WO1998026751A1

WO1998026751A1 - Anhydrous cosmetic composition containing a fatty constituent and a polymeric colouring agent

Info

Publication number: WO1998026751A1
Application number: PCT/FR1997/002306
Authority: WO
Inventors: Patricia Lemann; Isabelle Bara
Original assignee: L'oreal
Priority date: 1996-12-16
Filing date: 1997-12-15
Publication date: 1998-06-25
Also published as: CA2275935A1; FR2757051A1; JP2000513006A; FR2757051B1; EP0944378A1

Abstract

The invention concerns an anhydrous cosmetic composition containing at least a wax and/or a filler, an optionally an oil, and at least a polymeric colouring agent selected among polyester, polyamide, polyurethane, polyacrylic polymers or their mixtures.

Description

Anhydrous cosmetic composition comprising a fatty component and a polymeric dye

The subject of the invention is new anhydrous cosmetic compositions, comprising at least one wax and / or a filler, and optionally an oil, and at least one particular dye.

Usually used as coloring matter in cosmetic compositions are either inorganic or organic pigments or lacquers, which are generally insoluble in aqueous and organic media, or dyes soluble in aqueous or organic media.

The pigments and lacquers used in the make-up field are of very diverse origin and chemical nature. Their physicochemical properties, such as: grain size, specific surface, density, etc. are therefore very different. These differences are reflected in particular in behavioral variations: the ease of implementation, of dispersion, the stability to light, to temperature and the mechanical properties in the case of powders are specific to each coloring matter. These differences in behavior frequently require the formulator to readjust the composition of the formula when the shade of this formula is changed. They also limit the production of certain formulas in the form of monochrome. In particular, certain shades are impracticable because the pigments or lacquers which theoretically allow them to be obtained are incompatible with one another.

Mineral oxides are preferably used for coloring cosmetic compositions, because the organic lacquers show too much bleeding, which in particular has the effect of staining the ocular lenses in the case of eyeliners or mascaras. However, these mineral pigments are dull and bland in color; it is therefore necessary to introduce a large amount of it into the mascara and eyeliner formulas to obtain a sufficiently saturated makeup line. This high percentage of mineral particles strongly affects the gloss of the makeup film. In the case of lipsticks, the the problem is identical since it is known that the brilliant compositions must be formulated with small quantities of pigments. Color coverage and saturation are therefore often associated with the dullness of the make-up film.

In the field of make-up, only organic lacquers have so far made it possible to obtain bright and intense colors (mineral oxides having a very bland color). However, most organic lacquers exhibit very poor light fastness, which results in a very clear attenuation of their color over time. This phenomenon is further aggravated when these lakes are combined with photoreactive pigments such as titanium dioxide. However, these photoreactive pigments are very widely used in makeup for protection against ultraviolet radiation. Consequently, the use of organic lacquers is fairly limited, which results in a limitation of the achievable shades.

The association of certain pigments, in particular iron oxides, with oils and certain active agents, in particular vitamins, often results in the oxidation of these oils and these active agents.

In the mascara compositions, up to 10% of mineral oxide pigments are used to obtain a visible and acceptable coloration on the eyelashes. However, such a high concentration of pigments leads to a strong decrease in the rheological performance of the mascara, and therefore produces a heterogeneous makeup on the eyelashes. Organic lacquers, which allow much brighter colors to be obtained at lower percentages, are of little use for this application because, as already indicated, they stain easily and therefore risk staining the lenses.

In addition, the use of soluble dyes in makeup compositions has the effect of accentuating the wrinkles or streaks of the skin, the dye coming to be fixed, by migration, preferably in these wrinkles or streaks. This effect is contrary to that of attenuation of the skin defects that one seeks to obtain by the ma- skittle. In addition, these soluble dyes often have the drawback of leaving spots on the skin and nails after makeup removal, with which they have a great affinity.

In addition, it has been found that during storage, the makeup powders colored by pigments tend to sediment: the pigments separate from the rest of the components. Also, one cannot keep loose makeup powders after their manufacture.

Finally, if the mineral pigments must be used in large quantities to obtain a satisfactory coloring, on the other hand, the soluble dyes have a very high coloring power, which leads to using them in infinitesimal quantities. Therefore, their dosage in a cosmetic formula under reproducible conditions is an extremely delicate operation.

There therefore remained the need to have new coloring material making it possible to overcome the drawbacks of the prior art.

Also it is with astonishment that the Applicant has discovered that the use of a polymeric dye belonging to a particular family, could make it possible to prepare new cosmetic compositions, which no longer have the drawbacks of the prior art.

In particular, these compositions do not release dye on the skin, which avoids the appearance of streaks on the made-up skin or spots after makeup removal. They thus allow non-permanent coloring of the skin, nails, lips or eyelashes: after removing makeup, the skin, nails, lips or eyelashes are not colored. This gives a clean makeup removal. It is said that the compositions "do not scratch". These compositions are prepared from quantities of polymeric dye low enough not to destabilize the formulas, but in quantities large enough to be easily dosed in a reproducible manner. In addition, these compositions can be prepared according to invariable formulas whatever the desired shade, with a very wide and very nuanced range of shades, with a high intensity of coloring associated with a shiny effect if desired, with good hold. in the light, including when the composition also comprises photoreactive pigments.

The subject of the invention is therefore an anhydrous cosmetic composition comprising at least one wax and / or a filler, and optionally an oil, and at least one polymeric dye chosen from polyester, polyamide, polyurethane, polyacrylic polymers or mixtures thereof.

The invention also relates to a process for the preparation of a composition as defined above, characterized in that the polymeric dye is introduced into the composition in the form of a dispersible powder or of a crude powder.

FR 2 681 329 discloses an anhydrous cosmetic composition comprising a melanin pigment. Nowhere in FR 2 681 329 is it said or suggested to incorporate a polymeric dye chosen from polyester, polyamide, polyurethane, polyacrylic polymers or their mixtures in an anhydrous cosmetic makeup composition.

By polymeric dye is meant in the present description, a copolymer based on at least two distinct monomers, at least one of which is an organic dye monomer.

Such polymeric dyes are known to those skilled in the art. One can, for example, refer to the documents: US-5,032,670; US-4, 999.418; US-5,106,942; US-5,030,708; US-5,102,980; US-5,043,376; US-5, 104, 913; US-5,281, 659, US-5, 194,463; US-4,804,719; WO92 / 07913.

It is stated in these documents that these dyes have the property of not migrating, of not exuding, of not being extractable or sublimable. They are also deemed to be light-stable and to have a high coloring power. However, the media in which their use is envisaged are thermoplastic media, essentially for the manufacture of packaging. Nothing suggested the surprising properties of these polymers once incorporated into cosmetic compositions.

US 5, 043, 376 describes polyester dyes which can be ground in castor oil. However, nowhere in US 5,043,376 is it said or suggested that the incorporation of a polymeric dye chosen from polyester, polyamide, polyurethane, polyacrylic polymers or their mixtures in an anhydrous cosmetic composition as in the present invention makes it possible to obtain compositions which do not release dye on the skin and therefore which do not stain the skin after removing makeup as explained above.

The polymeric dyes which can be used in the present invention can be of any kind: polyester, polyamide, polyurethane, polyacrylic, mixtures thereof.

Usually, polyester polymeric dyes have an intrinsic viscosity of at least 0.20 and can result from the polymerization of several monomers including:

(i) at least one dicarboxylic acid residue; (ii) at least one dioi residue; and (iii) at least one coloring monomer.

The polymeric dyes which can be used in the present invention are preferably sulfopolyester or polyurethane polymers. These polyester or polyurethane polymeric dyes can be of the crystalline, semi-crystalline or amorphous type. The sulfopolyester polymeric dyes which can be used according to the present invention preferably result from the polymerization of several monomers including: (i) at least one dicarboxylic acid residue carrying at least one sulfonic group; (ii) at least one diol residue; and

(iii) at least one coloring monomer.

The polyurethane polymers which can be used according to the present invention have an intrinsic viscosity of at least 0.20 and can result from the polymerization of several monomers including:

(i) at least one di-isocyanate residue;

(ii) at least one diol residue; and

(iii) at least one coloring monomer.

The dicarboxylic acid residues carrying a sulfonic group can be chosen from cycloaliphatic diacids such as the sulfo diacid 1,4-cyclohexane carboxylic acid, or alternatively from aromatic diacids such as sulfophthalic acids, 4-sulfonaphthalene-2,7- acid. dicarboxylic.

The di-isocyanate residues can be of aliphatic, alicyclic or aromatic type, such as for example 2,4-tolylene di-isocyanate, 2,6-tolylèπe di-isocyanate, 4,4'-biphenylene di-isocyanate, p-xylene di-isocyanate, methylene di-p-phenyl di-isocyanate, p-phenylene di-isocyanate, m-phenylene di-isocyanate, hexamethylene di-isocyanate, isophorone di-isocyanate, etc.

The diol residues can be chosen, for example, from ethylene glycol, 1, 2-propane diol, 1, 3-propane diol, 2-methyl-1, 3-propanediol, 1, 4-butane diol, 2,2-dimethyl-1, 3-propanediol, 1, 6-hexanediol, 1, 10-decane diol, 1, 12-dodecane diol, 1, 2-cyclohexane diol, 1, 4-cyclohexanediol, 1,2-cyclohexane dimethanol, x, 8-bis (hydroxymethyl) -tricyclo- [5.2.1 .0] decane, in which x represents 3, 4 or 5; diols comprising at least one oxygen atom gene in the chain such as for example diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-bis (2-hydroxyethyl) benzene, 1,4-bis (2-hydroxyethyl) benzene, etc.

Generally, these diols contain 2 to 18 and preferably 2 to 12 carbon atoms.

In addition, the sulfopolyester dyes may contain dicarboxylic acid residues free of sulfonic groups; such residues can be of the aliphatic, alicyclic or aromatic type, such as, for example, terephthalic, isophthalic acids, 1,4-cyclohexane dicarboxylic, 1,3-cyclohexane dicarboxylic, succinic, glutaric, adipic, sebacic, 1, 2-dodecanedioic, 2,6-naphthalene dicarboxylic, etc.

Preferably, the sulfopolyester polymer is a water-dispersible polymeric material having linking groups comprising at least about 20 mol% of carbonyloxy and up to about 80 mol% of carbonylamido, said material containing water-soluble sulfonate groups and having about

0.01 to about 40 mole%, based on the total of all hydroxy, carboxy or reactive amino equivalents, of a colorant comprising one or more thermostable organic compounds initially having at least one con- densable, which has been reacted on or in the polymeric trunk. The aforementioned equivalents include their various condensable derivatives, including carbalkoxy, carbaryloxy, N-alkylcarbamyloxy, acyloxy, chlorocarbonyl, carbamyloxy,

N- (alkyl) ₂ carbamyloxy, alkylamino, N-phenylcarbamyloxy, cyclohexanoyloxy and carbocyclohexyloxy.

In a highly preferred embodiment of the present invention, the polymeric material contains carbonyloxy linking groups in the linear molecular structure, where up to 80% of said linking groups can be carbonylamido linking groups, the polymer having a viscosity inherent from about 0.1 to about 1, measured in a solution of 60-40 parts by weight of phenol / tetrachioroethane, at 25 ° C and at a concentration of 0.25 grams of po- lymer in 100 ml of the solvent, the polymer containing essentially equimolar proportions of acid equivalents (100 mole percent) relative to the hydroxy and amino equivalents (100 mole percent), the polymer comprising Reaction residues of the following reagents (a), (b), (c), (d) and (e) or their ester-generating derivatives or esteramide-generating derivatives:

(a) at least one difunctional dicarboxylic acid;

(b) from about 4 to about 25 mole percent, based on a total of all equivalents of acid, hydroxyl and amino being 200 mole percent, of at least 1 difunctional sulfomonomer containing at least one cationic sulfonate group linked to an aromatic or cycloaliphatic ring where the functional groups are hydroxy, carboxyl or amino;

(c) at least one difunctional reagent chosen from a glycol or a mixture of a glycol and a diamine having two -NRH groups, the glycol containing two -CH ₂ -OH groups of which

(1) at least 10 mole percent, based on the total mole percentage of hydroxy or hydroxy and amino equivalents, is a polyethylene glycol of structural formula:

H- (OCH ₂ -CH ₂ ) _n -OH

n being an integer from 2 to about 20 or

(2) from about 0.1 to less than about 15 mole percent, based on the total mole percentage of hydroxy or hydroxy and amino equivalents, are a polyethylene glycol of structural formula:

H- (OCH ₂ -CH ₂ ) _n -OH n being an integer between 2 and about 500, and provided that the mole percentage of said polyethylene glycol in said range is inversely proportional to the value of n in said range;

(d) from zero to at least one difunctional reagent chosen from a hydroxycarboxylic acid having a group -C (R) ₂ -OH, an aminocarboxylic acid having a group -NRH, and an amino alcohol having a group - C ( R) ₂ -OH and a group -NRH, or mixtures of said difunctional reagents; wherein each R in reactants (c) or (d) is an H atom or an alkyl group having from 1 to 4 carbon atoms; and

(e) from about 0.1 mol% to about 15 mol%, based on a total of all the equivalents of acid, hydroxyl and amino being 200 mol%, coloring monomer having at least one acid, hydroxy or amino group which has been reacted on or in the polymer chain.

Advantageously, the water-dispersible sulfopolyester comprises:

(a) an acid monomer comprising from 75 mol% to 84 mol% of isophthalic acid and from 25 mol% to 16 mol% of sodium salt of 5-isophthalic acid,

(b) a glycol monomer comprising from 45 to 60 mol% of diethylene glycol and from 55 to 40 mol% of 1, 4-cyclohexanedimethanol or of ethylene glycol or their mixture,

(c) from 0.5 to 10 mol% of coloring monomer.

In particular, the polyurethane polymeric dyes which can be used according to the present invention can be those described in patent US-A-5194463 and corresponding to the following formula (I):

(I)

in which :

R is a divalent radical chosen from the C2-C10 alkylene, C3-C8 cycloalkylene, arylene, alkylene (C1 -C4) -arylene-alkylene (C1-C4), alkylene (C1 -C4) radicals - cycloalkylene (C3-C8) -alkylene (C1-C4), alkylene (C1-C4) -1, 2,3,4, 5,6,7-octahydronaphthalene-2,6-diyl-alkylene (C1-C4),

R ¹ is an organic divalent radical comprising (a) from 1 to 100 mol% of coloring organic diol in which the hydroxyl groups of said diol are linked by an alkylene unit to the rest of the coloring compound, and (b) from 0 to 99 mol% of organic diols of formula HO-R ² -OH, in which R ² is a divalent radical chosen from C2-C18 alkylene, C3-C8 cycloalkylene, (C1-C4) alkylene-arylene-C1-alkylene radicals ), alkylene (C1 -C4) -cycloalkylene (C3-C8) -alkylene (C1 -C4), alkylene (C1-C4) -1, 2,3,4,5,6,7-octahydronaphthalene-2,6- diyl-alkylene (C1-C4), alkylene (C2-C4) -0-alkylene (C2-C4), alkylene (C2-C4) -S-alkylene (C2-C4), alkylene (C2-C4) -0- alkylene (C2-C4) -0-alkylene (C2-C4), and n is 2 or more.

Preferably, R1 comprises from 5 to 50 mole percent of coloring diol, and π ranges from 2 to 100.

For polyurethane polymers, the coloring diol monomers are chosen from a variety of classes of chromophores. These classes of chromophores can be chosen from anthraquinones, methines, bis-methines, azo-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, phthaloylphenonxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles , phthalocyanines, quinophthalones, indophenols, perinones, nitroarylamines, benzodifurane, 2 H-1-benzopyran-2-one, quinophthalones, triphenodioxazines, fluoridines, benzanthrones, indigo, thioindigo, xanthene, acridine, azine, oxazine, etc., These coloring monomers must bear at least two hydroxyl groups. Reference may be made to US Patents 5,194,463 to find examples of coloring monomers. The organic dye monomers according to the invention must contain at least two substituents capable of reacting with at least one of the other monomers used for the preparation of the polymeric dye and must be stable at the temperature and under the conditions for preparing said polymer.

Apart from these two preliminary conditions, the chemical nature of the coloring monomers does not matter for the implementation of the invention. These can, for example, be chosen from anthraquinones, methines, bis-methines, aza-methines, arylidenes, 3H-dibenzo [7, ij] isoquinolines, 2,5-diarylaminoterephthalic acids and their esters, phthaloylphenothiazines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinones, nitroarylamines, benzodifuran, 2 H-1-benzopyran-2-one, quinophenes, quinophenes , quinacridones, triphenodioxazines, fluoridines, 4-amino-1, 8-naphthalimides, thioxanthrones, benzanthrones, indanthrones, indigo, thioindigo, xanthene, acridine, azine, oxazine, etc. Reference may be made to US Patents 4,267,306; US-4, 359, 570; US-4,403,092; US-4, 617, 373; US-4,080,355; US-4,740,581; US-4, 116, 923; US-4,745,173; US-4, 804, 719, US-5, 194.463; US-4,804,719; WO92 / 07913 for finding examples of coloring monomers which can be used in the preparation of polymeric dyes.

The substituents carried by the coloring monomer and capable of reacting with the other monomers can for example be chosen from the following groups:

- hydroxy,

- carboxy, ester, amino, alkylamino:

O O O O

IIIIO - C - OR - o— C- R -C - OR -O - C - NHR in which R represents a group chosen from alkyls, aryls. Preferably R is chosen from C1-C8 alkyl groups and phenyl. Even more preferably, R is chosen from methyl, ethyl and phenyl groups.

Usually, the polymeric dye comprises at least 5% by weight of coloring monomer, and does not comprise more than 55% by weight. Preferably, the percentage by weight of coloring monomer relative to the total weight of the copolymer ranges from 10 to 40%.

For the preparation of the polymeric dyes, reference may be made to the methods described in the documents: US Pat. No. 5,032,670; US-4,999,418; US-5, 106.942; US-5,030,708; US-5,102,980; US-5,043,376, US-5, 194,463; US-4,804,719; WO92 / 07913.

The polymeric dye which can be used in the present invention may be in crude form or in the form of a dispersible powder or of a dispersion in an oily medium.

Preferably, a polymeric dye is used in the form of a dispersible powder or a crude powder.

For the preparation of a dispersible powder: A dispersion in aqueous medium of the polymeric dye can be prepared in a known manner from water, of crude polymeric dye as described in documents US Pat. No. 5,032,670; US-4,999,418; US-5, 106.942; US-5,030,708; US-5,102,980; US-5,043,376, US-5,194,463.

For example, it is possible to start with the polymeric dye in the form of a powder or granule, and at least one ionic surfactant, preferably an anionic or amphoteric surfactant. The anionic and amphoteric surfactants can be preferably chosen from alkaline salts of C12-C24 fatty acids, soy phosphatides, phospholipids, lysophospholipids. These ionic surfactants are intro- added in amounts preferably between 0.5 and 30%, and even more preferably between 1 and 10% by weight relative to the weight of the polymeric dye.

Preferably, these dispersions further comprise at least one nonionic surfactant, which is advantageously chosen from polyoxyethylenated derivatives having a molecular weight greater than 300, preferably around 1000 to 15000 and a hydrophilic balance. -lipophilic (or HLB balance) greater than or equal to 10.

For example, an aqueous dispersion of polymeric dye can be prepared by following the following steps:

(i) preparation of an oil-in-water emulsion from water, of a solution of the polymeric dye in a volatile organic solvent in which it is soluble, in the presence of at least one ionic surfactant and optionally a nonionic surfactant as described above; then (ii) evaporation of the volatile organic solvent.

The volatile organic solvent which can be used for the implementation of this process must be immiscible with water and capable of dissolving the polymer. Preferably its boiling point is less than 100 ° C.

It can for example be chosen from: hydrocarbon solvents such as n-hexane, cyclohexane, cyclopentane; chlorinated solvents such as methylene chloride, chloroform; alkyl esters of carboxylic acids, such as ethyl acetate; dialkyl ethers such as diisopropyl ether. A mixture of solvents is preferably used for the implementation of this process, comprising, in addition to the solvents described above, a volatile, polar, water-miscible solvent, such as acetone or a low molecular weight alkanol. For more information on such a process, reference can be made to US Pat. No. 5,043,376 and US Pat. 5,104,913.

The water of the aqueous dispersions described above can then be evaporated, for example by atomization or by lyophilization, in order to obtain a powder of a polymeric dye composition dispersible in other media, in particular in organic media such as oils and waxes to lead to fatty dispersions.

Using methods known to those skilled in the art, an anhydrous dispersion of polymeric dye in a fatty phase is prepared, from oil and / or wax and from at least one polymeric dye as described above. This polymeric dye can be incorporated in the form of a dispersible powder or a crude powder. It can be introduced into an oily phase to give a basic fatty dispersion in which other oils, waxes and / or other cosmetic additives are then incorporated.

The polymeric dyes which can be used in the compositions according to the invention can be introduced therein in amounts ranging from 0.1 to 20% by weight.

The polymeric dyes described above have the advantage of having the same general chemical structure and the same physicochemical properties, in very different color ranges. Thus, a red dye will have the same behavior as a yellow dye. This homogeneity of behavior allows the manufacture of make-up compositions in the form of monochrome. When mixing monochrome to achieve a shade, there is no problem of incompatibility between the different colors.

These polymeric dyes have a coloring power superior to mineral oxides and close to that of organic lakes: 4 to 5% is enough to give a mascara of bright and intense color. The rheology problems are therefore greatly reduced. In addition, these polymeric dyes do not release dye. There is therefore no problem with the appearance of streaks, staining of the skin or ocular lenses. These polymeric dyes have a coloring power very close to that of organic lakes, and have a very high light stability, this even in the presence of titanium dioxide or zinc. They can therefore be used in place of organic lacquers in all makeup formulas. Their high light stability makes it possible to present the cosmetic compositions comprising them in transparent packaging. Thus, the user can choose more precisely the color of the product she is buying. In addition, they do not interfere with oils and / or active ingredients

These brightly colored and intense polymeric dyes have the particularity of being sufficiently covering so that a small quantity is enough to color a cosmetic formula. The gloss of the film is therefore significantly improved. We obtain a makeup that is both covering, saturated and shiny.

The compositions according to the invention also comprise at least one fatty component chosen from oils and / or waxes.

According to the invention, the wax can be an animal, vegetable, mineral or synthetic wax. Among animal waxes, mention may in particular bees beeswax, whale wax. Among the vegetable waxes, mention may be made, among others, of Camauba, Candellila and Ouricoury waxes, cork fiber waxes, sugar cane waxes and Japanese waxes. Among the mineral waxes, mention may in particular be made of paraffin waxes, lanolin, microcrystalline waxes, lignite waxes and ozokerites. Among the synthetic waxes, mention may be made, in particular, of polyethylene waxes and the waxes obtained by synthesis of Fisher and Tropsch. All of these waxes are well known to those skilled in the art.

Mention may be made, among the oils which can be used in the present invention, of mink oil, turtle oil, soybean oil, grape seed oil, sesame oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, avocado oil, olive oil, castor oil, jojoba oil, peanut oil hydrocarbon oils such as paraffin oils, squalane, petrolatum; esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, isononyl isononanoate, 2-ethyl hexyl palmitate, 2-hexyl decyl laurate, 2-octyl decyl palmitate, 2-octyl dodecyl myristate, 2-diethylhexyl succinate, diisostearyl malate, 2-octyl dodecyl lactate, glycerin triisostearate, glycerin triisostearate, etc .; silicone oils such as polymethylsiloxanes, polymethylphenylsiloxanes, polysiloxanes modified by fatty acids, polysiloxanes modified by fatty alcohols, polysiloxanes modified by polyoxyalkylenes, fluorinated silicones, etc .; perfluorinated and / or organofluorinated oils; higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linoleπic acid, isostearic acid, higher fatty alcohols such as cetanol, stearyl alcohol, oleic alcohol etc .;

The fatty phase may also contain volatile oils, which will evaporate on contact with the skin, but the presence of which in the cosmetic composition is useful because they facilitate spreading of the composition during application to the skin. Such spreading agents called volatile oils here are generally oils having at 25 ° C a saturated vapor pressure at least equal to 0.5 millibar (or 50 Pa). Volatile oils when present generally represent less than 10% by weight of the final composition and less than 20% by weight of the fatty binder. Among the volatile oils which can be used in the present invention, mention will be made, for example, of silicone oils such as hexamethyldisiloxane, cyciopentadimethylsiloxane, cyclotetramethylsiloxane, fluorinated oils such as those sold under the name Galden (Montefluos) or isoparaffinic oils such as those sold under the name ISOPAR (E, G, L or H).

The composition according to the invention can also comprise at least one emulsifier. This emulsifier can be a surfactant chosen from nonionic, cationic, anionic or amphoteric surfactants. In addition to the surfactants described above for the preparation of aqueous dispersions of polymeric dye As an example, surfactants which can be used in the invention can be cited: silicone-based emulsifiers and lipid emulsifiers such as fatty alcohols, glycerol esters, sorbitan esters, methyl glycoside esters and esters of sucrose.

The compositions according to the invention may also comprise the ingredients usually used in cosmetics, among which there may be mentioned perfumes, adjuvants customary in the cosmetic and dermatological fields, such as lipophilic gelling agents, lipophilic active agents, preservatives, antioxidants. , solvents, perfumes, coloring matters, fillers. The amounts of these various adjuvants are those conventionally used in the fields considered, and for example from 0.01% to 20% of the total weight of the composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, affected by the 'proposed addition.

As solvents which can be used in the invention, mention may be made of lower alcohols, in particular ethanol and isopropanol, propylene glycol. As lipophilic gelling agents, mention may be made of modified clays such as bentones, metal salts of fatty acids such as aluminum stearates, hydrophobic silica, polyethylenes and ethylcellulose.

As lipophilic active agents, one can use tocopherol (vitamin E) and its derivatives, essential fatty acids, ceramides, essential oils. It is possible, among other things, to introduce into the compositions according to the invention active agents intended in particular for the prevention and / or treatment of skin conditions. Among these active agents, mention may be made, by way of example: - agents modulating differentiation and / or proliferation and / or skin pigmentation such as vitamin D and its derivatives, estrogens such as oestradiol, kojic acid or hydroquinone; - anti-free radical agents, such as alpha-tocopherol or its esters, superoxide dismutases, certain metal chelators or ascorbic acid and its esters.

As fillers which can be used in the present invention, mention may in particular be made of talc, silica, mica, boron nitride, and, as examples of organic fillers, nylon powder, silicone powder and polymethylene methacrylate powder.

The anhydrous cosmetic compositions according to the invention can be used as such, mainly as a make-up product for the face, that is to say in the form of eyeshadows or blushes, of eyeliners, of mascaras, of powders, foundations, lipsticks.

The anhydrous compositions according to the invention can also be used to prepare water-in-oil, oil-in-water emulsions, multiple emulsions, water-in-wax, wax-in-water emulsions, in particular for the preparation of transparent tinted creams, foundations, eye-liners, mascaras, lip care products, cast powders, eyeshadows. They then constitute all or part of the fatty phase of the emulsion.

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

Another subject of the present invention is the use of a polymeric dye as defined above in an anhydrous cosmetic composition to form a colored film on the skin, the eyelashes, the nails or the lips.

The present invention also relates to the use of a polymeric dye as defined above in an anhydrous cosmetic composition which does not color the skin, the eyelashes, the nails or the lips after makeup removal. The present invention finally relates to a method for making up the eyes, the eyelashes, the nails or the lips, characterized in that an anhydrous cosmetic composition is applied to the nails, the eyelashes, the skin or the lips. defined above.

The invention is illustrated by the following examples.

Example 1: Composition of lipstick

Esters of fatty alcohols in C8-C10 30%

C10 fatty alcohols 7%

10% aluminum octylsuccinate starch

Ozokerite 10%

Camauba wax 4% Beeswax 3%

3% titanium dioxide

Red polymer dye ( ^* ) 1%

Perfume 0.5%

Castor oil qsp100

( ^* ) coloring sulfopolyester comprising 10% of red coloring monomer prepared according to Example 1 of US Pat. No. 4,804,719 (concentration different from that of the example cited).

Procedure: the polymeric dyes are ground in the mixture of fatty alcohols, fatty alcohol esters and castor oil. The ozokerite, Camauba wax and beeswax are melted extemporaneously in a container and are introduced into the mixture with continuous stirring. The aluminum octylsuccinate starch is introduced under vacuum and finally the perfume is incorporated.

Example 2 Composition of Eyeshadow An eyeshadow composition is prepared from the formulas given below.

Talc qs 100 Mica 22%

Bismuth oxychloride 8%

Zinc stearate 3%

Nylon-12 20%

Red polymeric dye ( ^* ) 4% Vaseline oil 3%

Isopropyl myristate 3%

TiO ₂ 8%

( ^* ) Coloring polyester comprising 30% of red coloring monomer prepared in accordance with reference example 2 of patent WO92 / 07913.

Preparation of the eyeshadow: The fillers are ground with the pigments, the binder (vaseline oil and isopropyl myristate) is added and again ground. The formulas (2g) are compacted in metal cups having the following dimensions: length: 25 mm, width: 22 mm, height: 3.5 mm, at a pressure of 70 bars using a manual compactor type Kemwall.

The cohesion of the compacted eyeshadow was measured by measuring the loss of mass of powder after 10 normalized falls from a height of 20 cm: the mass loss measured is 15%.

The hardness of the compacted eyeshadow was also measured. This measurement is carried out by indentation using a durometer of the brand “ZWICK” reference 3114. The hardness measured is 77 + 1 ° Shore A.

Claims

1 - Anhydrous cosmetic composition comprising at least one wax and / or a filler, and optionally an oil, and at least one polymeric dye chosen from polyester, polyamide, polyurethane, polyacrylic polymers or mixtures thereof.

2- Composition according to claim 1, characterized in that the polymeric dye results from the polymerization of several monomers including: (i) at least one dicarboxylic acid residue carrying at least one sulfonic group; (ii) at least one diol residue; and (iii) at least one coloring monomer.

3- Composition according to any one of the preceding claims, characterized in that the polymeric dye is a water-dispersible dye polymer having linking groups comprising at least about 20 mol% of carbonyloxy and up to about 80% in moles of carbonylamido, said material containing water-soluble sulfonate groups and having from about 0.01 to about 40 mole%, based on the total of all equivalents of reactive hydroxy, carboxy or amino, of dye comprising one or more thermostable organic compounds initially having at least one condensable group, which has been reacted on or in the polymeric backbone.

4- Composition according to claim 3, characterized in that the polymeric dye comprises:

(a) an acid monomer comprising from 75 mol% to 84 mol% of isophthalic acid and from 25 mol% to 16 mol% of sodium salt of 5-isophthalic acid, (b) a glycol monomer comprising from 45 to 60 mol% of diethylene glycol and from 55 to 40 mol% of 1, 4-cyclohexanedimethanol or of ethylene glycol or their mixture,

(c) from 0.5 to 10 mol% of coloring monomer.

5- Composition according to claim 1, characterized in that the polymeric dye is a polyurethane and results from the polymerization of several monomers including:

(i) at least one di-isocyanate residue; (ii) at least one diol residue; and

(iii) at least one coloring monomer.

6- Composition according to any one of the preceding claims, characterized in that the polymeric dye comprises 5% to 55% by weight of at least one dye monomer.

7- Composition according to claim 6, characterized in that the polymeric dye comprises 10% to 40% by weight of at least one dye monomer.

8- Composition according to any one of claims 2 to 7, characterized in that the coloring monomer is chosen from anthraquinones, methines, bis-methines, aza-methines, aryiidenes, 3H-dibenzo [7, ij ] isoquinolines, 2,5-diarylaminoterephthalic acids and their esters, phthaloylphenothiazines, phthaloylphenoxazines, phthaloylacridone, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perinurins, benzoinurans, nitrourines -1 -benzopyran-2-one, quinophthalones, perylenes, quinacridones, triphenodioxazines, fluoridines, 4-amino-1, 8-naphthalimides, thioxanthrones, benzanthrones, indanthrones, indigo, thioindigo , xanthene, acridine, azine, oxazine.

9- Composition according to any one of the preceding claims, characterized in that it comprises 0.1 to 20% by weight of polymeric dye. 10- Composition according to any one of the preceding claims, characterized in that it further comprises at least one compound chosen from titanium dioxide and zinc dioxide.

1 1 - Composition according to any one of the preceding claims, characterized in that it comprises at least one wax chosen from beeswax, whale wax; Camauba, Candellila, Ouricoury waxes, cork fiber waxes, sugar cane waxes and Japanese waxes; paraffin waxes, lanolin, microcrystalline waxes, lignite waxes, ozokerites; polyethylene waxes; the waxes obtained by synthesis of Fisher and Tropsch.

12- Composition according to one of the preceding claims, characterized in that it comprises at least one oil chosen from mink oil, turtle oil, soybean oil, seed oil of grape, sesame oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, avocado oil, olive oil, castor oil, jojoba oil, peanut oil; hydrocarbon oils such as paraffin oils, squalane, petrolatum; esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, isoniazone isononanoate, 2-ethyl hexyie palmitate, 2-hexyl decyl laurate, 2-octyl decyl palmitate, 2-octyl dodecyl myristate, 2-diethylhexyl succinate, diisostearyl malate, 2-octyl dodecyl lactate, glycerin triisostearate, glycerin triisostearate, etc .; silicone oils such as polymethylsiloxanes, polymethylphenylsiioxanes, polysiloxanes modified with fatty acids, polysiloxanes modified with fatty alcohols, polysiloxanes modified with polyoxyalkyienes, fluorinated silicones, etc .; perfluorinated and / or organofluorinated oils; higher fatty acids such as myristic acid, paimitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid, higher fatty alcohols such as cetanol, stearyl alcohol, oleic alcohol. 13- Composition according to one of the preceding claims, characterized in that it comprises at least one volatile oil chosen from silicone oils such as hexamethyldisiloxane, cyclopentadimethylsiloxane, cyclotetra-methylsiioxane; volatile fluorinated oils; isoparaffinic oils.

14- Composition according to any one of the preceding claims, characterized in that it is in the form of a product for making up the face, in particular in the form of eyeshadows or cheeks, of eye-liners, mascaras, powders, foundations, lipsticks.

15- Cosmetic composition in the form of an emulsion, characterized in that its fatty phase comprises a composition according to any one of the preceding claims.

16- Process for preparing a composition according to any one of the preceding claims, characterized in that the polymeric dye is introduced into the composition in the form of a dispersible powder or of a crude powder.

17- Use of a polymeric dye according to one of claims 1 to 9 in an anhydrous cosmetic composition to form a colored film on the skin, the eyelashes, the nails or the lips.

18- Use of a polymeric dye according to one of claims 1 to 9 in an anhydrous cosmetic composition which does not color the skin, the eyelashes, the nails or the lips after makeup removal.

19- A method for making up the eyes, the eyelashes, the skin or the lips, characterized in that an anhydrous cosmetic composition according to any one of the claims is applied to the nails, the eyelashes, the skin or the lips. 1 to 15.