WO2002056848A1

WO2002056848A1 - Nail varnish comprising a polymer

Info

Publication number: WO2002056848A1
Application number: PCT/FR2002/000144
Authority: WO
Inventors: Xavier Blin; Véronique Ferrari; Frédéric Auguste
Original assignee: L'oreal
Priority date: 2001-01-17
Filing date: 2002-01-15
Publication date: 2002-07-25
Also published as: JP2005500249A; EP1353635A1; FR2819402A1; FR2819402B1

Abstract

The invention relates to a nail varnish composition comprising at least one organic liquid phase containing at least one volatile organic solvent. Said organic liquid phase is structured by at least one polymer having an average molecular mass that is less than or equal to 100,000, comprising a) a polymer backbone, having hydrocarbon repeat units provided with at least one heteroatom, and possibly b) pendant and/or terminal fatty chains, which may be functionalised, having between 6 and 120 carbon atoms and being chained to said repeat units. The inventive composition can take the form of a nail varnish stick.

Description

Nail polish comprising a polymer

The present invention relates to a composition for caring for and / or treating and / or making up human nails, containing a liquid organic phase containing a volatile organic solvent, structured by a particular polymer. This composition is in particular in the form of a nail varnish stick.

The makeup composition can also be applied to makeup accessories (support) such as false nails.

In organic solvent-based nail varnishes, it is common to thicken the organic phase with thickening agents.

By “liquid organic phase”, within the meaning of the invention, is meant an organic phase liquid at ambient temperature (25 ° C.), composed of one or more organic compounds liquid at ambient temperature, also called organic solvents or oils, generally compatible with each other. The thickened compositions make it easier to take the product out of its packaging without significant loss, to distribute the varnish on the surface of the nail or even to be able to use the varnish in sufficient quantities to obtain the desired cosmetic effect. In addition, the thickening agent makes it possible to prevent the sedimentation of the pigments often present in nail varnishes, during storage.

To thicken the compositions, it is known to use clays such as organomodified montmorillonites as described in application GB-A-2021411. However, the clays cloud the composition and do not allow the preparation of a translucent composition. In addition, clays are often formulated with an agent promoting their swelling such as citric acid or orthophosphoric acid which can cause instability of the composition. Furthermore, the nail varnishes known to date are generally in the form of a fluid composition which is applied using a brush or even a pen (see in particular US-A-4712571).

There therefore remains the need for a composition which does not have the above drawbacks. Furthermore, it is desirable to be able to have a new dosage form of nail varnish different from the nail varnishes known to date.

The subject of the invention is precisely a composition for caring for and / or making up and / or treating the nails which makes it possible to remedy the drawbacks mentioned above.

Surprisingly, the applicant has found that the use of particular polymers associated with one or more volatile organic solvents makes it possible to obtain structured nail varnishes, in particular of. gel and more particularly a stick, the application of which on the nails results in a film having good cosmetic properties.

The invention applies not only to nail makeup products but also to nail care and / or treatment products.

More specifically, the subject of the invention is a structured nail varnish composition containing at least one liquid organic phase comprising at least one volatile organic solvent, the liquid organic phase being structured by at least one first polymer of average molecular mass in weight less than or equal to 100,000, comprising a) a polymer backbone, having hydrocarbon repeating units provided with at least one heteroatom, and b) optionally functional pendant and / or terminal fatty chains having from 6 to 120 atoms carbon and being linked to these hydrocarbon units.

The subject of the invention is also a composition of nail polish in stick comprising an organic phase containing a volatile organic solvent and a first polymer of average molecular mass by weight less than or equal to 100,000, comprising a) a polymer backbone, having hydrocarbon repeating units provided with at least one heteroatom, and b) optionally functional pendant and / or terminal fatty chains, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units.

The subject of the invention is also a cosmetic method for caring for, making up or treating the nails, comprising the application to the nails of the composition, in particular the cosmetic composition as defined above.

The subject of the invention is also the use of an organic liquid phase containing at least one volatile organic solvent and a sufficient quantity of a first polymer of average molecular mass by weight less than or equal to 100,000, comprising a) a polymer backbone, having hydrocarbon repeating units provided with at least one heteroatom, and b) optionally pendant and / or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units, in a composition of nail polish, to obtain a stick.

The composition of nail varnish of the invention can be in the form of a paste, a solid, a gel, a cream, a thickened liquid. It can be an oil-in-water or water-in-oil emulsion, a rigid or flexible anhydrous gel. In particular, it is in the form of a stick or cup, and more especially in the form of an anhydrous rigid gel, in particular an anhydrous stick. More specifically, it is in the form of a rigid gel which can be translucent or transparent, the liquid organic phase forming the continuous phase.

The gelling of the solvent phase is adjustable according to the nature of the heteroatom polymer used, and can be such that a rigid structure is obtained in the form of a stick or a stick. The structuring polymer of the composition of the invention is a non-deformable solid at room temperature (25 ° C).

By “functionalized chains” within the meaning of the invention, is meant an alkyl chain comprising one or more functional or reactive groups chosen in particular from amide, hydroxyl, ether, oxyalkylene or polyoxyalkylene, halogen groups, including fluorinated or perfluorinated groups, ester , siloxane, polysiloxane. In addition, the hydrogen atoms of one or more fatty chains can be substituted at least partially by fluorine atoms.

According to the invention, these chains can be linked directly to the polymer backbone or via an ester function or a perfluorinated group.

By "polymer" is meant within the meaning of the invention a compound having at least 2 repeating units, and preferably at least 3 repeating units, which are identical.

By "hydrocarbon repeating units" is meant within the meaning of the invention a unit comprising from 2 to 80 carbon atoms, and preferably from 2 to 60 carbon atoms, carrying hydrogen atoms and optionally atoms of oxygen, which can be linear, branched or cyclic, saturated or unsaturated. These patterns further comprise each of one to several heteroatoms which are advantageously non-pendant and which are found in the polymer backbone. These heteroatoms are chosen from nitrogen, sulfur and phosphorus atoms and their associations, possibly associated with one or more oxygen atoms. Preferably, the units comprise at least one nitrogen atom, in particular not pendant. These units also advantageously comprise a carbonyl group.

The heteroatom units are in particular amide units forming a skeleton of the polyamide type, carbamate and / or urea units forming a polyurethane, polyurea and / or polyurea-urethane skeleton. Preferably, these patterns are amide patterns. Advantageously, the pendant chains are linked directly to at least one of the heteroatoms of the polymer backbone. According to one embodiment, the first polymer comprises a polyamide skeleton.

The first polymer can comprise, between the hydrocarbon units, silicone units or oxyalkylene units.

In addition, the first polymer of the composition of the invention advantageously comprises a total number of fatty chains which represents from 40 to 98% of the total number of heteroatom units and fatty chains, and better still from 50 to 95%. The nature and proportion of the heteroatom units depends on the nature of the organic phase and is in particular similar to the polar nature of the organic phase. Thus, the more polar the heteroatom units and in high proportion in the first polymer, which corresponds to the presence of several heteroatoms, the more the first polymer has affinity with polar oils. On the other hand, the more the heteroatom units are not very polar or even nonpolar or in low proportion, the more the first polymer has affinity with nonpolar oils.

The first polymer is advantageously a polyamide. Also, the subject of the invention is also a structured nail varnish composition containing at least one liquid organic phase comprising at least one volatile organic solvent, the liquid organic phase being structured by at least one polyamide of lower average molecular weight or equal to 100,000, comprising a) a polymer backbone, having repeating amide units, and b) optionally pendant and / or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these amide units.

The subject of the invention is also a composition of nail polish in a stick comprising a volatile organic solvent and a first polyamide polymer of average molecular mass by weight less than or equal to 100,000, comprising a) a polymer backbone, having repeating amide units, and b) optionally functional pendant and / or terminal fatty chains, having from 6 to 120 carbon atoms and being linked to these amide units.

Preferably, the pendant fatty chains are linked to at least one of the nitrogen atoms of the amide units of the first polymer.

In particular, the fatty chains of this polyamide represent from 40 to 98% of the total number of amide units and fatty chains, and better still from 50 to 95%.

Advantageously, the first polymer, and in particular the polyamide, of the composition according to the invention has a weight-average molecular mass less than or equal to 100,000 (in particular ranging from 1,000 to 100,000), in particular less than 50,000 (in particular ranging from 1000 to 50,000), and more particularly ranging from 1000 to 30,000, preferably from 2000 to 20,000, and better still from 2000 to 10,000.

The first polymer, and in particular polyamide, is advantageously not soluble in water, in particular at 25 ° C. In particular, it does not contain an ionic group.

As first preferred polymers which can be used in the invention, mention may be made of polyamides branched by pendant fatty chains and / or terminal fatty chains having from 6 to 120 carbon atoms and better still from 8 to 120 and in particular from 12 to 68 carbon atoms. carbon, each terminal fatty chain being linked to the polyamide skeleton by at least one linking group, in particular an ester. Preferably, these polymers comprise a fatty chain at each end of the polymer backbone and in particular of the polyamide backbone. As other linking group, mention may be made of the ether, amino, urea, urethane, thioether, thioester, thiourea, thiourethane groups. These first polymers are preferably polymers resulting from a polycondensation between a dicarboxylic acid having at least 32 carbon atoms (having in particular from 32 to 44 carbon atoms) with an amine chosen from diamines having at least 2 carbon atoms ( in particular from 2 to 36 carbon atoms) and the triamines having at least 2 carbon atoms (in particular from 2 to 36 carbon atoms. The diacid is preferably a dimer derived from ethylenically unsaturated fatty acid having at least 16 atoms of carbon, preferably from 16 to 24 carbon atoms, such as oleic, linoleic or linolenic acid. The diamine is preferably ethylene diamine, hexylene diamine, hexamethylene diamine. Triamine is for example ethylene For polymers comprising one or two terminal carboxylic acid groups, it is advantageous to esterify them with a monoalcohol having at least 4 carbon atoms, preferably from 10 to 36 carbon atoms and better from 12 to 24 and even better from 16 to 24, for example 18 carbon atoms.

These polymers are more especially those described in document US-A-5783657 from the company Union Camp. Each of these polymers satisfies in particular the following formula (I):

R ⁴ R ⁴

I I

R ¹ - O— [- C— R ² - C— N— R ³ - N— ^• ] „- C— R ² - C— O— R ¹ (I)

M I I I I I I

O O O O

in which n denotes an integer number of amide units such that the number of ester groups represents from 10% to 50% of the total number of ester and amide groups; R ¹ is independently at each occurrence an alkyl or alkenyl group having at least 4 carbon atoms and in particular from 4 to 24 carbon atoms; R ² independently represents a group at each occurrence C ₄ to C ₄₂ hydrocarbon provided that 50% of the R ² groups represent a C ₃₀ to C ₄₂ hydrocarbon group; R ³ independently represents, on each occurrence, an organic group provided with at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and R ⁴ independently represents at each occurrence a hydrogen atom, a C ₁ to C ₁₀ alkyl group or a direct bond to R ³ or to another R ⁴ so that the nitrogen atom to which are bonded to the times R ³ and R ⁴ are part of a heterocyclic structure defined by R ⁴ -NR ³ , with at least 50% of R ⁴ representing a hydrogen atom.

In the particular case of formula (I), the terminal fatty chains optionally functionalized within the meaning of the invention are terminal chains linked to the last heteroatom, here nitrogen, of the polyamide skeleton.

In particular, the ester groups of formula (I), which are part of the terminal and / or pendant fatty chains within the meaning of the invention, represent from 15 to 40% of the total number of ester and amide groups and better still from 20 to 35%. In addition, n advantageously represents an integer ranging from 1 to 5, and better still greater than 2, in particular ranging from 3 to 5. Preferably, R ¹ is a C ₁₂ to C ₂₂ and preferably C ₁₆ to C ₂₂ . Advantageously, R ² can be a C ₁₀ to C ₄₂ hydrocarbon (alkylene) group. Preferably, at least 50% and better still at least 75% of the R ² are groups having from 30 to 42 carbon atoms. The other R ² are hydrogenated groups from C ₄ to C ₁₉ and even from C ₄ to C ₁₂ . Preferably, R ³ represents a C ₂ to C ₃₆ hydrocarbon group or a polyoxyalkylenated group and R ⁴ represents a hydrogen atom. Preferably, R ³ represents a C ₂ to C ₁₂ hydrocarbon group.

The hydrocarbon groups can be linear, cyclic or branched, saturated or unsaturated groups. Furthermore, the alkyl and alkylene groups may be linear or branched groups, saturated or not. In general, the polymers of formula (I) are in the form of polymer blends, these blends can also contain a synthetic product corresponding to a compound of formula (I) where n is 0, that is to say a diester.

By way of example of the first polymers according to the invention, mention may be made of the commercial products sold by the company Arizona Chemical under the names Uniclear® 80 and Uniclear® 100. They are sold respectively in the form of an 80% gel (in terms of active) in mineral oil and 100% (active ingredient). They have a softening point of 88 to 94 ° C. These commercial products are a mixture of copolymers of a C ₃₆ diacid condensed on ethylene diamine, with a weight average molecular weight of approximately 6000. The terminal ester groups result from the esterification of the remaining acid terminations by l cetyl alcohol, stearyl alcohol or their mixtures (also called cetylstearyl alcohol).

As the first polymer which can be used in the invention, mention may also be made of polyamide resins resulting from the condensation of an aliphatic di-carboxylic acid and a diamine (including compounds having more than 2 carbonyl groups and 2 amino groups), carbonyl and amine groups of adjacent unitary units being condensed by an amide bond. These polyamide resins are especially those sold under the Versamid® brand by the companies General Mills, Inc. and Henkel Corp. (Versamid® 930, 744 or 1655) or by the company Olin Mathieson Chemical Corp., under the brand Onamid® in particular Onamid® S or C. These resins have a weight average molecular weight ranging from 6000 to 9000. For more information on these polyamides, reference can be made to documents US-A-3645705 and US-A-3148125. More specifically, Versamid® 930 or 744 are used.

It is also possible to use the polyamides sold by the company Arizona Chemical under the references Uni-Rez® (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554,

2623, 2662) and the product sold under the reference Macromelt 6212 by the company Henkel. For more information on these polyamides, reference can be made to document US-A-5500209.

It is also possible to use polyamide resins obtained from vegetables such as those described in patents US-A-5783657 and US-A-5998570, the content of which is incorporated by reference into the present application.

The first polymer present in the composition according to the invention advantageously has a softening temperature above 65 ° C and up to 190 ° C. Preferably, it has a softening temperature ranging from 70 to 130 ° C and better still from 80 to 105 ° C. The first polymer is in particular a non-waxy polymer.

Preferably, the first polymer according to the invention corresponds to the formula (I) mentioned above. This first polymer has, due to their fatty chain (s), good solubility in oils and therefore leads to macroscopically homogeneous compositions even with a high rate (at least 25%) of polymer. , unlike polymers free from fatty chains.

The first polymer may be present in the composition according to the invention in a content ranging from 0.1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 0.5% to 30% by weight , and better ranging from 1% to 20% by weight.

The liquid organic phase of the composition according to the invention also contains at least one volatile organic solvent, namely one or more volatile solvents.

By "volatile organic solvent" is meant within the meaning of the invention any non-aqueous medium capable of evaporating on contact with the skin or the nails in less than an hour, at room temperature and atmospheric pressure. The volatile solvent (s) of the invention are organic solvents and in particular volatile cosmetic oils, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging in particular from 10 ^-3 to 300 mm Hg (0.013 Pa to 40,000 Pa) and preferably greater than 0, 1 mm Hg (10 Pa) and better than 0.3 mm Hg (30 Pa).

According to the invention, these volatile solvents facilitate, in particular, the application of the composition to the nails. These solvents can be hydrocarbon solvents, silicone solvents optionally comprising alkyl or aikoxy groups pendant or at the end of the silicone chain or a mixture of these solvents. Preferably, these solvents are not alcohols with at least 7 carbon atoms.

Advantageously, the liquid organic phase of the composition contains at least one volatile organic solvent or a mixture of volatile organic solvents (in the sense of the final mixture) having average solubility parameters dD, dP, dH at 25 ° C of HANSEN which satisfy under the following conditions:

15 <dD <19 dP <10 dH <10

Also, the subject of the invention is a cosmetic composition comprising an organic phase, a first polymer, a second additional film-forming polymer, the organic phase containing at least one volatile organic solvent or a mixture of volatile organic solvents having average solubility parameters dD , dP, dH at 25 ° C from HANSEN which satisfy the conditions defined above.

The invention also relates to a nail varnish composition comprising an organic phase, a first polymer, a second additional film-forming polymer, the organic phase containing at least one volatile organic solvent or a mixture of volatile organic solvents having mean solubility parameters dD, dP, dH at 25 ° C from HANSEN which satisfy the conditions defined above.

The definition of solvents in the three-dimensional solubility space according to HANSEN is described in the article by C. M. HANSEN: "The three dimensional solubility parameters" J. Paint Technol. 39, 105 (1967).

- dD characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular shocks. - dP characterizes the DEBYE interaction forces between permanent dipoles as well as the KEESOM interaction forces between induced dipoles and permanent dipoles.

- dH characterizes the specific interaction forces (hydrogen bond type, acid / base, donor / acceptor, etc.).

The parameters dD, dP, dH are expressed in (J / cm).

Preferably, an organic solvent is used such as dP <5; dH <9.

Advantageously, dD, dP and dH verify the relation

3 1/2 3 1/2

L being equal to 10 (J / cm), and better 9 (J / cm)

As volatile organic solvent which can be used in the invention, there may be mentioned volatile hydrocarbon oils having from 4 to 16 carbon atoms and their mixtures and in particular linear C ₆ -C ₁₀ alkanes such as n-hexane, n-heptane, n-octane, branched alkanes, C ₈ -C ₁₆ isoalkanes (also called isoparaffins) C ₈ -C _16, isododecane, isodecane, isohexadecane, and for example the oils sold under the trade names of Isopars' or Peutyls, esters having 4 to 8 carbon atoms such as ethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate , esters branched in C ₈ -C ₁₆ such as iso-hexyl neopentanoate and their mixtures. Preferably, the volatile organic solvent is chosen from volatile hydrocarbon oils having from 4 to 10 carbon atoms and their mixtures.

As another volatile organic solvent which can be used in the invention, mention may be made of linear or cyclic silicone oils having a viscosity at room temperature of less than 8 centistokes (8 10 ~ 6 m ² / s) and in particular having from 2 to 7 atoms of silicon, these silicones optionally comprising alkyl or aikoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil which can be used in the invention, there may be mentioned in particular octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisox tetrasiloxane, dodecamethyl pentasiloxane and mixtures thereof.

It is also possible to use volatile fluorinated solvents.

Preferably, a volatile organic solvent chosen from ethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, heptane and their mixtures is used.

The volatile organic solvent can be present in the composition according to the invention in a content ranging from 20% to 98% by weight, relative to the total weight of the composition, preferably from 30% to 90% by weight, and better still from 40% to 85% by weight.

The organic phase of the composition according to the invention can also comprise a non-volatile oil which can be a polar oil or a non-polar oil. The non-volatile oil can be present in a content ranging from 0.01% to 10% by weight, relative to the total weight of the composition.

In particular, the polar oils can be chosen from: - hydrocarbon-based vegetable oils with a high triglyceride content consisting of fatty acid and glycerol esters, the fatty acids of which may have varying chain lengths from C ₄ to C ₂₄ , the latter possibly being linear or branched, saturated or unsaturated ; these oils are in particular the oils of wheat germ, corn, sunflower, shea, castor, sweet almonds, macadamia, apricot, soy, cotton, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, avocado, hazelnut, grape or blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, bancoulier , passion flower, muscat rose; or the triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel;

- synthetic oils or synthetic esters of formula R ₅ COOR ₆ in which R ₅ represents the remainder of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R ₆ represents a notably branched hydrocarbon chain containing 1 with 40 carbon atoms provided that R ₅ + R ₆ is> 10, such as, for example, Purcellin oil (ketostearyl octanoate), isononyl isononanoate, C ₁₂ to C ₁₅ alcohol benzoate, isopropyl myristate, ethyl 2-hexyl palmitate, isostearate isostearate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols; hydroxylated esters such as isostearyl lactate, di-isostearyl malate; and pentaerythritol esters;

- synthetic ethers having from 10 to 40 carbon atoms;

- C ₈ to C ₂₆ fatty alcohols such as oleic alcohol;

- their mixtures.

The apolar oils according to the invention are in particular silicone oils such as polydimethylsiloxanes (PD S), linear or cyclic, liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant and / or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates; linear or branched hydrocarbons of synthetic or mineral origin such as paraffin oils and its derivatives, petroleum jelly, liquid lanolin, polydecenes, hydrogenated polyisobutene such as parieam, squalane; and their mixtures.

Preferably, the oils are non-polar oils and more especially an oil or a mixture of oils of the hydrocarbon type of mineral or synthetic origin, chosen in particular from hydrocarbons, in particular alkanes such as paria oil, isoparaffins such as l 'isododecane and squalane and their mixtures. Advantageously, these oils are combined with one or more phenylated silicone oils.

Preferably, a non-volatile oil is used such that the mixture of volatile organic solvent and non-volatile oil has mean solubility parameters dD, dP, dH at 25 ° C. of HANSEN which satisfy the conditions defined above.

According to a particular embodiment of the invention, for a liquid organic phase structured by a polymer comprising a partially silicone skeleton, this organic phase preferably contains more than 40% of the total weight of the liquid organic phase and better still from 50 to 100% , of volatile organic silicone solvent or of non-volatile silicone oils, relative to the total weight of the liquid organic phase.

According to another particular embodiment of the invention, for a liquid organic phase structured by an apolar polymer of the hydrocarbon type, this organic phase advantageously contains more than 40% by weight and better still from 50 to 100%, volatile organic hydrocarbon solvent or d non-volatile oil, non-volatile hydrocarbon based on the total weight of the liquid organic phase. The total liquid organic phase represents, in practice, from 5 to 99% of the total weight of the composition, preferably from 20 to 75%.

According to the invention, the composition can be a stick having a hardness ranging from 30 to 300 g, and better still from 30 to 250 g, in particular from 30 to 150 g, preferably from 30 to 120 g and for example from 30 to 50 g. The hardness of the composition according to the invention can be measured by the so-called butter cutting wire method, which consists in cutting a stick of lipstick with a diameter of 12.7 mm and in measuring the hardness at 20 ° C., using a DFGHS 2 dynamometer from the company Indelco-Chatillon moving at a speed of 100 mm / minute. It is expressed as the shear force (expressed in grams) necessary to cut a stick under these conditions.

The hardness of the composition can also be measured by the method of penetration of a probe into said composition and in particular using a texture analyzer (for example TA-XT2i; from Rhéo) equipped with a cylinder. ebonite 25 mm high and 8 mm in diameter. The hardness measurement is carried out at 20 ° C. in the center of 5 samples of the said composition. The cylinder is introduced into each composition sample at a pre-speed of 2mm / s, then at a speed of 0.5 mm / s and finally at a post-speed of 2mm / s, the total displacement being 1mm. The value recorded for hardness is that of the maximum peak. The measurement error is +/- 50 g. According to this method, the hardness of the stick of composition can range from 20 to 2,000 g in particular from 20 to 1,500 g and better still from 20 to 900 g, for example from 50 to 600 g or even better from 150 to 450

9-

The hardness of the composition according to the invention is such that the composition is advantageously self-supporting and can disintegrate easily to form a satisfactory deposit on the nails. In addition, with this hardness, the composition of the invention resists impact well. The hardness of the composition according to the invention is such that the composition is self-supporting and can disintegrate easily to form a satisfactory deposit on the nails. In addition, with this hardness, the composition of the invention resists impact well.

Advantageously, the composition of the invention contains, in addition, at least one auxiliary film-forming polymer, different from said first polymer as described above.

The film-forming polymer can be chosen from cellulosic polymers such as nitrocellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate, ethyl cellulose, or alternatively polyurethanes, acrylic polymers, polymers vinyl, polyvinylbutyrals, alkyd resins, resins derived from aldehyde condensation products such as arylsulfonamide formaldehyde resins such as toluene sulfonamide formaldehyde resin, aryl sulfonamide epoxy resins.

As film-forming polymer, it is possible in particular to use nitrocellulose RS 1/8 dry; RS VA sec. ; ^_1/2 sec. ; RS 5 sec. ; RS 15 sec. ; RS 35 sec. ; RS 75 sec; RS 150 sec; AS VA sec. ; AS Vz sec. ; SS VA sec. ; SS Vz sec. ; SS 5 sec, notably marketed by HERCULES; toluene sulfonamide formaldehyde "Ketjentflex MS80" resin from AKZO or "Santolite HP", "Santolite M ^' S 80" from FAÇONNIER or "RESIMPOL 80" from PAN AMERICANA, alkyd resin "BECKOSOL ODE 230-70 -E "from the company DAINIPPON, the acrylic resin" ACRYLOID B66 "from the company ROHM & HAAS, the polyurethane resin" TRIXENE PR 4127 "from the company BAXENDEN.

The auxiliary film-forming polymer may be present in the composition according to the invention in a content ranging from 0.1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 2% to 40% by weight, and better from 5% to 25% by weight. The composition of the invention may comprise, in addition, any additive usually used in the field concerned, chosen in particular from coloring matters, antioxidants, preservatives, perfumes, fillers, waxes, neutralizers, cosmetic active agents or dermatological, such as emollients, moisturizers, vitamins, spreading agents, sun filters, and mixtures thereof. These additives can be present in the composition at a rate of 0 to 20% (in particular from 0.01 to 20%) of the total weight of the composition and better still from 0.01 to 10%.

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

Of course, the composition of the invention must be cosmetically or dermatologically acceptable, ie contain a physiologically acceptable medium which is non-toxic and capable of being applied to the skin or the integuments of human beings. By cosmetically acceptable is meant within the meaning of the invention a composition of pleasant appearance, odor and feel.

The coloring matter according to the invention can be chosen from lipophilic dyes, pigments and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof. This coloring material is generally present in an amount of 0.01 to 10% of the total weight of the composition, preferably 0.1 to 8%, if it is present.

The fat-soluble dyes are for example Sudan red, DC Red 17, DC Green 6, β-carotene, soybean oil, Sudan brown, DC Yellow 11, DC Violet 2, DC orange 5, quinoline yellow. They can represent from 0.1 to 10% of the weight of the composition and better still from 0.1 to 6%. The pigments can be white or colored, mineral and / or organic, coated or not. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, hydrate of chrome and ferric blue. Among the organic pigments, there may be mentioned carbon black, pigments of the D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum. The pigments can represent from 0.1 to 50% and better still from 2 to 30% of the total weight of the composition, if they are present.

The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. They can represent from 0.1 to 20% of the total weight of the composition and better still from 0.1 to 15%, if they are present.

The composition according to the invention can be produced by known methods, generally used in the cosmetic or dermatological field.

The invention is illustrated in more detail in the following example. The percentages are given by weight.

Example 1:

A nail varnish having the following composition was prepared:

- Polyamide resin with terminal ester groups sold under the name "UNICLEAR® 100" by the company Arizona Chemical 20 g - Nitrocellulose 8 g

- Pigments 1 g

- Butyl acetate qs 100 g

The nail polish is in the form of a structured solid composition such as a stick.

Claims

1. Structured nail polish composition containing at least one liquid organic phase comprising at least one volatile organic solvent, the liquid organic phase being structured by at least one first polymer of weight average molecular mass less than or equal to 100,000, comprising a ) a polymeric skeleton, having hydrocarbon repeat units provided with at least one heteroatom, and b) optionally functionalized pendant and/or terminal fatty chains, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units.

2. Stick nail polish composition comprising a liquid organic phase containing a volatile organic solvent and a first polymer of weight average molecular mass less than or equal to 100,000, comprising a) a polymeric skeleton, having hydrocarbon repeat units provided of at least one heteroatom, and b) pendant and/or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units.

3. Cosmetic composition comprising an organic phase, a first polymer with a weight average molecular mass less than or equal to 100,000, comprising a) a polymeric skeleton, having hydrocarbon repeat units provided with at least one heteroatom, and b) pendant and/or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units, a second additional film-forming polymer, the organic phase containing at least one volatile organic solvent or a mixture of volatile organic solvents having average solubility parameters dD, dP, dH at 25°C from HANSEN which satisfy the following conditions:

15 (J/cm ³ ) ¹ ' ² ≤ dD ≤ 19 (J/cm ³ ) ¹ ' ² ^ 1 /9 dP ≤ 10 (J/cm ) dH < 10 (J/cm ³ ) ^1/2

4. Nail polish composition comprising a liquid organic phase, a first polymer with a weight average molecular mass less than or equal to 100,000, comprising a) a polymer skeleton, having hydrocarbon repeat units provided with at least one heteroatom, and b) pendant and/or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units, a second additional film-forming polymer, the organic phase containing at least one volatile organic solvent or a mixture of volatile organic solvents having average solubility parameters dD, dP, dH at 25°C from HANSEN which satisfy the following conditions:

15 (J/cm ³ ) ^1/2 < dD < 19 (J/cm ³ ) ^{1 2}

? 1/9 dP ≤ 10 (J/cm ) dH < 10 (J/cm ³ ) ¹ ' ²

5. Composition according to any one of the preceding claims, characterized in that the average molar mass of the first polymer is less than 50,000.

6. Composition according to any one of the preceding claims, characterized in that the heteroatom units of the first polymer comprise a nitrogen atom.

7. Composition according to any one of the preceding claims, characterized in that the heteroatom units are amides.

8. Composition according to any one of the preceding claims, characterized in that the fatty chains represent 40 to 98% of the total number of heteroatom units and fatty chains.

9. Composition according to one of the preceding claims, characterized in that the fatty chains represent 50 to 95% of the total number of heteroatom units and fatty chains.

10. Composition according to one of the preceding claims, characterized in that the pendant fatty chains are linked directly to at least one of said heteroatoms.

11. Structured nail polish composition containing at least one liquid organic phase comprising at least one volatile organic solvent, the liquid organic phase being structured by at least one polyamide with a weight average molecular mass less than or equal to 100,000, comprising a) a polymer skeleton, having amide repeating units, and b) optionally optionally functionalized pendant and/or terminal fatty chains, having from 6 to 120 carbon atoms and being linked to these amide units.

12. Stick nail polish composition comprising a volatile organic solvent and a first polyamide polymer of weight average molecular mass less than or equal to 100,000, comprising a) a polymeric skeleton, having amide repeating units, and b) pendant and/or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these amide units.

13. Cosmetic composition comprising an organic phase, a first polyamide polymer with a weight average molecular mass less than or equal to 100,000, comprising a) a polymeric skeleton, having repeating amide units, and b) pendant fatty chains and/or optionally functionalized terminals, having from 6 to 120 carbon atoms and being linked to these amide units, a second additional film-forming polymer, the organic phase containing at least one volatile organic solvent or a mixture of volatile organic solvents having average solubility parameters dD, dP, dH at 25°C from HANSEN which satisfy the following conditions:

15 (J/cm ³ ) ^1/2 ≤ dD ≤ 19 (J/cm ³ ) ^1/2 dP ≤ 10 (J/cm ³ ) ^1/2 dH ≤ 10 (J/cm ³ ) ^/2

14. Nail polish composition comprising an organic phase, a first polyamide polymer of weight average molecular mass less than or equal to 100,000, comprising a) a polymeric skeleton, having repeating amide units, and b) pendant fatty chains and/or terminals optionally functionalized, having from 6 to 120 carbon atoms and being linked to these amide units, a second additional film-forming polymer, the organic phase containing at least one volatile organic solvent or a mixture of volatile organic solvents having average parameters of solubility dD, dP, dH at 25 °C from HANSEN which satisfy the following conditions:

15 (J/cm ³ ) ¹ ' ² < dD < 19 (J/cm ³ ) ¹ ' ² dP ≤ 10 (J/cm ³ ) ¹ ' ² dH < 10 (J/cm ³ ) ¹ ' ²

15. Composition according to one of claims 11 to 14, characterized in that the fatty chains represent 40 to 98% of the total number of amide units and fatty chains.

16. Composition according to one of claims 11 to 15, characterized in that the fatty chains represent 50 to 95% of the total number of amide units and fatty chains.

17. Composition according to one of claims 11 to 16, characterized in that the pendant fatty chains are linked directly to at least one of the nitrogen atoms of the amide units.

18. Composition according to one of the preceding claims, characterized in that the weight average molar mass of the first polymer ranges from 2,000 to 20,000 and better still from 2,000 to 10,000.

19. Composition according to any one of the preceding claims, characterized in that the terminal fatty chains are linked to the skeleton by linking groups.

20. Composition according to claim 19, characterized in that the linking groups are ester groups.

21. Composition according to one of the preceding claims, characterized in that the fatty chains have from 12 to 68 carbon atoms.

22. Composition according to one of the preceding claims, characterized in that the first polymer is chosen from the following polymers of formula (I) and their mixtures:

^R4 ^R4

I I

R ¹ — O— [— C— R ² — C— N— R ³ — N— ] _n — C— R ² — C— O— R ¹ (I)

O O O O

in which n designates a number of amide units such that the number of ester groups represents from 10% to 50% of the total number of ester and amide groups; R ¹ is at each independent occurrence an alkyl or alkenyl group having at least 4 carbon atoms; R ² represents at each occurrence independently a C ₄ to C ₄₂ hydrocarbon group provided that 50% of the R ² groups represent a C ₃₀ to C ₄₂ hydrocarbon group; R ³ represents at each occurrence independently an organic group provided with at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and R ⁴ represents at each independent occurrence a hydrogen atom, a C , C ₁₀ alkyl group or a direct bond to R ³ or another R ⁴ such that the nitrogen atom to which both are bonded R ³ and R ⁴ is part of a heterocyclic structure defined by R ⁴ -NR ³ , with at least 50% of the R ⁴ representing a hydrogen atom.

23. Composition according to the preceding claim, characterized in that R ¹ is a C ₁₂ to C ₂₂ alkyl group.

24. Composition according to one of claims 22 or 23, characterized in that R ² are groups having 30 to 42 carbon atoms.

25. Composition according to one of the preceding claims, characterized in that the first polymer is present in a content ranging from 0.1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 0 .5% to 30% by weight, and better ranging from 1% to 20% by weight.

26. Composition according to one of claims 1, 2 and 5 to 25, characterized in that the volatile organic solvent is chosen from volatile organic solvents or mixtures of volatile organic solvents having average solubility parameters dD, dP, dH at 25°C from HANSEN which satisfy the following conditions:

15 (J/cm ³ ) ^1/2 < dD < 19 (J/cm ³ ) ¹ ' ²

"3 1 /9 dP ≤ 10 (J/cm ) dH < 10 (J/cm ³ ) ¹ ' ²

27. Composition according to any one of claims 3 to 26, characterized

3.1/2 by the fact that dP < 5 (J/cm)

28. Composition according to any one of claims 3 to 27, characterized

3. 1/2 by the fact that dH < 9 (J/cm)

29. Composition according to any one of claims 3 to 28, characterized in that dD, dP and dH verify the relationship

4(17 - hard + dP 2-- dUl-r2 < L

3 1/2 3 1/9

L being equal to 10 (J/cm), and better 9 (J/cm)

30. Composition according to any one of the preceding claims, characterized in that the volatile organic solvent is chosen from the group formed by esters having from 4 to 8 carbon atoms, alkanes having from 6 to 10 carbon atoms.

31. Composition according to any one of the preceding claims, characterized in that the volatile organic solvent is chosen from the group formed by ethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, heptane.

32. Composition according to any one of claims 1, 2, 5 to 12, 15 to 25, characterized in that the volatile organic solvent is chosen from branched C ₈ -C ₁₆ alkanes, branched C ₈ esters -C ₁₆ and their mixtures.

33. Composition according to any one of claims 1, 2, 5 to 12, 15 to 25, characterized in that the volatile organic solvent is chosen from C ₈ -C ₁₆ isioparaffins, isododecane and their mixtures .

34. Composition according to one of the preceding claims, characterized in that the volatile organic solvent is present in a content ranging from 20% to 98% by weight, relative to the total weight of the composition, preferably from 30% to 90% by weight, and better 40% to 85% by weight.

35. Composition according to any one of the preceding claims, characterized in that the liquid organic phase also contains at least one non-volatile oil.

36. Composition according to one of the preceding claims, characterized in that the liquid organic phase represents 5 to 99% of the total weight of the composition, preferably 20 to 75%.

37. Composition according to any one of the preceding claims, characterized in that it comprises a second film-forming polymer.

38. Composition according to claim 37, characterized in that the second film-forming polymer is chosen from the group formed by cellulosic polymers, polyurethanes, acrylic polymers, vinyl polymers, polyvinyl butyrals, alkyd resins, resins derived from aldehyde condensation products, aryl-sulfonamide epoxy resins.

39. Composition according to claim 37 or 38, characterized in that the second film-forming polymer is present in a content ranging from 0.1% to 60% by weight, relative to the total weight of the composition, preferably ranging from 2 % to 40% by weight, and better from 5% to 25% by weight.

40. Composition according to one of the preceding claims, characterized in that it contains at least one additive chosen from coloring materials, antioxidants, preservatives, perfumes, fillers, waxes, neutralizers, cosmetic active ingredients or dermatological, dispersants, spreading agents, sunscreens, and mixtures thereof.

41. Composition according to one of the preceding claims, characterized in that it is in the form of a rigid gel, and in particular an anhydrous stick.

42. Composition according to one of the preceding claims, characterized in that it is in the form of a stick with a hardness ranging from 30 to 300 g measured by the so-called butter cutting wire method.

43. Cosmetic method of makeup or non-therapeutic treatment of the nails of human beings, comprising the application to the nails of a cosmetic composition according to one of the preceding claims.

44. Use of an organic liquid phase containing at least one volatile organic solvent and a sufficient quantity of a first polymer with a weight average molecular mass less than or equal to 100,000, comprising a) a polymeric skeleton, having patterns of repeat hydrocarbons provided with at least one heteroatom, and b) optionally pendant and/or terminal fatty chains optionally functionalized, having from 6 to 120 carbon atoms and being linked to these hydrocarbon units, in a nail polish composition, for obtain a stick having a hardness ranging from 30 to 300 g measured by the so-called butter cutting wire method.

45. Use according to the preceding claim, characterized in that the polymer is a polyamide comprising terminal groups with an ester group comprising a hydrocarbon chain having from 10 to 42 carbon atoms.

46. Use according to claim 44 or 45 characterized in that the organic liquid phase contains a volatile organic solvent or a mixture of volatile organic solvents having average solubility parameters dD, dP, dH at 25 ° C of HANSEN which satisfy the HANSEN following conditions:

15 (J/cm ³ ) ¹ ' ² ≤ dD < 19 (J/cm ³ ) ¹ ' ² 1/9 dP ≤ 10 (J/cm )

3 1/9 dH ≤ 10 (J/cm )

47. Use according to one of claims 44 to 46 characterized in that the volatile organic solvent is chosen from the group formed by ethyl acetate, n-propyl acetate, isobutyl acetate, n-butyl acetate, heptane.

48. Use according to one of claims 44 to 47, characterized in that the composition comprises a second film-forming polymer.