WO2006008616A1

WO2006008616A1 - Structured cosmetic composition

Info

Publication number: WO2006008616A1
Application number: PCT/IB2005/001975
Authority: WO
Inventors: Véronique Ferrari; Sylvie Guillard; Nathalie Julien
Original assignee: L'oreal
Priority date: 2004-07-13
Filing date: 2005-07-12
Publication date: 2006-01-26

Abstract

The present invention relates to a nonfluid cosmetic composition comprising at least one liquid fatty phase and containing at least: - an effective amount of at least one semicrystalline polymer with (a) crystallizable side chain(s), - a nonpigmentary mineral filler, and - a nonpigmentary organic filler.

Description

Structured cosmetic composition

The present invention relates to a nonfluid care and/or treatment and/or makeup composition for the skin, including the scalp, and/or the lips, of the human face, comprising at least one structured liquid fatty phase.

Many cosmetic or dermatological products are formulated using a structured or rigidified liquid fatty phase. Illustrations of these products that may especially be mentioned include products that are especially in the form of products cast in stick or dish form, for instance lipsticks or lip balms, cast foundations, concealer products, eyeshadows, makeup rouges, in paste or cream form, eyeliners, body makeup products (for example semipermanent tattoos), deodorants, antisun compositions or skin-coloring compositions. In point of fact, this structuring of the liquid fatty phase is advantageous in several respects. It makes it possible, firstly, to limit its exudation from the solid compositions, and, secondly, its migration after application to the skin and more particularly the lips, over time in the wrinkles and fine lines.

This structuring was initially mainly obtained by means of solid particles, fillers and/or waxes, introduced into the liquid fatty phase. However, the use of these particles or fillers has a tendency to make the composition matt, and thus to affect its glossy nature that is particularly appreciated by users. To overcome this drawback, it has been proposed to structure the liquid fatty phases of cosmetic compositions using semicrystalline polymers (EP 1 262 163, EP 1 262 164, EP 1 114 636 and WO 02/47626).

However, the cosmetic compositions thus prepared are also not entirely satisfactory. They may in particular show large sensitivity to temperature variations, and especially in the range of "high temperatures", i.e. above about 30⁰C, and may then become subject to the phenomenon of exudation of the oily phase at the surface of the compositions. Similarly, certain sticks may, after having been subjected to significant temperature variations, especially of the order of 15 to 20⁰C, become unslippery and dry, and thus give a matt film. Consequently, there is still at the present time a need for cosmetic compositions that have satisfactory stability, especially with regard to significant temperature variations, and which are moreover satisfactory in terms of cosmetic quality, for instance gloss and migration resistance.

The subject of the invention is, specifically, a care and/or makeup and/or treatment composition for keratin materials, for instance the skin and/or the lips of the face, for satisfying all of the requirements mentioned above.

More specifically, according to a first aspect, the invention relates to a nonfluid cosmetic composition comprising at least one liquid fatty phase containing at least an effective amount of at least one semicrystalline polymer with (a) crystallizable side chain(s), at least one nonpigmentary mineral filler and at least one nonpigmentary organic filler.

For the purposes of the present invention, the term "nonfluid" means any cosmetic composition lacking the ability to flow under the action of its own weight.

More particularly, this type of cosmetic composition is also termed a "cast composition" as opposed to "fluid" compositions. These compositions are characterized by a pasty appearance at room temperature (20-25°C).

Thus, a cosmetic composition may be in accordance with the invention provided that it has a melting point of greater than 25°C, especially ranging from 25 to 6O⁰C and in particular ranging from 30 to 45°C and/or a hardness ranging from 0.001 to 0.5 MPa and especially ranging from 0.005 to 0.4 MPa. The composition of the invention may be in the form of a paste, a solid or a cream. It may be a simple emulsion of oil-in-water or water-in-oil type or a multiple emulsion, or a solid or soft gel. It is preferably in anhydrous form and more especially in the form of an anhydrous gel, especially cast in stick or dish form.

In particular, the present invention is directed toward covering a lipstick comprising at least one liquid fatty phase containing at least an effective amount of at least one semicrystalline polymer with (a) crystallizable side chain(s), at least one nonpigmentary mineral filler and at least one nonpigmentary organic filler.

According to another of its aspects, the present invention also relates to a cosmetic process for caring for, making up or treating the skin or the lips of the human face, comprising the application to the skin or the lips of the human face of a cosmetic composition in accordance with the present invention. According to another of its aspects, the present invention is also directed toward protecting the use of at least one nonpigmentary mineral filler and at least one nonpigmentary organic filler, in a cosmetic composition comprising a physiologically acceptable medium and containing at least one liquid fatty phase structured with at least an effective amount of at least one semicrystalline polymer with (a) crystallizable side chain(s), and having improved stability with regard to exudation.

The inventors have thus found, surprisingly, that the use of two nonpigmentary fillers of defined nature, i.e. one organic and the other mineral, allows the production of nonfluid cosmetic compositions, especially in stick form, whose application to the skin and in particular the lips gives a glossy, comfortable, nontacky film with good coverage, which does not migrate, while at the same time showing good resistance to significant temperature variations, at high temperatures, especially above about 30⁰C, as is illustrated in the examples.

In particular, the combination of semicrystalline polymers with (a) crystallizable side chain(s) with at least one nonpigmentary organic filler and at least one nonpigmentary mineral filler makes it possible to give the composition good stability over time and with respect to temperature. Thus, it is possible to obtain a composition that remains macroscopically homogeneous, without exudation of the liquid fatty phase, even in a humid atmosphere, for at least 2 months at abo.ut 25 °C or higher, especially at about 30°C and in particular at about 45°C, and atmospheric pressure.

Nonpigmentary mineral and organic fillers

As stated previously, the incorporation of at least one nonpigmentary mineral filler and of at least one nonpigmentary organic filler makes it possible to improve the resistance with respect to significant temperature variations or with respect to a given temperature, especially above 30°C. This resistance is reflected especially by improved stability with regard to exudation.

The stability with regard to exudation (or syneresis) of the composition according to the invention is evaluated by placing the composition in an oven for eight weeks at 25°C. In this test, the physical appearance of the sample is monitored at the time that it is placed in the chamber. The sample is then monitored at 24 hours, at three days, at one week, at two weeks, at four weeks and finally at eight weeks. The stability may also be evaluated by repeating the eight-week cycle in the oven at 4°C, 37°C, 45°C or 50°C, and under freezing/thawing conditions.

At the end of the stability test under consideration, the sample is monitored as regards its physical appearance, its form (it is examined to see whether it folds, if the composition is in the form of a tube or wand of lipstick, or whether it twists), phase separation, melting or syneresis (exudation).

For the purposes of the present invention, the terms "syneresis" and "exudation" are used interchangeably and correspond to the appearance of droplets, which are visible to the naked eye, at the surface of the composition. For the purposes of the present invention, the term "filler" denotes solid particles of any form, which are in an insoluble form and dispersed in the medium of the composition, even at temperatures that may be up to the melting point of all the fatty substances of the composition.

Generally, the fillers used according to the invention are colorless or white, i.e. nonpigmentary, i.e. they are not used to give the composition according to the invention a particular color or shade, even if their use may inherently lead to such a result.

They are therefore, in this respect, different than nacres, organic pigmentary materials, for instance carbon black, pigments of D & C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminum, and than mineral pigmentary materials, for instance titanium dioxide, zirconium oxide or cerium oxide, and also iron oxides (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, which are, themselves, used to give a shade and coloring effect to the compositions in which they are incorporated.

Such compounds are not covered, for the purposes of the invention, by the definition of nonpigmentary organic or mineral fillers.

The nonpigmentary fillers used in the compositions according to the present invention may be of lamellar, globular, spherical or fibrous form, or in any other form intermediate between these defined forms.

The form of the particles of the same filler may be homogeneous, i.e. the particles are predominantly present in only one type of form, or heterogeneous, i.e. the particles are present in a set of varied forms. The form of particles of different fillers may be homogeneous or heterogeneous. The form of the particles of the fillers is chosen by a person skilled in the art so as to ensure their good dispersion in the composition.

The size of the particles, i.e. their granulometry, is chosen so as to ensure good dispersion of the fillers in the composition according to the invention. The granulometry of the particles may be distributed in the range from 5 μm to 10 nm and in particular from 10 μm to 10 nm.

The fillers according to the invention may or may not be surface-coated, in particular surface-treated with silicones, amino acids, fluoro derivatives or any other substance that promotes the dispersion and compatibility of the filler in the composition. The amounts of the nonpigmentary mineral and organic fillers are adjusted taking into account the amount of the semicrystalline polymer with (a) crystallizable side chain(s), so as to contribute toward the desired hardness and to ensure the stability of the compositions as a function of the specific applications envisioned.

This amount may especially range from 0.1% to 10% and in particular from 2% to 7% relative to the total weight of the composition.

More particularly, the weight ratio of fillers/polymers is less than 1, or even less than or equal to 0.9 and in particular less than or equal to 0.6.

In general, it is greater than 0.015, and less than 1 and more particularly less than or equal to 0.6. According to one embodiment, the composition according to the invention comprises at least one nonpigmentary mineral filler and at least one nonpigmentary organic filler present in a weight ratio that is within the range from 1:1 to 10:1, in particular from 2:1 to 6:1 and more particularly from 3:1 to 5:1.

Mineral fillers

For the purposes of the present invention, the terms "mineral" and "inorganic" are used interchangeably.

Among the nonpigmentary mineral fillers that may be used in the compositions according to the invention, mention may be made of talc, mica, silica, kaolin, bentone, precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, hydroxyapatite, boron nitride, hollow silica microspheres (Silica Beads from Maprecos), and glass or ceramic microcapsules, and mixtures thereof. According to one embodiment, the cosmetic composition according to the invention comprises at least one nonpigmentary mineral filler chosen from the group comprising kaolin, silica and bentone, and mixtures thereof.

According to one particular embodiment, the composition according to the invention comprises a nonpigmentary mineral filler in a proportion of from 0.1% to 15%, in particular from 1% to 10% and more particularly from 2% to 6% by weight relative to the total weight of the composition.

Organic fillers Among the organic fillers that may be mentioned are polyamide powder

(Orgasol Nylon^® from Atochem), poly-β-alanine powder and polyethylene powder, Teflon, lauroyllysine, starch, tetrafluoroethylene polymer powders, hollow polymer microspheres such as Expancel (Nobel Industrie), Polytrap (Dow Corning), acrylate copolymers, PMMA, 12-hydroxystearic acid oligomer stearate and silicone resin microbeads (for example Tospearls from Toshiba), precipitated calcium carbonate, magnesium carbonate, magnesium hydrogen carbonate, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms and preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium stearate, lithium stearate, zinc laurate or magnesium myristate, and mixtures thereof. For the purposes of the present invention, the organic fillers are different than the pigments.

According to one embodiment, the composition according to the invention comprises at least one nonpigmentary organic filler chosen from the group comprising Nylon^®, Polytrap or acrylate copolymers such as Polytrap 603 sold by Lambert Riviere (or ethylene glycol dimethacrylate/lauryl methacrylate copolymer), PMMA and 12-hydroxy- stearic acid oligomer stearate (Octacare DSI OL300 from Avecia), and mixtures thereof.

According to one particular embodiment, the composition according to the invention comprises a nonpigmentary organic filler in an amount of from 0.01% to 5%, in particular from 0.1% to 3% and more particularly from 0.5% to 2% by weight relative to the total weight of the composition. As particular combinations of nonpigmentary organic and mineral fillers that may be used in the composition according to the invention, mention may be made of the mixture of kaolin, of 12-hydroxystearic acid oligomer stearate, for instance the product sold under the name Octacare DSP OL300 from Avecia, and of an acrylate copolymer (for instance ethylene glycol dimethacrylate/lauryl methacrylate copolymer) in a 4:2:1 ratio, in particular in a 4.5:4:1 ratio, in particular in a 4:4:1 ratio and more particularly in a 4.5:2:1 ratio. One or more dispersants may be used, where appropriate, to protect the dispersed fillers or particles against aggregation or flocculation. They may be added independently of the solid fillers or particles or in the form of a colloidal dispersion of particles.

The concentration of dispersants is chosen so as to obtain satisfactory dispersion of the solid particles (without flocculation) and especially a stable colloidal dispersion of particles. It should be adapted as a function of the total amount of fillers to be introduced into the composition. It may be from 0.3 to 5 mg/m² and in particular from 0.5 to 4 mg/m² of surface area of particles.

This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, poly(12-hydroxystearic acid) esters are used, such as poly(12-hydroxystearic acid) stearate with a molecular weight of about 750 g/mol, such as the product sold under the name Solsperse 21 000^® by the company Avecia, esters of poly(12-hydroxystearic acid) with polyols such as glycerol or diglycerol, such as polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymuls PGPH^® by the company Henkel (or diglyceryl poly(12-hydroxystearate))₅ or alternatively poly(12-hydroxystearic acid), such as the product sold under the reference Arlacel PlOO by the company Uniqema, and mixtures thereof.

As other dispersants that may be used in the composition of the invention, mention may be made of quaternary ammonium derivatives of polycondensate fatty acids, for instance Solsperse 17 000^® sold by the company Avecia, and mixtures of polydimethylsiloxane/oxypropylene such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C. Semicrystalline polymers with (a) crystallizable side chain(s)

For the purposes of the invention, the term "polymers" means compounds comprising at least two repeating units, preferably at least three repeating units and more especially at least ten repeating units. For the purposes of the invention, the term "semicrystalline polymer" means polymers comprising at least one crystallizable side chain with a temperature of first-order reversible phase change, in particular of melting (solid-liquid transition).

The term "crystallizable chain" means a chain comprising at least six carbon atoms and which, if it were alone, would change reversibly from the amorphous state to the crystalline state, depending on whether the system is above or below the melting point.

For the purposes of the invention, a chain is a group of atoms, which is pendent or lateral relative to the polymer skeleton.

The composition according to the invention advantageously comprises one or more semicrystalline polymers with (a) crystallizable side chain(s) and in particular at least one low-melting semicrystalline polymer with (a) crystallizable side chain(s) (also known as the first polymer), combined with at least one high-melting semicrystalline polymer with (a) crystallizable side chain(s) (also known as the second polymer).

These polymers in particular have a melting point higher than the temperature of the keratin support intended to receive the composition and more especially keratin materials, for instance the lips or the skin, including the scalp.

The terms "organic compound", "of organic structure" and "organic chain" mean compounds or chains containing carbon atoms and hydrogen atoms and possibly hetero atoms such as S, O, N or P, alone or in combination.

In the description hereinbelow, the semicrystalline polymer(s) or compound(s) with (a) crystallizable side chain(s) with a melting point m.p.2 of less than 50°C will be referred to as "low-melting semicrystalline polymers with (a) crystallizable side chain(s)" and the semicrystalline polymer(s) or compound(s) with (a) crystallizable side chain(s) with a melting point m.p.l of greater than or equal to 50⁰C will be referred to as "high- melting semicrystalline polymers with (a) crystallizable side chain(s)". This melting point (m.p.) may be measured by any known method and in particular with a differential scanning calorimeter (DSC). According to one particular embodiment, the cosmetic composition according to the present invention comprises at least one low-melting semicrystalline polymer with (a) crystallizable side chain(s) with a melting point of less than 50°C and in particular in a range from 30°C to less than 50°C. According to another embodiment, the cosmetic composition according to the present invention comprises at least one high-melting semicrystalline polymer with (a) crystallizable side chain(s) with a melting point at least equal to or greater than 5O⁰C, in particular in a range from 55 to 160°C and more particularly in a range from 60 to 130⁰C.

According to another particular mode of the invention, the cosmetic composition according to the present invention comprises a mixture of at least one low- melting semicrystalline polymer with (a) crystallizable side chain(s) and of at least one high-melting semicrystalline polymer with (a) crystallizable side chain(s).

The structuring or gelation of the liquid fatty phase according to the invention is due to crystallization of the semicrystalline polymer(s) with (a) crystallizable side chain(s) in the liquid fatty phase, possibly combined with one or more crystalline compounds, and is not in any way a matter of physical interaction of the dipole or hydrogen type between polymer chains.

The semicrystalline polymers to which the invention applies especially comprise a polymer skeleton and at least one crystallizable organic side chain. The semicrystalline pόlymer(s) with (a) crystallizable side chain(s) to which the invention applies advantageously has (have) a number-average molecular mass of greater than 2000.

The high-melting semicrystalline polymers with (a) crystallizable side chain(s) that may be used in the invention are in particular semicrystalline polymers of organic structure, which are solid at room temperature and which have a melting point of greater than or equal to 50°C, comprising a polymeric organic skeleton and at least one crystallizable organic side chain and having a number-average molecular mass of greater than 2000.

It is possible to use as high-melting compound semicrystalline polymers that are solid at room temperature and that have a melting point of greater than 50°C of random polymers comprising controlled crystallization, as described in document EP-A-O 951 897 and more especially the commercial products Engage 8 401 and Engage 8 402 from Dupont de Nemours, having respective melting points of 51°C and 64°C and which are ethylene/1 -octene random bipolymers.

Advantageously, the (high-melting or low-melting) semicrystalline polymer(s) of the composition of the invention comprise(s) a number-average molecular mass Mn ranging from 2000 to 800 000 and preferably from 3000 to 500 000, for example from 4000 to 150 000, and especially less than 100 000, and better still from 4000 to 99 000. Preferably, they have a number-average molecular mass of greater than 5600, for example ranging from 5700 to 99 000.

The semicrystalline polymer(s) according to the invention serving as structuring agent are nondeformable solids at room temperature (about 20-25°C) and atmospheric pressure (760 mmHg). They are capable of structuring, alone or as a mixture, the composition without addition of a particular surfactant, or of filler or wax.

According to the invention, the low-melting semicrystalline polymers and/or the high-melting compounds are advantageously soluble in the fatty phase to at least 1% by weight, at a temperature above their melting point. Apart from the crystallizable chains, the polymer blocks are amorphous, hi particular, the polymer skeleton of the semicrystalline polymers is soluble in the liquid fatty phase.

According to the invention, the high-melting semicrystalline compound(s) is (are) advantageously polymers with a melting point m.p.l such that 50°C< m.p.l≤ 150°C, in particular 55°C< m.p.l≤ 15O⁰C and more particularly 60°C< m.p.l≤ 13O⁰C, and the low-melting polymers advantageously have a melting point m.p.2 such that 30°C≤ m.p.2< 50°C and in particular 35°C< m.p.2< 45°C. This melting point is a temperature of first- order change of state.

In general, the low-melting polymers have a melting point m.p.2 at least equal to the temperature of the keratin support intended to receive the composition according to the invention. hi particular, the crystallizable chain(s) of the semicrystalline polymers represent(s) at least 30% and better still at least 40% of the total weight of each polymer. The polymers with (a) crystallizable side chain(s) according to the invention is (are) advantageously in random form.

In particular, the semicrystalline polymers of the invention are of synthetic origin. In general, the crystallizable units (chains) of the semicrystalline polymers according to the invention are derived from monomer(s) with crystallizable chain(s), used for the manufacture of the semicrystalline polymers.

According to the invention, the low-melting semicrystalline polymer and the high-melting semicrystalline polymer are chosen from homopolymers and copolymers bearing at least one crystallizable side chain per repeating unit.

The semicrystalline polymers that may be used in the invention are in particular:

- homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or copolymers bearing at least one crystallizable block in the skeleton, for instance those described in document US-A-5 156 911,

- homopolymers or copolymers bearing at least one crystallizable side chain, in particular bearing fluoro group(s), such as those described in document WO-A-01/19333, and

- mixtures thereof. They are homopolymers or copolymers comprising from 50% to 100% by weight of units resulting from the polymerization of one or more monomers bearing a crystallizable hydrophobic side chain.

These homopolymers or copolymers are of any nature, provided that they meet • the conditions mentioned hereinbelow with, in particular, the characteristic of being soluble or dispersible in the liquid fatty phase, by heating above their melting point m.p. They can result:

- from the polymerization, especially the free-radical polymerization, of one or more monomers containing reactive or ethylenic double bond(s) with respect to a polymerization, namely a vinyl, (meth)acrylic or allylic group, - from the polycondensation of one or more monomers bearing co-reactive groups (carboxylic acid, sulfonic acid, alcohol, amine or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas or polyamides.

In general, these polymers are chosen especially from homopolymers and copolymers resulting from the polymerization of at least one monomer containing crystallizable chain(s) that may be represented by formula X: — M<

in which:

- M represents an atom of the polymer skeleton, S represents a spacer and C represents a crystallizable group.

The crystallizable chains "-S-C" may be aliphatic or aromatic, and optionally fluorinated or perfluorinated. "S" especially represents a group (CHa)_n or (CH₂CH₂O)_n or (CH₂O), which may be linear or branched or cyclic, with n being an integer ranging from 0 to 22. Preferably, "S" is a linear group. Preferably, "S" and "C" are different.

When the crystallizable chains are hydrocarbon-based aliphatic chains, they comprise hydrocarbon-based alkyl chains containing at least 11 carbon atoms and not more than 40 carbon atoms and better still not more than 24 carbon atoms. They are especially aliphatic chains or alkyl chains containing at least 12 carbon atoms, and they are preferably C₁₄-C₂₄ alkyl chains. When they are fluoroalkyl or perfluoroalkyl chains, they contain at least 6 fluorinated carbon atoms and especially at least 11 carbon atoms, at least 6 of which carbon atoms are fluorinated. As examples of semicrystalline polymers or copolymers containing crystallizable chain(s), mention may be made of those resulting from the polymerization of one or more of the following monomers: (meth)acrylates of saturated alkyls with the alkyl group being C₁₄-C₂₄, perfluoroalkyl (meth)acrylates with a C₁₁-C₁₅ perfluoroalkyl group, N-alkyl(meth)acrylarnides with the alkyl group being C₁₄ to C₂₄ with or without a fluorine atom, vinyl esters containing alkyl or perfluoro(alkyl) chains with the alkyl group being C₁₄ to C₂₄ (with at least 6 fluorine atoms per perfluoroalkyl chain), vinyl ethers containing alkyl or perfluoro(alkyl) chains with the alkyl group being C₁₄ to C₂₄ and at least 6 fluorine atoms per perfluoroalkyl chain, C₁₄ to C₂₄ α-olefins, for instance octadecene, para- alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, and mixtures thereof.

When the polymers result from a polycondensation, the hydrocarbon-based and/or fluorinated crystallizable chains as defined above are borne by a monomer that may be a diacid, a diol, a diamine or a diisocyanate. When the polymers that are the subject of the invention are copolymers, they additionally contain from 0 to 50% of groups Y or Z resulting from the copolymerization: α) of Y which is a polar or nonpolar monomer or a mixture of the two:

- when Y is a polar monomer, it is either a monomer bearing polyoxyalkylene groups (especially oxyethylene and/or oxypropylene groups), a hydroxyalkyl

(meth)acrylate, for instance hydroxyethyl acrylate, (meth)acrylamide, an N- alkyl(meth)acrylamide, an N,N-dialkyl(meth)acrylamide such as, for example, N₅N- diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinylcaprolactam, a monomer bearing at least one carboxylic acid group, for instance (meth)acrylic acids, crotonic acid, itaconic acid, maleic acid or fumaric acid, or bearing a carboxylic acid anhydride group, for instance maleic anhydride, and mixtures thereof.

- when Y is a nonpolar monomer, it may be an ester of the linear, branched or cyclic alkyl (meth)acrylate type, a vinyl ester, an alkyl vinyl ether, an α-olefm, styrene or styrene substituted with a C₁ to C_1O alkyl group, for instance α-methylstyrene, or a macromonomer of the polyorganosiloxane type containing vinyl unsaturation.

For the purposes of the invention, the term "alkyl" means a saturated group especially of C₈ to C₂₄ and in particular of C₁₄ to C₂₄, except where otherwise mentioned. β) of Z which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as the "polar Y" defined above. Preferably, the semicrystalline polymers containing (a) crystallizable side chain(s) are alkyl (meth)acrylate or alkyl(meth)acrylamide homopolymers with an alkyl group as defined above, and especially of C₁₄-C₂₄, copolymers of these monomers with a hydrophilic monomer preferably of different nature than (meth)acrylic acid, for instance N- vinylpyrrolidone or hydroxyethyl (meth)acrylate, and mixtures thereof. According to one particular embodiment of the invention, the polymer is chosen from copolymers resulting from the polymerization of at least one monomer containing a crystallizable chain chosen from saturated C₁₄ to C₂₄ alkyl (meth)acrylates, C₁₁ to C₁₅ perfluoroalkyl (meth)acrylates, C₁₄ to C₂₄ N-alkyl(meth)acrylamides with or without a fluorine atom, vinyl esters containing C₁₄ to C₂₄ alkyl or perfluoroalkyl chains, vinyl ethers containing C₁₄ to C₂₄ alkyl or perfluoroalkyl chains, C₁₄ to C₂₄ α-olefms, para- alkylstyrenes with an alkyl group containing from 12 to 24 carbon atoms, with at least one optionally fluorinated C₁ to C₁₀ monocarboxylic acid ester or amide, which may be represented by the following formula:

in which R₁ is H or CH₃, R represents an optionally fluorinated C₁-C₁₀ alkyl group and X represents O, NH or NR₂ in which R₂ represents an optionally fluorinated C₁-C₁₀ alkyl group.

According to one more particular embodiment of the invention, the polymer is derived from a monomer containing a crystallizable chain, chosen from saturated C₁₄ to C₂₂ alkyl (meth)acrylates.

As specific examples of semicrystalline polymers that may be used in the composition according to the invention, mention may be made of the products Intelimer^® from the company Landec, described in the brochure "Intelimer^® polymers", Landec IP22

(Rev. 4-97). These polymers are in solid form at room temperature (25°C). They bear crystallizable side chains and have the formula X above.

The low-melting semicrystalline polymers are especially those described in examples 3, 4, 5, 7 and 9 of patent US-A-5 156 911 containing a -COOH group, resulting from the copolymerization of acrylic acid and of a C₅ to C₁₆ alkyl (meth)acrylate with an m.p.2 ranging from 20⁰C to 35°C, and more particularly from the copolymerization: - of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate in a 1/16/3 ratio,

- of acrylic acid and of pentadecyl acrylate in a 1/19 ratio,

- of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in a 2.5/76.5/20 ratio, - of acrylic acid, of hexadecyl acrylate and of methyl acrylate in a 5/85/10 ratio,

- of acrylic acid and of polyoctadecyl methacrylate in a 2.5/97.5 ratio.

It is also possible to use the polymer Structure "O" from National Starch, as described in document US-A-5 736 125, with an m.p.2 of 44°C, and also semicrystalline polymers with crystallizable pendent chains comprising fluoro groups, as described in examples 1, 4, 6, 7 and 8 of document WO- A-01/19333.

It is also possible to use low-melting semicrystalline polymers obtained by copolymerization of stearyl acrylate and of acrylic acid or NVP as described in document US-A-5 519 063 and more especially those described in examples 1 and 2 of patent application EP 1 262 163, with respective melting points of 40°C and 38°C.

The high-melting semicrystalline polymers are especially Intelimer described in the document "Intelimer^® polymers", Landec IP22 (Rev 4.97) with a melting point m.p.l of 56°C, which is an impermeable, nontacky viscous product at room temperature. In particular, among the low-melting semicrystalline polymers that are suitable for preparing the compositions according to the present invention, mention may be made of polystearyl acrylate, such as the product sold under the name Intelimer^® IPA 13-1 from the company Landec.

In particular, among the high-melting semicrystalline polymers that are suitable for preparing the compositions according to the invention, mention may be made of polybehenyl acrylate.

The structuring of the fatty phase may advantageously be modified as a function of the nature of the polymers and their respective concentrations, and may be such that a rigid structure in the form of a wand or a tube is obtained. In particular, the amount of polymer(s) is adjusted so as to give the composition under consideration the desired hardness and as a function of the particular application envisioned.

The hardness of the compositions according to the present invention, which are especially in the form of a tube or wand of lipstick, may be, for example, from 30 gf to 300 gf, in particular from 30 gf to 250 gf and more particularly from 30 gf to 200 gf.

The hardness may be measured according to the "cheese wire" method, which consists in cutting tubes 12.7 mm in diameter of the composition and measuring its hardness at 20°C using a DFGHS2 force gauge from the company Indelco-Chatillon Co. traveling at a speed of 100 mm/minute. The value of the hardness measured by this method is expressed as the shear force (expressed in gram-force) required to cut a tube under these conditions. It is, however, possible to use an amount of semicrystalline polymer such that the composition is in the form of a soft paste that may be applied to the keratin materials by finger or using an applicator.

In particular, the composition according to the invention may be in cast form. In practice, the total amount of semicrystalline polymer represents from 0.1% to 80%, better still from 0.5% to 40% and even better still from 3% to 30% of the total weight of the composition.

The composition according to the invention advantageously comprises a high- melting semicrystalline polymer with (a) crystallizable side chain(s) and a low-melting semicrystalline polymer with (a) crystallizable side chain(s) in a weight ratio in the range from 10/90 to 90/10 and in particular from 40/60 to 60/40.

Advantageously, the weight ratio of semicrystalline polymers with (a) crystallizable side chain(s) relative to the liquid fatty phase is from 0.20 to 0.60 and better still from 0.25 to 0.50, in order to obtain a hard stick that disintegrates on contact with the skin or the lips and in particular with a hardness ranging from 100 to 350 gf.

Liquid fatty phase

For the purposes of the patent application, the term "liquid fatty phase" means a fatty phase that is liquid at room temperature (20-25⁰C) and atmospheric pressure (760 mmHg), composed of one or more mutually compatible fatty substances that are liquid at room temperature, also known as oils. This fatty phase is macroscopically homogeneous and constitutes the continuous phase of the composition.

The liquid fatty phase structured with the semicrystalline polymer(s) and in which are dispersed the nonpigmentary organic and mineral fillers may comprise one or more cosmetically and dermatologically acceptable oils, and in general physiologically acceptable oils, chosen especially from carbon-based oils, hydrocarbon-based oils, fluoro oils and/or silicone oils, of mineral, animal, plant or synthetic origin, alone or as mixtures provided that they form a stable homogeneous mixture and that they are compatible with the intended use. The oil(s) of which the fatty phase is composed may also be selected on the basis of its (their) polar or apolar properties.

For the purposes of the invention, the term "hydrocarbon-based oils" means oils predominantly containing carbon atoms and hydrogen atoms, and in particular alkyl or alkenyl chains, for instance alkanes or alkenes, but also oils containing alkyl or alkenyl chains comprising ether, ester, hydroxyl or carboxylic acid groups. It is possible to add to the apolar oils polar oils, or apolar oils serving especially as cosolvent for the polar oils.

Mention may thus be made of: - hydrocarbon-based oils of animal origin, for instance perhydrosqualene, squalane, mink oil or turtle oil, or mixtures thereof;

- liquid linear or branched hydrocarbons or fluorocarbons of mineral or synthetic origin, for instance liquid paraffins and derivatives thereof or petroleum jelly, hydrogenated polyisobutylene (such as Parleam^®, a hydrogenated isoparaffin sold by the company Nippon Oil Fats), isododecane, polydecenes or Isopars, and isoparaffins; linear or cyclic, volatile or nonvolatile silicone oils such as polydimethylsiloxanes (PDMS); polydimethylsiloxanes that are liquid at room temperature, comprising alkyl, alkoxy or phenyl groups, which are pendent and/or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl PDMSs such as phenyl trimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyl dimethyl trisiloxanes, diphenyl dimethicones, phenyl dimethicones and polymethylphenylsiloxanes; PDMSs substituted with aliphatic and/or aromatic groups, which are optionally fluorinated, or with functional groups such as hydroxyl, thiol and/or amine groups; polysiloxanes modified with fatty acids, fatty alcohols or polyoxyalkylenes, in particular polyoxyalkylenes or copoly(oxyethylene-oxypropylene)s such as dimethicone copolyols, silicones bearing both hydrocarbon-based hydrophobic groups (for example C₂-C₃₀ alkyl groups) and polyoxyethylene or copoly(oxyethylene/oxypropylene) blocks or grafts, such as alkyl dimethicone copolyols; fluoro or perfluoro silicones, such as perfluoroalkyl polydimethylsiloxanes and perfluoroalkyl polymethylphenylsiloxanes; fluoro oils and especially perfluoro oils,

- hydrocarbon-based oils of plant origin, for instance liquid triglycerides of C₈ to C₂₄ fatty acids and of glycerol, the acids of which may have varied chain lengths, these chains possibly being linear or branched, and saturated or unsaturated, for instance soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, sesame oil, shea oil, corn oil, arara oil, rapeseed oil, sunflower oil, cottonseed oil, apricot oil, castor oil, avocado oil, jojoba oil, olive oil, cereal germ oil, wheatgerm oil, alfalfa oil, poppyseed oil, pumpkin oil, marrow oil, avocado oil, hazelnut oil, blackcurrant pip oil, evening primrose oil, millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower oil, candlenut oil, passionflower oil or musk rose oil; or alternatively caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; lanolic acid, oleic acid, lauric acid or stearic acid esters; fatty esters and fatty ethers such as esters and ethers derived from long-chain acids or alcohols (i.e. containing from 6 to 30 carbon atoms), especially esters of formula RCOOR', in which R represents a linear or branched higher fatty acid residue containing from 7 to 40 carbon atoms and R' represents a branched or unbranched hydrocarbon-based chain containing from 3 to 40 carbon atoms, such as purcellin oil (cetostearyl octanoate), C₁₂-C₁₅ alkyl benzoates, palmitates, adipates and benzoates, especially diisopropyl adipate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2- octyldodecyl myristate or lactate, 2-diethylhexyl succinate, diisostearyl malate, tridecyl trimellitate, glyceryl or diglyceryl triisostearate triisocetyl citrate; octanoates, decanoates or ricinoleates of alcohols or of polyalcohols, hydroxylated esters, for instance isostearyl lactate or diisostearyl malate; pentaerythritol esters; C₈-C₂₆ fatty acids such as myristate acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid; C₈-C₂₆ fatty alcohols such as stearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol or octyldodecanol; and mixtures thereof. According to one particular embodiment, the liquid fatty phase that is suitable for use in the compositions in accordance with the invention is advantageously chosen from hydrogenated polyisobutene, triisocetyl citrate, isononyl isononanoate and octyldodecanol, and mixtures thereof.

The liquid fatty phase represents, in practice, from 5% to 99% and preferably from 20% to 80% of the total weight of the composition. It advantageously represents at least 60% of the total weight of the composition.

Volatile oil

According to one embodiment, the composition according to the invention comprises a fatty phase containing at least one volatile oil. The term "volatile oil" means any nonaqueous medium capable of evaporating on contact with the skin in less than one hour, at room temperature (20-25°C) and atmospheric pressure (760 mrnHg).

The volatile cosmetic oil(s), which are liquid at room temperature, especially have a vapor pressure, measured at room temperature and atmospheric pressure, ranging from 10^~3 to 300 mmHg (0.266 Pa to 40 000 Pa), preferably from 0.02 to 300 mrnHg (2.66 Pa to 40 000 Pa) and better still ranging from 0.1 to 90 mmHg (13 Pa to 12 000 Pa).

According to the invention, these volatile oils especially facilitate the application of the composition to the skin or the lips. These volatile oils are favorable toward obtaining a film with total "transfer-resistance" properties. After evaporation of these oils, a flexible film-forming deposit that is not tacky on the skin and mucous membranes, which follows the movements of the skin or, respectively, the lips onto which the composition is applied, is obtained. These oils may be hydrocarbon-based oils or silicone oils optionally comprising alkyl or alkoxy groups that are pendent or at the end of a silicone chain, or a mixture of these oils.

In particular, the volatile oils are cosmetic oils chosen from oils that do not have a flash point, oils with a flash point ranging from 40°C to 100⁰C, and mixtures thereof, so as to facilitate their use. In addition, they advantageously have a boiling point at atmospheric pressure of less than 22O⁰C and better still less than 210°C, especially ranging

As volatile oils that may be used in the invention, mention may be made of linear or cyclic silicone oils with a viscosity at room temperature of less than 8 cSt and especially containing from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may be made especially of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisilox- ane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, deca- methyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

As other volatile oils that may be used in the invention, mention may be made of hydrocarbon-based volatile oils containing from 8 to 16 carbon atoms and mixtures thereof, and especially C₈-C₁₆ branched alkanes, for instance isoalkanes (also known as isoparaffins), isododecane, isodecane and isohexadecane, for example the oils sold under the trade names Isopar and Permethyl, and C₈-C₁₆ branched esters, for instance isohexyl neopentanoate, and mixtures thereof.

Isododecane (Permethyl 99 A), C₈-C₁₆ isoparaffms, for instance Isopar L, E, G or H, and mixtures thereof, optionally combined with decamethyltetrasiloxane or cyclopentasiloxane, are preferably used.

Volatile fluoro oils may also be used. These volatile oils especially represent from 5% to 97.5% of the total weight of the composition, better still from 10% to 75% and in particular from 30% to 75% of the total weight of the composition. In general, the amount of volatile solvent used is an amount that is sufficient to obtain "transfer- resistance" properties. This amount will be adapted by a person skilled in the art as a function of the desired intensity of the "transfer-resistance" properties.

The volatile oil in particular represents 20% to 50%, preferably from 30% to 40% and in particular about 35% by weight of the composition.

The volatile oil in particular represents 40% to 60% and in particular from 45% to 55% of the liquid fatty phase.

The weight ratio of volatile oil relative to the semicrystalline polymer is advantageously between 1 and 2.5 and preferably from 1.5 to 2.

Solid fatty phase The composition according to the invention may comprise, besides the liquid fatty phase in which the polymer(s) is (are) stabilized, a solid fatty phase that may be chosen from waxes, gums and/or pasty fatty substances, of plant, animal, mineral or synthetic origin, or even silicone origin, and mixtures thereof.

Pasty fatty substance

A "pasty fatty substance" is a viscous product containing a liquid fraction and a solid fraction. For the purposes of the invention, the term "pasty fatty substance" means fatty substances with a melting point ranging from 20 to 55°C and in particular from 25 to 45°C and/or a viscosity at 40°C ranging from 0.1 to 40 Pa.s (1 to 400 poises) and in particular from 0.5 to 25 Pa.s, measured using a Contraves TV or a Rheomat 80 viscometer, equipped with a spindle rotating at 60 Hz. A person skilled in the art may select the spindle for measuring the viscosity from the spindles MS-r3 and MS-r4, on the basis of his general knowledge, so as to be able to measure the viscosity of the pasty compound tested.

The melting point values correspond, according to the invention, to the melting peak measured by the "Differential Scanning Calorimetry" method with a temperature rise of 5 or lO°C/minute.

According to the invention, one or more pasty fatty substances are used. In particular, these fatty substances are hydrocarbon-based compounds (mainly containing carbon and hydrogen atoms and possibly ester groups), optionally of polymeric type; they may also be chosen from silicone and/or fluoro compounds; they may also be in the form of a mixture of hydrocarbon-based and/or silicone and/or fluoro compounds. In the case of a mixture of different pasty fatty substances, the hydrocarbon-based pasty compounds are preferably used in major proportion.

Among the pasty compounds that may be used in the composition according to the invention, mention may be made of lanolins and lanolin derivatives, for instance acetylated lanolins or oxypropylenated lanolins or isopropyl lanolate, with a viscosity of from 18 to 21 Pa.s and preferably 19 to 20.5 Pa.s, and/or a melting point of from 30 to 55°C, and mixtures thereof. Esters of fatty acids or of fatty alcohols may also be used, especially those containing 20 to 65 carbon atoms (melting point from about 20 to 35°C and/or viscosity at 4O⁰C ranging from 0.1 to 40 Pa.s), for instance triisostearyl citrate or cetyl citrate; arachidyl propionate; polyvinyl laurate; cholesterol esters, for instance triglycerides of plant origin such as hydrogenated plant oils, viscous polyesters, for instance poly(12-hydroxystearic acid), and mixtures thereof. Triglycerides of plant origin that may be used include hydrogenated castor oil derivatives, such as "Thixinr" from Rheox. Mention may also be made of silicone-based pasty fatty substances such as polydimethylsiloxanes (PDMS) with pendent chains of the alkyl or alkoxy type containing from 8 to 24 carbon atoms and having a melting point of 20-55°C, for instance stearyl dimethicones, especially those sold by the company Dow Corning under the trade names DC2503 and DC25514, and mixtures thereof. The pasty fatty substance(s) may be present in a proportion of from 0.5% to

60% by weight, relative to the total weight of the composition, in particular in a proportion of 2-45% by weight and more particularly in a proportion of 5-30% by weight in the composition.

Waxes At least one wax or a mixture of waxes such as those used to date in cosmetics may also be used in the composition of the invention.

For the purposes of the present invention, a wax is a lipophilic fatty compound, which is solid at room temperature (20-25°C) and atmospheric pressure (760 rnmHg), with a reversible solid/liquid change of state, which has a melting point of greater than 40⁰C, in particular greater than 45°C and better still greater than 50⁰C, which may be up to 200°C, and which has an anisotropic crystal organization in the solid state. The size of the crystals is such that the crystals scatter and/or diffuse light, giving the composition a more or less opaque cloudy appearance. By bringing the wax to its melting point, it is possible to make it miscible with the oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture to room temperature, recrystallization of the wax in the oils of the mixture is obtained. This recrystallization in the mixture may be responsible for the reduction in the gloss of said mixture. Thus, advantageously, the composition contains little or no conventional waxes, especially less than 20% by weight and better still less than 10% by weight of conventional wax relative to the total weight of the composition.

For the purposes of the patent application, the conventional waxes are those generally used in cosmetics and dermatology; they are especially of natural origin, for instance beeswax, carnauba wax, candelilla wax, ouricurry wax, Japan wax, cork fiber wax, sugarcane wax, paraffin wax, lignite wax, macrocrystalline waxes with a melting point > 55°C, lanolin wax, montan wax, ozokerites, and hydrogenated oils, for instance hydrogenated jojoba oil, but also of synthetic origin, for instance the polyethylene waxes derived from the polymerization of ethylene, and the waxes obtained by Fisher-Tropsch synthesis with a melting point > 55°C, hydrogenated oils, fatty acid esters and glycerides that are solid at 55°C, and silicone waxes, for instance alkyl, alkoxy and/or esters of poly(di)methylsiloxane that are solid at 55°C.

The waxes may be present in the form of stable dispersions of colloidal wax particles such that they may be prepared according to known methods, such as those of "Microemulsions Theory and Practice, L. M. Prince, published by Academic Press (1977, pages 21-32)". As wax that is liquid at room temperature, mention may be made of jojoba oil.

Aqueous phase The cosmetic compositions according to the invention may also comprise water or a mixture of water and of hydrophilic organic solvents, for instance linear or branched lower alcohols and especially monoalcohols containing from 2 to 5 carbon atoms, for instance ethanol, isopropanol or n-propanol, polyols, for instance glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols. The hydrophilic phase may also contain hydrophilic C₂ ethers and C₂-C₄ aldehydes. The aqueous phase may essentially be water.

The water or the mixture of water and of hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0 to 90% (especially 0.1% to 90%) by weight, in particular from 0 to 70% by weight (especially 0.1% to 70% by weight) and more particularly from 0 to 60% by weight (especially 0.1% to 60% by weight) relative to the total weight of the composition.

The composition may contain, for example, a continuous fatty phase that may contain less than 10% by weight of water, especially less than 5% by weight of water or even less than 1% by weight of water relative to its total weight. According to one particular embodiment, the composition according to the invention is in anhydrous form. For the purposes of the present invention, the term "anhydrous composition" means a composition comprising less than 5% by weight of water, in particular less than 2% and more particularly less than 1% by weight of water relative to the total weight of the composition.

Additives

The composition of the invention may also comprise any additive usually used in the field under consideration, chosen from dyestuffs that are soluble in the medium, antioxidants, essential oils, preserving agents, fragrances, neutralizers and surfactants, and mixtures thereof. These additives may be present in the composition in the amounts generally used in cosmetics and dermatology, and especially in a proportion of from 0.01% to 50% and better still from 0.1% to 20% of the total weight of the composition.

Needless to say, a person skilled in the art will take care to select the optional additional additives and/or the amount thereof such that the advantageous properties of the composition according to the invention, i.e. gloss, absence of tack, covering power and migration resistance in particular, are not, or are not substantially, adversely affected by the envisioned addition.

According to one embodiment, the composition according to the invention also contains at least one dyestuff.

According to another embodiment, the composition according to the invention also contains at least one dyestuff chosen from lipophilic dyes, hydrophilic dyes, pigments and nacres, and mixtures thereof.

Advantageously, the composition contains a dyestuff that may be chosen from the lipophilic dyes, hydrophilic dyes, pigments and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof. This dyestuff is generally present in a proportion of from 0.01% to 50% by weight, in particular from 0.5% to 40%, more particularly from 5% to 25%, especially from 0.01% to 20% and in particular from 0.1% to 10%, if it is present, relative to the total weight of the composition. According to one embodiment, the composition according to the invention comprises a dyestuff in a proportion of from 0.01% to 50% of the total weight of the composition.

The liposoluble 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 or quinoline yellow. They may represent from 0 to 20% (0.001 % to 20%) and better still from 0.1% to 6% of the weight of the composition (if present). The water-soluble dyes are, for example, beetroot juice and methylene blue, and may represent up to 6% of the total weight of the composition.

The pigments may be white or colored, mineral and/or organic, and coated or uncoated. Among the mineral pigments that may be mentioned are titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxide, and also iron oxides (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue. Among the organic pigments that may be mentioned are carbon black, pigments of D&C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminum. The pigments may represent from 0 to 50% (0.01% to 50%), preferably from 0.5% to 40% and better still from 2% to 25% of the total weight of the composition (if present).

The nacreous pigments (or nacres) may be chosen from white nacreous pigments such as mica coated especially with titanium or with bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica especially with ferric blue or with chromium oxide, titanium mica with an organic pigment of the abovementioned type, and also nacreous pigments based on bismuth oxychloride or interference pigments, especially liquid-crystal interference pigments or multilayer interference pigments. They may represent from 0 to 20% (0.05% to 20%) and better still from 0.1% to 15% of the total weight of the composition (if present).

According to one embodiment of the invention, the pigments and nacres are introduced into the composition in the form of a pigmentary paste.

The pigments may or may not be surface-coated, in particular surface-treated with silicones, amino acids, fluoro derivatives or any other substance that promotes the dispersion and compatibility of the pigment in the composition.

The composition according to the invention may also contain cosmetic, dermatological or hygiene active agents.

Among the cosmetic, dermatological or hygiene active agents that may be used in the compositions according to the invention, mention may be made of cosmetic oils, moisturizers, vitamins, essential fatty acids, sphingolipids, sunscreens, antioxidants, antiacne agents, anti-inflammatory agents, tanning agents (in the absence of UV), depigmenting agents and matting agents, and mixtures thereof. Among the moisturizers that may be mentioned are glycerol, polyglyceryl methacrylate, sodium hyaluronate and polyol or sugar esters. These active agents are used in an amount that is usual for those skilled in the art, and especially in concentrations of from 0.001% to 20% of the total weight of the composition. The compositions according to the invention may be manufactured via known processes generally used in cosmetics or dermatology. In particular, they may be manufactured according to a process that includes heating the mixture of the liquid fatty phase and of the semicrystalline polymer at least to its melting point, adding the nonpigmentary mineral and organic fillers and, where appropriate, the optional amphiphilic compound(s), dyestuffs that are soluble in the medium, pigmentary pastes and additives, and then mixing everything together until a solution is obtained. The homogeneous mixture obtained may then be cast in a suitable mold, for instance a lipstick mold, or directly into the packaging articles (especially a case or dish).

During the preparation of a cosmetic composition according to the invention, the nonpigmentary organic and mineral fillers may be introduced either directly in the form of a mixture, or one after the other, or in the form of a colloidal dispersion that may contain a nonpigmentary mineral or organic filler or a mixture of nonpigmentary mineral and/or organic fillers.

Advantageously, these nonpigmentary organic and mineral particles or fillers are introduced into the composition in the form of a colloidal dispersion, known as a "particulate paste", i.e. a concentrated colloidal dispersion of coated or uncoated solid fillers or particles, in a continuous medium, surface-stabilized with the aid of a dispersant or, optionally, without dispersant.

According to one particular embodiment, the nonfluid cosmetic composition in accordance with the present invention comprises at least one liquid fatty phase and contains, as semicrystalline polymer with (a) crystallizable side chain(s), a mixture of polystearyl acrylate and of polybehenyl acrylate, kaolin as nonpigmentary mineral filler, and, as nonpigmentary organic filler, a mixture of 12-hydroxystearic acid oligomer stearate and of ethylene glycol dimethacrylate/lauryl methacrylate copolymer.

The composition according to the invention may be in the form of a dermatological composition or a skincare and/or lipcare composition or in the form of an antisun composition, a facial care or body care composition or a body hygiene composition, especially in the form of a deodorant. More specifically, the compositions may be lip makeup products, but also care and/or treatment products for the skin, including the scalp, and the lips, for instance daily care creams, lip balms, lipsticks, lip glosses, lip pencils and antisun products for facial skin or the lips, skin makeup products for either the human face or body, for instance foundations cast especially in stick or dish form, concealer products, makeup rouges, skin coloring products and temporary tattoo products, body hygiene products, for instance deodorants, especially in stick form, and eye makeup products, for instance eyeliners, in particular in the form of pencils, mascaras, especially in the form of cakes, or eyeshadows.

Advantageously, the composition of the invention is in the form of a makeup product for keratin materials and more especially a lipstick. The invention is illustrated in greater detail in the examples that follow. The amounts are given as percentages by mass.

Examples of compositions

Example I: Lipstick formula Four compositions of lipstick type are prepared. The compositions corresponding to formula 2 or 4 are in accordance with the present invention.

The compositions prepared on the basis of formula 1 or 3 correspond to formulations of the prior art and were produced for comparative purposes.

Preparation of polybehenyl acrylate

120 g of hydrogenated polyisobutene are introduced into a 1 liter reactor equipped with a central paddle stirrer, a condenser and a thermometer, and are brought from room temperature to 80°C over 45 minutes. At 80⁰C, the mixture C₁ below is introduced over 2 hours:

- 40 g of cyclohexane + 4 g of Trigonox 141 [2,5-bis(2-ethylhexanoylperoxy)- 2,5-dimethylhexane] .

30 minutes after the start of addition of the mixture C₁, a mixture C₂ consisting of:

- 200 g of behenyl acrylate + 400 g of cyclohexane is introduced over 1 hour 30 minutes.

At the end of the two additions, the mixture is stirred for 3 hours at 80⁰C, and all of the cyclohexane present in the reaction medium is then distilled off at atmospheric pressure. The polymer is thus obtained at an active material concentration of 60% by weight in Parleam. Its weight-average molecular mass is from 17 000 to 27 000 and its m.p. is 58°C.

■ Preparation The semicrystalline polymers with (a) crystallizable side chain(s) are dissolved in a portion of the oil at 100⁰C, and the nonpigmentary mineral and organic oils are then added with a portion of the oily phase. The mixture is stirred using a magnetic bar for about 40 minutes, and then cast into lipstick molds. The lipsticks obtained with a comparative formulation (formula 1 or 3) show very mild exudation after exposure to room temperature (20-25⁰C) for 24 hours. The tubes of lipstick obtained with a formulation in accordance with the invention (formula 2 or 4) show good stability at 24 hours. The lipsticks were subsequently exposed for two months in an oven at 47°C. The tubes of lipstick corresponding to the comparative formulae show substantial exudation as drops over the entire stick, and also blisters and cracks. The lipstick wands made with a formulation in accordance with the invention show none of these impairments. The lipstick obtained is glossy, nontacky and migration-resistant. Example II: Lipstick formulations

Two compositions of lipstick type were prepared. Formulation B is a composition in accordance with the invention, whereas formulation A is a control composition.

Preparation

The lipsticks were prepared according to the procedure described in example I. After exposure for 24 hours to room temperature, the control lipstick shows exudation as a trickle and as large droplets on the stick.

In contrast, the tube of lipstick made with the formulation in accordance with the present invention, after exposure to room temperature for 24 hours, has a smooth glossy appearance, with no trace of exudation.

Claims

1. A nonfluid cosmetic composition comprising at least one liquid fatty phase and containing at least: - an effective amount of at least one semicrystalline polymer with (a) crystallizable side chain(s),

- a nonpigmentary mineral filler, and

- a nonpigmentary organic filler.

2. The composition as claimed in claim 1, characterized in that it comprises at least one low-melting semicrystalline polymer with (a) crystallizable side chain(s) with a melting point of less than 50°C, in particular within a range from 30⁰C to less than 50°C.

3. The composition as claimed in claim 1 or 2, characterized in that it comprises at least one high-melting semicrystalline polymer with (a) crystallizable side chain(s) with a melting point at least equal to or greater than 50°C, in particular within a range from 55 to 150°C and more particularly within a range from 60 to 13O⁰C.

4. The composition as claimed in any one of the preceding claims, characterized in that it comprises a mixture of at least one low-melting semicrystalline polymer with (a) crystallizable side chain(s) and at least one high-melting semicrystalline polymer with (a) crystallizable side chain(s).

5. The composition as claimed in claim 4, characterized in that the weight ratio of the high-melting semicrystalline polymer with (a) crystallizable side chain(s) and of the low-melting semicrystalline polymer with (a) crystallizable side chain(s) is in the range from 10/90 to 90/10 and in particular from 40/60 to 60/40.

6. The composition as claimed in any one of claims 2 to 5, characterized in that the low-melting semicrystalline polymer with (a) crystallizable side chain(s) is polystearyl acrylate.

7. The composition as claimed in any one of claims 3 to 5, characterized in that the high-melting semicrystalline polymer with (a) crystallizable side chain(s) is polybehenyl acrylate.

8. The composition as claimed in any one of the preceding claims, characterized in that the weight ratio between the nonpigmentary mineral filler and the nonpigmentary organic filler is in the range from 1:1 to 10:1, in particular from 2:1 to 6:1 and more particularly from 3:1 to 5:1.

9. The composition as claimed in any one of the preceding claims, characterized in that the nonpigmentary mineral filler is present in a proportion of from 0.1% to 15% by weight relative to the total weight of the composition, in particular from 1% to 10% and more particularly from 2% to 6% by weight relative to the total weight of the composition.

10. The composition as claimed in any one of the preceding claims, characterized in that the nonpigmentary organic filler is present in a proportion of from 0.01% to 5% by weight relative to the total weight of the composition, in particular from 0.1% to 3% and more particularly from 0.5% to 2% by weight relative to the total weight of the composition.

11. The composition as claimed in any one of the preceding claims, characterized in that the nonpigmentary mineral filler is chosen from the group comprising kaolin, silica and bentone, and mixtures thereof.

12. The composition as claimed in any one of the preceding claims, characterized in that the nonpigmentary organic filler is chosen from the group comprising Nylon^®, Polytrap, 12-hydroxystearic acid oligomer stearate and PMMA, and mixtures thereof.

13. The composition as claimed in any one of the preceding claims, characterized in that the liquid fatty phase is chosen from an oil of mineral, animal, plant or synthetic origin, and mixtures thereof.

14. The composition as claimed in any one of the preceding claims, characterized in that the liquid fatty phase is chosen from hydrogenated polyisobutene, triisocetyl citrate, isononyl isononanoate and octyldodecanol, and mixtures thereof.

15. The composition as claimed in any one of the preceding claims, characterized in that it also contains at least one dyestuff.

16. The composition as claimed in the preceding claim, characterized in that the dyestuff is chosen from lipophilic dyes, hydrophilic dyes, pigments and nacres, and mixtures thereof.

17. The composition as claimed in claim 15 or 16, characterized in that the dyestuff is present in a proportion of from 0.01% to 50% and in particular from 5% to 25% by weight relative to the total weight of the composition.

18. The composition as claimed in claim 16, characterized in that the pigments and nacres are introduced in the form of a pigmentary paste.

19. The composition as claimed in any one of the preceding claims, characterized in that it contains at least one solid fatty phase chosen from waxes, gums and pasty fatty substances, and mixtures thereof.

20. The composition as claimed in any one of the preceding claims, characterized in that it contains at least one additive chosen from antioxidants, essential oils, preserving agents, neutralizers, fragrances and surfactants, and mixtures thereof.

21. The composition as claimed in any one of the preceding claims, characterized in that the composition is in anhydrous form.

22. The composition as claimed in any one of the preceding claims, characterized in that it is in cast form.

23. The composition as claimed in any one of the preceding claims, characterized in that it is in the form of a mascara, an eyeliner, a foundation, a lipstick, a deodorant, a body makeup product, an eyeshadow, a makeup rouge or a concealer product.

24. A lipstick comprising at least one liquid fatty phase containing: - at least an effective amount of at least one semicrystalline polymer with (a) crystallizable side chain(s),

- at least one nonpigmentary mineral filler, and

- at least one nonpigmentary organic filler.

25. A cosmetic process for caring for, making up or treating the skin or the lips of the human face, comprising the application to the skin or the lips of the face of the cosmetic composition in accordance with any one of the preceding claims.

26. The cosmetic use of at least one nonpigmentary mineral filler and of at least one nonpigmentary organic filler in a cosmetic composition comprising a physiologically acceptable medium containing at least one liquid fatty phase structured with at least a sufficient amount of at least one semicrystalline polymer with (a) crystallizable side chain(s), and having improved stability with regard to exudation.