane; aromatic cyclic compounds which are liquid at ambient temperature, such as toluene and xylene; aldehydes which are liquid at ambient temperature, such as benzaldehyde or acetaldehyde, and their mixtures.

The composition according to the invention is advantageously provided in the anhydrous thickened form. Consequently, the invention relates more specifically to an anhydrous thickened composition for making up or caring for the lips comprising at least one thickening agent chosen from gelling agents for a fatty phase, waxes, fillers and their mixtures.

Mention may be made, as gelling agent for an oil, of optionally modified clays, such as hectorites modified by a (Ci₀ to C₂₂ fatty acid) ammonium chloride, such as hectorite modified by distearyldimethylammonium chloride; silica; elastomeric organopolysiloxanes which are partially or completely crosslinked and which have a three-dimensional structure, such as those sold under the names KSGβ, KSG16 or KSG18 by Shin-Etsu, Trefil E-505C or Trefil E-506C from Dow Corning, Gransil SR-CYC, SR DMFlO, SR-DC556, SR 5CYC gel, SR DMF 10 gel or SR DC 556 gel from Grant Industries, or SF 1204 and JK 113 from General Electric; galactomannans comprising one to six and better still from two to four hydroxyl groups per saccharide unit which are substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated by Ci to Ce and better still Ci to C₃ alkyl chains and more particularly ethylated guar having a degree of substitution of 2 to 3, such as that sold by Aqualon under the name N-Hance-AG; or gums, in particular silicone gums, such as PDMSs having a viscosity > 500 000 centistokes. These gelling agents are used, for example, at concentrations of 0.2 to 15% of the total weight of the composition.

The composition according to the invention can also comprise at least one fatty substance which is solid at ambient temperature chosen in particular from waxes, pasty fatty substances and their mixtures. These fatty substances can be of animal, vegetable, mineral or synthetic origin.

The composition can also additionally comprise at least one pasty compound. The term "pasty", within the meaning of the present invention, is understood to denote a lipophilic fatty compound exhibiting a reversible solid/liquid change in state and comprising, at a temperature of 23⁰C, a liquid fraction and a solid fraction. The term "pasty" is also understood to mean poly (vinyl laurate) .

The pasty compound is advantageously chosen from:

- lanolin and its derivatives,

- polymeric or nonpolymeric fluorinated compounds ,

- polymeric or nonpolymeric silicone compounds,

- vinyl polymers, in particular:

- homopolymers of olefins,

- copolymers of olefins,

- homopolymers and copolymers of hydrogenated dienes,

- linear or branched oligomers which are homo- or copolymers of alkyl

(meth) acrylates preferably having a C₈-C₃₀ alkyl group, - oligomers which are homo- and copolymers of vinyl esters having C₈-C3o alkyl groups,

- oligomers which are homo- and copolymers of vinyl ethers having C₈-C₃₀ alkyl groups,

- fat-soluble polyethers resulting from the polyetherification between one or more C₂-Ci_Oo, preferably C₂-C₅O, diols, - esters, and their mixtures .

Mention may in particular be made, by way of illustration of the lanolin derivatives which are conventionally used, of liquid lanolin, reduced lanolin, lanolin purified by adsorption, acetylated lanolin, oxypropylenated (5 PO) lanolin wax, liquid lanolin acetate, hydroxylanolin, polyoxyethylene lanolin, lanolin fatty acid, hard lanolin fatty acid, cholesteryl esters of lanolin fatty acid, lanolin alcohol, acetylated lanolin alcohol, isopropyl lanolate and others.

Preference is given in particular, among fat- soluble polyethers, to copolymers of ethylene oxide and/or of propylene oxide with alkylene oxides possessing a long Cg-C₃₀ chain, more preferably such that the ratio by weight of the ethylene oxide and/or propylene oxide to alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will in particular be made of the copolymers such that the long-chain alkylene oxides are arranged in blocks having an average molecular weight of 1000 to 10 000, for example a polyoxyethylene/polydodecyl glycol block copolymer, such as the ethers of dodecanediol (22 mol) and of polyethylene glycol (45 EO) sold by Akzo Nobel under the trade name Elfacos ST9. Preference is given in particular, among pasty esters, to:

- esters of an oligoitieric glycerol, in particular esters of diglycerol, especially condensates of adipic acid and of glycerol, for which a portion of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids, such as stearic acid, capric acid, isostearic acid and 12-hydroxystearic acid, such as in particular those sold under the trade name Softisan 649 by Sasol,

- arachidyl propionate, sold under the trade name Waxenol 801 by Alzo,

- phytosterol esters,

- noncrosslinked polyesters resulting from the polycondensation between a linear or branched C₄-C₅₀ di- or polycarboxylic acid and a C₂-C₅₀ diol or polyol, other than the polyester described above,

- ester aliphatic esters resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with an aliphatic monocarboxylic acid, and their mixtures, such as

- the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in the proportions of 1 to 1 (1/1) or hydrogenated castor oil monoisostearate,

- the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in the proportions of 1 to 2 (1/2) or hydrogenated castor oil diisostearate,

- the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in the proportions of 1 to 3 (1/3) or hydrogenated castor oil triisostearate,

- and their mixtures.

The choice will preferably be made, among pasty compounds of vegetable origin, of a mixture of soybean sterols and of oxyethylenated (5 EO) oxypropylenated (5 PO) pentaerythritol sold under the reference Lanolide by Vevy.

The pasty compound preferably represents 1 to 99%, better still 1 to 60%, better still 2 to 30% and even better still 5 to 15% by weight of the composition.

The composition of the invention can advantageously comprise, in addition, at least one colouring material which can be chosen from dyes, pigments, pearlescent agents and their mixtures. This colouring material can represent from 0.001 to 98%, preferably from 0.5 to 85% and better still from 1 to 60% of the total weight of the composition.

The dyes are preferably fat-soluble dyes, although water-soluble dyes can be used. The fat- soluble dyes are, for example, Sudan red, D & C Red 17, D & C Green 6, β-carotene, soybean oil, Sudan brown, D & C Yellow 11, D & C Violet 2, D & C Orange 5, quinoline yellow or annatto. They can represent from 0 to 20% of the weight of the composition and better still from 0.1 to 6%. The water-soluble dyes are in particular beetroot juice or methylene blue and can represent from 0.1 to 6% by weight of the composition (if present) .

For a composition in the paste or cast form, such as lipsticks or products for making up the body, use is generally made of 0.5 to 50% of colouring material, preferably of 2 to 40% and better still of 5 to 30%, with respect to the total weight of the composition.

The term "pigments" should be understood as meaning white or coloured and inorganic or organic particles which are insoluble in the liquid fatty phase and which are intended to colour and/or to opacify the composition. The term "fillers" should be understood as meaning colourless or white, inorganic or synthetic and lamellar or nonlamellar particles. The term

"pearlescent agents" should be understood as meaning iridescent particles, in particular produced by certain shellfish in their shells or else synthesized. These fillers and pearlescent agents are used in particular to modify the texture of the composition.

The pigments can be present in the composition in a proportion of 0.05 to 30% of the weight of the final composition and preferably in a proportion of 2 to 20%. Mention may be made, as inorganic pigments which can be used in the invention, of titanium, zirconium or cerium oxides and also zinc, iron or chromium oxides and ferric blue. Mention may be made, among the organic pigments which can be used in the invention, of carbon black and barium, strontium, calcium (D & C Red No. 7) and aluminium lakes.

The pearlescent agents can be present in the composition in a proportion of 0.001 to 20% of the total weight of the composition, preferably at a level of the order of 1 to 15%. Mention may be made, among the pearlescent agents which can be used in the invention, of mica covered with titanium oxide, with iron oxide, with natural pigment or with bismuth oxychloride, such as coloured titanium oxide-coated mica.

The composition advantageously comprises goniochromatic pigments, for example interferential multilayer pigments, and/or reflecting pigments. These two types of pigments are disclosed in Application FR 0 209 246, the content of which is incorporated by reference in the present application.

The composition according to the invention can additionally comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, with respect to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. The term "fillers" should be understood as meaning colourless or white and inorganic or synthetic particles of any shape which are insoluble in the medium of the composition, whatever the temperature at which the composition is manufactured. These fillers are used in particular to modify the rheology or the texture of the composition.

The fillers can be inorganic or organic and of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, and the like) . Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem) , poly-β-alanine powders, polyethylene powders, powders formed of tetrafluoroethylene polymers (Teflon®) , lauroyllysine, starch, boron nitride, polymeric hollow microspheres, such as those of polyvinylidene/acrylonitrile chloride, such as Expancel® (Nobel Industrie) or of acrylic acid copolymers (Polytrap® 603 from Dow Corning) , silicone resin microbeads (Tospearls® from Toshiba, for example) , polyorganosiloxane elastomer particles, precipitated calcium carbonate, magnesium carbonate, basic magnesium carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos) , glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate, or Polypore® L 200 (Chemdal Corporation) . Mention may also be made of silica-based fillers, such as Aerosil 200 or Aerosil 300; Sunsphere L-31 or Sunsphere H-31, sold by Asahi Glass; Chemicelen, sold by Asahi Chemical; or composites of silica and of titanium dioxide, such as the TSG series sold by Nippon Sheet Glass. Finally, mention may be made of polyurethane powders, in particular powders formed of crosslinked polyurethane comprising a copolymer, the said copolymer comprising trimethylol hexyllactone . In particular, a hexamethylene diisocyanate/trimethylol hexyllactone polymer may be involved. Such particles are in particular available commercially, for example under the name of Plastic Powder D-400^® or Plastic Powder D-800^® from Toshiki.

The filler can, for example, be a filler having a mean particle size of less than 100 μm, in particular of between 1 and 50 μm, for example between 4 and 20 μm.

The composition can additionally comprise at least one wax. The term "wax", within the meaning of the present invention, is understood to mean a lipophilic fatty compound which is solid at ambient temperature (25°C) , which exhibits a reversible solid/liquid change in state, which has a melting point of greater than 30⁰C which can range up to 200⁰C, which has a hardness of greater than 15 MPa and which exhibits, in the solid state, an anisotropic crystalline arrangement. On bringing the wax to its melting point, it is possible to render it miscible with oils and to form a microscopically homogeneous mixture but, on bringing the temperature of the mixture back to ambient temperature, recrystallization of the wax in the oils of the mixture is obtained.

The waxes which can be used in the invention are compounds which are solid at ambient temperature which are intended to structure the composition, in particular in the stick form; they can be hydrocarbon, fluorinated and/or silicone waxes and can be of plant, mineral, animal and/or synthetic origin. In particular, they exhibit a melting point of greater than 40⁰C and better still of greater than 45°C.

Mention may be made, as waxes which can be used in the invention, of those generally used in the cosmetics field: they are in particular of natural origin, such as beeswax, carnauba wax, candelilla wax, ouricury wax, Japan wax, cork fibre wax, sugarcane wax, rice wax, montan wax, paraffin wax, lignite wax, microcrystalline wax, ceresin or ozokerite, or hydrogenated oils, such as jojoba oil; synthetic waxes, such as the polyethylene waxes resulting from the polymerization or copolymerization of ethylene and Fischer-Tropsch waxes, or also fatty acid esters, such as octacosanyl stearate or glycerides, which are solid at 40⁰C and better still at 45°C; silicone waxes, such as alkyl or alkoxy dimethicones having an alkyl or alkoxy chain of 10 to 45 carbon atoms or poly(di)- methylsiloxane esters which are solid at 40⁰C, the ester chain of which comprises at least 10 carbon atoms; and their mixtures. Tacky wax

According to one embodiment, the composition comprises at least one "tacky" wax, that is to say a wax having a tack of greater than or equal to 0.1 N.s. The wax is generally a lipophilic compound which is solid at ambient temperature (25°C), which exhibits a reversible solid/liquid change in state and which has a melting point of greater than or equal to 30⁰C which can range up to 120 °C.

On bringing the wax to the liquid state (melting) , it is possible to render it miscible with oils and to form a microscopically homogeneous mixture but, on bringing the temperature of the mixture back to ambient temperature, recrystallization of the wax in the oils of the mixture is obtained. In particular, the waxes suitable for the invention can exhibit a melting point of greater than approximately 45°C, better still of greater than or equal to 50⁰C and in particular of greater than or equal to 55⁰C.

The melting point of the wax can be measured using a differential scanning calorimeter (DSC) , for example the calorimeter sold under the name MDSC 2929 by TA Instruments.

The measurement protocol is as follows: A 5 mg sample of the product placed in a crucible is subjected to a first rise in temperature ranging from 0⁰C to 120°C at a heating rate of

10°C/minute, is then cooled from 120⁰C to 0⁰C at a cooling rate of 10°C/minute and, finally, is subjected to a second rise in temperature ranging from 0°C to 120⁰C at a heating rate of 5°C/minute. During the second rise in temperature, the variation in the difference in power absorbed by the empty crucible and by the crucible comprising the sample of product is measured as a function of the temperature. The melting point of the compound is the value of the temperature corresponding to the tip of the peak of the curve representing the variation in the difference in power absorbed as a function of the temperature.

The waxes capable of being used in the compositions according to the invention are chosen from waxes of animal, vegetable, mineral or synthetic origin, and their mixtures, which are solid and stiff at ambient temperature. The tacky wax used can have in particular a tack ranging from 0.1 N.s to 10 N.s, in particular ranging from 0.1 N.s to 5 N.s, preferably ranging from 0.2 to 5 N.s and better still ranging from 0.3 to 2 N.s.

The tack of the wax is determined by the measurement of the change in the force (compressive force or stretching force) as a function of the time at 20⁰C using the texture analyser sold under the name "TA-XT2^®" by Rheo, equipped with a stainless steel cylinder with a diameter of 2 mm.

The measurement protocol is as follows: The wax is melted at a temperature equal to the melting point of the wax + 10⁰C. The molten wax is cast in a receptacle with a diameter of 25 mm and a depth of 20 mm. The wax is recrystallized at ambient temperature (25⁰C) for 24 hours, so that the surface of the wax is flat and smooth, and then the wax is stored at 20⁰C for at least 1 hour before measuring the tack. The rotor of the texture analyser is displaced at the rate of 0.1 mm/s and then penetrates the wax to a penetration depth of 0.3 mm. When the rotor has penetrated the wax to a depth of 0.3 mm, the rotor is held stationary for 1 second (corresponding to the relaxation time) and is then withdrawn at the rate of 0.5 mm/s.

The tacky wax which can be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, especially- ranging from 0.05 MPa to 3 MPa.

The hardness is measured according to the protocol described above.

Use may be made, as tacky wax, of a C₂₀-C₄₀ alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms) , alone or as a mixture. Such a wax is sold in particular under the names "Kester Wax K 82 P^®" and "Kester Wax K 80 P^®" by Koster Keunen.

The abovementioned waxes generally exhibit a starting melting point of less than 45°C. The composition according to the invention can comprise a total content of waxes ranging from 5 to 50% by weight, with respect to the total weight of the composition, preferably from 5 to 40% by weight, more particularly from 10 to 35% by weight. The wax or waxes (including the tacky wax) can be present in the form of an aqueous wax microdispersion. The term "aqueous wax microdispersion" is understood to mean an aqueous dispersion of wax particles in which the size of said wax particles is less than or equal to approximately 1 μm.

Wax microdispersions are stable dispersions of colloidal wax particles and are described in particular in "Microemulsions Theory and Practice", edited by L.M. Prince, Academic Press (1977), pages 21-32.

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

The wax microdispersions can also be obtained by stirring the mixture of wax, of surfactant and of water using stirring means, such as ultrasound, a high pressure homogenizer or turbine mixers.

The particles of the wax microdispersion preferably have mean sizes of less than 1 μm (in particular ranging from 0.02 μm to 0.99 μm) , preferably of less than 0.5 μm (in particular ranging from 0.06 μm to 0.5 μm) .

These particles are composed essentially of a wax or of a mixture of waxes. However, they can comprise a minor proportion of oily and/or pasty fatty additives, a surfactant and/or a conventional fat- soluble additive/active agent. When the wax or the mixture of waxes is present in the compositions according to the invention in the form of an aqueous dispersion of particles, the size of the particles, expressed as ^λλeffective" volume- average diameter D[4,3], can advantageously be less than or equal to 1 μm and in particular less than or equal to 0.75 μm.

The wax particles can exhibit various shapes. They can in particular be spherical. The composition can comprise at least one other wax than that mentioned above.

The wax can exhibit a hardness ranging from 0.05 MPa to 30 MPa, the hardness being determined by the method described above for the fatty phase. Use may in particular be made of hydrocarbon waxes, such as beeswax, lanolin wax, lemon wax, orange wax and Chinese insect waxes; rice wax, carnauba wax, candelilla wax, ouricury wax, Japan wax, berry wax, shellac wax and sumac wax; montan wax, microcrystalline waxes, paraffin waxes and ozokerite; polyethylene waxes, polymethylene waxes, waxes obtained by the Fischer-Tropsch synthesis and waxy copolymers, and also their esters.

Mention may also be made of the waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C₈-C₃₂ fatty chains . Mention may in particular be made, among these, of hydrogenated jojoba oil, isomerized jojoba oil, such as the trans-isomerized partially hydrogenated jojoba oil manufactured or sold by Desert Whale under the commercial reference Iso Jojoba 50^®, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, di (1, 1, 1-trimethylolpropane) tetrastearate, sold under the name "Hest 2T-4S" by Heterene, or di (1, 1, 1-tri- methylolpropane) tetrabehenate, sold under the name "Hest 2T-4B" by Heterene.

Mention may also be made of silicone waxes and waxes modified with silicones, such as, for example, candelilla wax modified with silicone, or fluorinated waxes.

Use may also be made of the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the name "Phytowax Olive 18 L 57" or else of the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the names "Phytowax castor 16L64" and "Phytowax castor 22L73" by Sophim. Such waxes are disclosed in Application FR-A-2 792 190.

According to one embodiment, the wax exhibits a hardness of less than 4 MPa, preferably of less than or equal to 3.5 MPa.

Such waxes are, for example, oxypropylenated (5 EP) lanolin wax, orange wax, lemon wax, hydrogenated castor oil wax, the mixture of esters of aliphatic acids and of primary alcohols sold under the reference Burco LB-02, the olive wax (hydrogenated unsaponifiable products from olive oil) sold under the reference

Inholive by Exa International, the PDMS-grafted behenyl methacrylate wax sold under the reference KP-562 by Shin-Etsu, fluoropolymethylalkyldimethylsiloxane wax, such as that sold under the reference Wax 23087 by Wacker, C₃₀-C₄₅ alkyl dimethicone wax, such as that sold under the reference SF 1642 by GE Bayer, or ethoxylated (5 EO) di (trimethylolpropane) tetrastearate, such as that sold under the reference SF 1642 by GE Bayer. The composition can comprise a micronized wax, also referred to as microwax.

Mention may in particular be made, as microwaxes which can be used in the compositions according to the invention, of carnauba microwaxes, such as those sold under the name of "MicroCare 350^®" by Micro Powders, synthetic wax microwaxes, such as those sold under the name of "MicroEase 114S^®" by Micro Powders, microwaxes composed of a mixture of carnauba wax and polyethylene wax, such as those sold under the names of "Micro Care 300^®" and "310^®" by Micro Powders, microwaxes composed of a mixture of carnauba wax and synthetic wax, such as that sold under the name "Micro Care 325^®" by Micro Powders, polyethylene microwaxes, such as those sold under the names of "Micropoly 200^®", "220^®", "220L^®" and "250S^®" by Micro Powders, and polytetrafluoroethylene microwaxes, such as those sold under the names of "Microslip 519^®" and "519 L^®" by Micro Powders.

Among the abovementioned microwaxes, some, such as, for example, the carnauba microwax, the synthetic wax microwax "MicroEase 114S" or the microwax composed of a mixture of carnauba wax and synthetic wax "MicroCare 325", exhibit a starting melting point of greater than or equal to 45°C.

The composition according to the invention advantageously comprises polyethylene wax with a weight-average molecular weight of between 300 and 700 g/mol, in particular of 500 g/mol.

By way of indication, the wax can represent from 0.01 to 65%, preferably from 2 to 50% and better still from 5 to 35%, of the total weight of the composition. The composition according to the invention can also comprise ingredients commonly used in cosmetics, such as antioxidants. Fibres

The composition can comprise fibres. The term "fibre" should be understood as meaning an object with a length L and with a diameter D such that L is much greater than D, D being the diameter of the circle in which the cross section of the fibre appears. In particular, the ratio L/D (or shape factor) is chosen within the range from 3.5 to 2500, preferably from 5 to 500 and better still from 5 to 150.

The fibres which can be used in the composition of the invention can be fibres of synthetic or natural and inorganic or organic origin. In particular, the fibres have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 1 mm to 3.5 mm. Their cross section can be included within a circle with a diameter ranging from 2 nm to 500 μm, preferably ranging from 100 nm to 100 μm and better still from 1 μm to 50 μm. The weight or count of the fibres is often given in denier or decitex and represents the weight in grams per 9 km of yarn. Preferably, the fibres according to the invention have a count chosen within the range from 0.15 to 30 deniers and better still from 0.18 to 18 deniers . The fibres can be those disclosed in

Application EP 1 201 221, the content of which is incorporated in the present application by reference.

Use is preferably made of fibres of synthetic origin and in particular of organic fibres, such as those used in surgery. Use may advantageously be made of water-insoluble fibres. The fibres which can be used in the composition according to the invention are preferably polyamide, cellulose, poly (p-phenylene terephthalamide) or polyethylene fibres. Their length (L) can range from 0.1 mm to 5 mm, preferably from 0.25 mm to 1.6 mm, and their mean diameter can range from 1 μm to 50 μm. Use may in particular be made of the polyamide fibres sold by Etablissements P. Bonte under the name of "Polyamide 0.9 Dtex 3 mm", having a mean diameter of 6 μm, a count of approximately 0.9 dtex and a length ranging from 0.3 mm to 5 mm. Use may also be made of poly (p-phenylene terephthalamide) fibres with a mean diameter of 12 μm and a length of approximately 1.5 mm, such as those sold under the name of "Kevlar Floe" by Du Pont Fibres, or alternatively of cellulose (or rayon) fibres having a mean diameter of 50 μm and a length ranging from 0.5 mm to 6 mm, such as those sold under the name of "Natural rayon flock fiber RClBE - N003 - M04" by Claremont Flock. Use may also be made of polyethylene fibres, such as those sold under the name of "Shurt Stuff 13 099 F" by Mini Fibers. The fibres can be present in the composition according to the invention in a content ranging from 0.01% to 10% by weight, with respect to the total weight of the composition, preferably from 0.1% to 5% by weight and better still from 0.3% to 2% by weight. Gelling agent

The first composition can comprise at least one gelling agent which can be inorganic or organic and polymeric or nonpolymeric. The gelling agent can be chosen in order to gel an aqueous phase or a fatty phase of the first composition, as the case may be.

The term "gelling agent" is understood to mean a compound which modifies the rheology of the medium in which it is incorporated.

The gelling agent for an aqueous medium can be chosen from:

- hydrophilic clays, - hydrophilic pyrogenic silica,

- water-soluble cellulose thickeners,

- guar, xanthan, locust bean, scleroglucan, gellan, rhamsan, karaya or carrageenan gums,

- alginates, maltodextrins, starch and its derivatives, or hyaluronic acid and its salts,

- the poly (glyceryl (meth) acrylate) polymers sold under the names of "Hispagel" or ^λλLubragel" by Hispano Quimica or Guardian,

- polyvinylpyrrolidone, - poly (vinyl alcohol),

- crosslinked polymers and copolymers of acrylamide, such as those sold under the names of "PAS 5161" or "Bozepol C" by Hoechst, of "Sepigel 305" by Seppic, - the crosslinked methacryloyloxyethyltri- methylammonium chloride homopolymers sold under the name of "Salcare SC95" by Allied Colloid, or - associative polymers and in particular associative polyurethanes .

Such gelling agents are disclosed in particular in Application EP-A-I 400 234, the content of which is incorporated by way of reference.

The gelling agent for an oily medium can be chosen from:

- organophilic clays,

- hydrophobic pyrogenic silicas, - alkylated guar gums (with Ci-C₆ alkyl group), such as those disclosed in EP-A-708 114;

- gelling polymers for an oil, such as triblock or star polymers resulting from the polymerization or copolymerization of at least one monomer comprising an ethylene group, such as the polymers sold under the name Kraton;

- polymers with a weight-average molecular weight of less than 100 000, comprising a) a polymer backbone having hydrocarbon repeat units which are provided with at least one heteroatom and optionally b) at least one optionally functionalized pendant fatty chain and/or at least one optionally functionalized terminal fatty chain, having from 6 to 120 carbon atoms, which are bonded to these hydrocarbon units, such as disclosed in Applications WO-A-02/056847 and WO-A-02/47619, the content of which is incorporated by way of reference; in particular, polyamide resins (in particular comprising alkyl groups having from 12 to 22 carbon atoms) , such as those disclosed in US-A-5 783 657, the content of which is incorporated by way of reference; - silicone-modified polyamide resins, such as disclosed in Application EP-A-I 266 647 and in the French patent application filed under No. 02/16039, the content of which is incorporated by way of reference. Such gelling agents are disclosed in particular in Application EP-A-I 400 234, the content of which is incorporated by way of reference.

The gelling agent can be an organic gelling agent, that is to say an agent comprising at least one organic compound. The organic gelling agents can be chosen from those disclosed in Application WO-A-03/105788, the content of which is incorporated by way of reference. Of course, a person skilled in the art will take care to choose this or these optional additional compounds and/or their amounts so that the advantageous properties of the corresponding composition according to the invention are not, or not substantially, detrimentally affected by the envisaged addition. The composition of the invention can be provided in the form of a coloured product for making up the lips, such as a lipstick or a lip gloss, exhibiting care or treatment properties. The compositions of the present invention can be care preparations for the skin, for example exfoliating or scrubbing preparations or exfoliating masks; makeup preparations for the face in the form of creams, sticks or rouges; preparations for the care of the eyes, for example eyeshadow, mascara, eye liner or creams for the eyes; preparations for the care of the lips, for example lipsticks, lip glosses or pencils for the contour of the lips; preparations for the care of the nails, such as colourless or coloured nail varnish; care preparations for the feet, for example creams for the feet or balms for the feet, specific deodorants and antiperspirants, or preparations for treating callosities; photoprotective preparations, such as sun milks, lotions, creams and oils, "tropical" sun compositions or sunscreens, preparations which produce tanning or aftersun preparations; tanning preparations, for example self tanning creams; or hair treatment or hair care preparations . The composition according to the invention can be in the powder form. The powders can comprise at least 70% by weight, preferably from 77 to 99.9% by weight, with respect to the total weight of the composition, of particulate or pulverulent phase comprising pigments and/or fillers as described above. They can also comprise a fatty phase as binder comprising fatty substances, such as oils, pastes or waxes described above, which facilitates the adhesion to the skin of the pulverulent compounds and their cohesion with one another in the final composition. This fatty phase can represent up to 30% by weight, preferably from 0.1 to 23% by weight and more preferably from 3 to 20% by weight, with respect to the total weight of the composition.

The composition can also be in the form of a composition which can be vaporized by conventional devices, pump-action sprays and aerosols, in all positions .

The composition can also be in the form of a foam produced by expansion of a gas, such as disclosed in Application US 2004/126345, the content of which is incorporated in the present application by reference. The composition according to the invention can be manufactured by known processes generally used in the cosmetics or dermatological field. In particular, it can be obtained by heating the various constituents at the melting point of the highest waxes and then casting the molten mixture in a mould (dish or thimble) . It can also be obtained by extrusion, as disclosed in Application EP-A-667 146.

The invention is illustrated in more detail in the following examples. The percentages are given by weight . Example 1: Preparation of zeolites Zn-NO and MN-NO The zeolites Zn-NO and Mn-NO are prepared according to Example 2b of Application WO 2005/003032, incorporated by reference.

Use is made of a zeolite A synthesized according to the procedure given by Robson H. and Lillerud K. P. in Verified Syntheses of Zeolitic Materials, International Zeolite Association (2001) ; www. iza-synthesis . org.

The sodium ions are subsequently replaced by transition metal cations known for binding nitrogen monoxide (for example: Mn²⁺ or Zn²⁺), in order to obtain ion-exchange zeolites, according to the following protocol: sodium zeolite A (5 g) is placed in a 0.05M metal acetate solution (400 ml, distilled water) and dried at 100⁰C overnight.

The zeolites are analyzed using the Agilent 7500 ICP-MS spectrometer.

The zeolites A respectively comprising Mn or Zn are subsequently dehydrated. 0.3 g of the zeolite A Mn or Zn thus prepared is dehydrated at 300⁰C for 2 hours (0.5 mmHg) . It is subsequently cooled to ambient temperature and exposed to a nitrogen monoxide/helium (10% NO, 90% He) gas mixture at a pressure of 3 atmospheres for 10 minutes and then exposed again to nitrogen monoxide at a pressure of 3 atmospheres. This stage is repeated 3 times . The ability of the NO to be released is subsequently measured in the presence of a stream of argon (either saturated with water vapour or taken directly from a gas cylinder, 5 ml.min^"1) . The gas is subsequently bubbled into a saline solution of phosphate buffer (pH 7.4, 10 ml) in which a nitrogen monoxide precalibrated electrode (World Precision Instruments, ISO-NO Mark II) is immersed. The concentration of NO released over time is thus measured.

Example 2 : Lip gloss

Polybutene 89.5%

Zeolite comprising nitrogen monoxide, prepared according to Example 1 with Mn²⁺ as metal cation 10%

Fragrance 0.5%

Example 3 : Lip gloss

Polybutene 86.5%

Zeolite comprising nitrogen monoxide, prepared according to Example 1 using

Zn²⁺ as metal cation 10%

Fragrance 0.5%

Pigments 3%

Example 4 : Lip gloss Polybutene 71.5%

Octyldodecanol 15%

Zeolite comprising nitrogen monoxide, prepared according to Example 1 using

Mn as metal cation 10%

Fragrance 0.5%

Pigments 3% Example 5 : Nail lacquer

Carnauba wax 7.7%

Paraffin wax 6%

Beeswax 10.2%

Black iron oxide 2.7% Talc 2%

Bentone 38V 5.5%

Propylene carbonate 1.83%

Zeolite comprising nitrogen monoxide, prepared according to Example 1 using Zn²⁺ as metal cation 2%

Preservative q. s .

Isododecane q.s. for 100%

Claims

1. Anhydrous cosmetic composition comprising nitrogen monoxide adsorbed in a microporous solid crystalline material.

2. Composition according to Claim 1, in which the size of the pores of the microporous solid crystalline material is less than or equal to 1 micron, preferably less than or equal to 1000 angstroms, preferably less than or equal to 50 angstroms, more preferably less than or equal to 30 angstroms.

3. Composition according to Claim 1 or 2, in which the pores of the microporous solid crystalline material form a repeating three-dimensional network.

4. Composition according to one of the preceding claims, in which the nitrogen monoxide is complexed, in the microporous solid crystalline material, with an organic or inorganic cation.

5. Composition according to one of the preceding claims, in which the microporous solid crystalline material is a zeolite of following general formula (I) :

[ (Miⁿ⁺) _x/n (M₂ ^p+) _y/p ... (M_n ^q+) _v/q] [Al₂Si₁^O₄] ( D in which Mi and M₂ to M_n are chosen independently from - extraframework metal cations chosen independently from the group consisting of Li, Na, K, Mn, Ca, Mg, Fe, Cu, Ru, Rh, Co, Ni, Zn and Ag, and organic cations, such as N (Ri) _a (R₂) b⁺, where Ri and R₂ are chosen independently from H, -CH₃, -CH₂CH₃ or -CH₂CH₂CH₃ and a and b are independently 0, 1, 2, 3 or 4, so that a + b = 4, x ranges from zero to nz, y ranges from zero to pz and v ranges from zero to qz, provided that x/n + y/p + ... + v/q = z, z is the number of silicon atoms replaced by aluminium atoms in the zeolite framework, n+, p+ and q+ are independently integers 1+,

2+ or 3+ when the associated cation is a metal cation or equal to 1+ when the associated cation is an organic cation. β. Composition according to Claim 5, in which Mi and/or M₂ represents NH₄ ⁺.

7. Composition according to the preceding claim, in which the zeolite has the following general formula (II) :

[ (Miⁿ⁺ ) _x/n (M₂ ^P+ ) _y/p] [Al_zSii__zO₄ ] ( H ) in which Mi, M₂, z, n+ and p+ are defined as in the preceding claim, x ranges from zero to nz, and y ranges from zero to pz, provided that x/n + y/p = z.

8. Composition according to either of

Claims 5 and 6, in which the metal cations are cations of elements Zn or Mn.

9. Composition according to one of the preceding claims, characterized in that it comprises at least one fatty substance chosen from oils, waxes and pasty fatty substances.

10. Composition according to the preceding claim, characterized in that it comprises a nonpolar oil such that its mean solubility parameter at 25°C δ_a = 0 (J/cm³)^1/2 or a weakly polar oil such that its mean solubility parameter at 25°C 0 < δ_a < 5.0 (J/cm³)¹⁷².

11. Composition according to the preceding claim, characterized in that the nonpolar or weakly polar oil represents from 5% to 99% by weight of the total weight of the composition, for example from 10% to 85% by weight or even from 15% to 80% by weight.

12. Composition according to one of the preceding claims, characterized in that it comprises at least one colouring material chosen from pigments, pearlescent agents and dyes.

13. Composition according to one of the preceding claims, characterized in that it comprises at least one filler.

14. Composition according to one of the preceding claims, characterized in that it comprises a gelling agent.

15. Composition according to one of the preceding claims, characterized in that it comprises fibres .

16. Composition according to one of the preceding claims, characterized in that it is in the form of a product for making up the lips or skin.

17. Cosmetic use of a composition according to one of Claims 1 to 16 for caring for or making up the skin, lips or nails.

18. Process for making up or caring for the skin or lips, which consists in applying a composition according to one of Claims 1 to 16.