FR2846552A1 - Make-up composition comprising a structured fatty liquid phase, a dye, and a polyester oil, useful for application to keratinic materials particularly the lips - Google Patents

Abstract

Three component composition comprising a fatty liquid phase structured by an organic semi-crystalline polymer of melting point equal to or greater than 30 degrees C, a dye and an oil with at least two ester functions. The components form a physiologically acceptable medium.

Description

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The present invention relates to a composition, in particular a cosmetic composition, containing at least one semi-crystalline polymer and an oil comprising at least two ester functions, called "polyester oil", in particular in the form of a stick and the application of which leads to a bright and comfortable deposit.

The subject of the invention is a composition whose thermal stability is improved. This composition also allows the application to keratin materials of a shiny, non-sticky film, of good coverage and non-migrating.

It has been described in application FR-A1-0001004, the combination of a polyester oil and a heteroatom polymer of the polyamide type in compositions of lipstick without wax. This document does not teach that a polyester oil makes it possible to improve the thermal stability of the compositions on keratin materials.

Cosmetic compositions, the fatty phase of which is gelled by semi-crystalline polymers, have been described in application FR 0106047 not yet published. The lipstick formulas resulting from these inventions are in the form of a stick which deposits a shiny, non-sticky and covering film. However, these compositions have the disadvantage of being sensitive to changes in temperature. This results in poor stability when applying the sticks at a temperature higher than room temperature. The stick tends to crash.

US Patents 5,736,125 and US 5,156,911, as well as the application WO 01/19333 illustrate certain types of semi-crystalline polymers which can enter into the composition of the formulas of the invention. However, these documents do not describe cosmetic compositions and do not suggest that the addition of a particular polyester oil makes it possible to improve the stability of the compositions.

Surprisingly, the applicant has found that the addition of a polyester oil in a composition containing a semi-crystalline polymer makes it possible to improve the thermal stability of the composition.

 The invention applies in particular to makeup products for the lips but also for the eyes, such as the eyeliners, in particular in the form of a pencil, and the mascaras, in particular in the form of bread, or of the skin, such as foundations.

 More specifically, the subject of the invention is a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting point is greater than or equal to 30 C, b ) a coloring matter and c) a polyester oil, the liquid fatty phase, the coloring matter, the polyester oil and the polymer forming a physiologically acceptable medium.

 The melting temperature of the semi-crystalline polymer is preferably less than 150 C.

 The composition of the invention can be in the form of a paste, a solid, a cream.

 It can be an oil-in-water or water-in-oil emulsion, an anhydrous, solid or flexible gel. Preferably, it is in anhydrous form, and more especially in the form of anhydrous gel, in particular cast in stick or in a dish.

 By “semi-crystalline polymer” is meant within the meaning of the invention, polymers comprising a crystallizable part and an amorphous part in the skeleton and having a reversible first-order phase change temperature, in particular of melting

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 (solid-liquid transition). The crystallizable part is either a side chain (or pendant chain) or a sequence in the skeleton.

By "polymers" is meant within the meaning of the invention compounds comprising at least 2 repeating units, preferably at least 3 repeating units and more especially at least 10 repeating units.

When the crystallizable part is a sequence of the polymer backbone, this crystallizable sequence is of a chemical nature different from that of the amorphous sequences; in this case, the semi-crystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type. When the crystallizable part is a chain hanging from the skeleton, the semi-crystalline polymer can be a homopolymer or a copolymer.

By "organic compound" or "with an organic structure" is meant compounds containing carbon atoms and hydrogen atoms and optionally heteroatoms such as S, 0, N, P alone or in combination.

Semi-crystalline polymers Advantageously, the semi-crystalline polymer (s) of the composition of the invention comprise a weight-average molecular mass Mp ranging from 5,000 to 1,000,000, preferably from 10,000 to 800,000, preferably from 15,000 to 500,000.

The semi-crystalline polymer (s) according to the invention serving as a structuring agent are solids at room temperature (25 C) and atmospheric pressure (760 mm Hg), the melting point of which is greater than or equal to 30 C. melting point values correspond to the melting point measured using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name DSC 30 by the company
METTLER, with a temperature rise of 5 or 10 C per minute. (The melting point considered is the point corresponding to the temperature of the most endothermic peak of the thermogram).

 The semi-crystalline polymer or polymers according to the invention preferably have a melting temperature higher than the temperature of the keratinous support intended to receive said composition, in particular the skin or the lips.

 The semi-crystalline polymer (s) according to the invention are capable of structuring, alone or as a mixture, the composition without adding any particular surfactant, nor filler, nor wax.

 According to the invention, the semi-crystalline polymers are advantageously soluble in the fatty phase, in particular at least 1% by weight, at a temperature above their melting temperature. Apart from the crystallizable chains or sequences, the sequences of the polymers are amorphous.

 By "crystallizable chain or sequence" is meant within the meaning of the invention a chain or sequence which if it were alone would pass from the amorphous state to the crystalline state, reversibly, depending on whether one is above or below the melting temperature. A chain within the meaning of the invention is a group of atoms, pendant or lateral with respect to the polymer backbone. A sequence is a group of atoms belonging to the skeleton, a group constituting one of the repeating units of the polymer.

 Preferably, the polymer backbone of semi-crystalline polymers is soluble in the liquid fatty phase.

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 Preferably, the crystallizable blocks or chains of the semi-crystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%.

 The semi-crystalline polymers with crystallizable side chains are homo or copolymers. The semi-crystalline polymers of the invention with crystallizable blocks are copolymers, block or multiblock. They can be obtained by polymerization of monomer with reactive (or ethylenic) double bonds or by polycondensation. When the polymers of the invention are polymers with crystallizable side chains, the latter are advantageously in random or statistical form.

 Preferably, the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not have a polysaccharide backbone.

 The semi-crystalline polymers which can be used in the invention are in particular: - block copolymers of polyolefins with controlled crystallization, the monomers of which are described in EP-A-0 951 897.

 polycondensates and in particular of polyester, aliphatic or aromatic or aliphatic / aromatic type, - homo- or co-polymers carrying at least one crystallizable side chain and homo- or co-polymers carrying in the skeleton at least one crystallizable block, like those described in document US-A-5,156,911, - homo- or co-polymers carrying at least one crystallizable side chain in particular with fluorinated group (s), as described in document WO-A -01/19333, - and mixtures thereof. In the latter two cases, the side chain (s) or crystallizable blocks are hydrophobic.

A) Semi-crystalline polymers with crystallizable side chains
Mention may be made in particular of those defined in documents US-A-5,156,911 and WO-A-
01/19333.

 . These are homopolymers or copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers carrying a hydrophobic crystallizable side chain.

 . These homo- or co-polymers are of any kind as long as they have the conditions indicated below with in particular the characteristic of being soluble or dispersible in the liquid fatty phase, by heating above their melting point. Pf. They can result:. of the polymerization, in particular radical, of one or more monomers with reactive or ethylenic double bond (s) with respect to a polymerization, namely with a vinyl, (meth) acrylic or allyl group.

 . polycondensation of one or more monomers carrying co-reactive groups (carboxylic or sulfonic acid, alcohol, amine or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas, polyamides. a) In general, the crystallizable units (chains or sequences) of the semi-crystalline polymers according to the invention come from monomer (s) with crystallizable block (s) or chain (s), used for the production of semi-crystalline polymers. These polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one monomer with crystallizable chain (s) which can be represented by formula X:

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- M - avec M représentant un atome du squelette polymérique 1 S représentant un espaceur S C représentant un groupe cristallisable C Les chaînes -S-C cristallisables peuvent être aliphatiques ou aromatiques, éventuellement fluorées ou perfluorées. S représente notamment un groupe (CH2)n ou (CH2CH20)n ou (CH20), linéaire ou ramifié ou cyclique, avec n entier allant de 0 à 22. De préférence S est un groupe linéaire. De préférence, S et C sont différents.

- M - with M representing an atom of the polymer backbone 1 S representing a spacer SC representing a crystallizable group C The crystallizable -SC chains can be aliphatic or aromatic, optionally fluorinated or perfluorinated. S represents in particular a group (CH2) n or (CH2CH20) n or (CH20), linear or branched or cyclic, with n integer ranging from 0 to 22. Preferably S is a linear group. Preferably, S and C are different.

When the crystallizable chains are aliphatic hydrocarbon chains, they comprise alkyl hydrocarbon chains with at least 11 carbon atoms and at most 40 carbon atoms and better still at most 24 carbon atoms. These are in particular aliphatic chains or alkyl chains having at least 12 carbon atoms and preferably, they are C14-C24, preferably C16-C22 alkyl chains. When they are alkyl chains fluorinated or perfluorinated, they contain at least 11 carbon atoms of which at least 6 carbon atoms are fluorinated.

As an example of homopolymers or semi-crystalline copolymers with crystallizable chain (s), mention may be made of those resulting from the polymerization of one or more of the following monomers: alkyl (meth) acrylates saturated with the alkyl group in C14C24, perfluoroalkyl (meth) acrylates with a C11-C15 perfluoro alkyl group, N-alkyl (meth) acrylamides with C14 to C24 alkyl group with or without fluorine atom, vinyl esters with alkyl chains or perfluoro (alkyl) with the C14 to C24 alkyl group (with at least 6 fluorine atoms for a perfluoro alkyl chain), vinyl ethers with alkyl chains or perfluoro (alkyl) with the C14 to C24 alkyl group and at least 6 fluorine atoms for a perfluoro alkyl chain, C14 to C24 alpha-olefins such as, for example, octadecene, para-alkyl styrenes with an alkyl group comprising from 12 to 24 carbon atoms, their mixtures.

When the polymers result from a polycondensation, the crystallizable hydrocarbon and / or fluorinated chains as defined above, are carried by a monomer which can be a diacid, a diol, a diamine, a di-isocyanate.

When the polymers which are the subject of the invention are copolymers, they contain, in addition, from 0 to 50% of groups Y or Z resulting from the copolymerization: a) of Y which is a polar or non-polar monomer or a mixture of the two :. When Y is a polar monomer, it is either a monomer carrying polyoxyalkylenated groups (in particular oxyethylenated and / or oxypropylenated), a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, (meth) acrylamide, an N - alkyl (meth) acrylamide, an NN-dialkyl (meth) acrylamide such as for example NN-diisopropylacrylamide or N-vinyl-pyrolidone (NVP), N-vinyl caprolactam, a monomer carrying at least one carboxylic acid group such as (meth) acrylic, crotonic, itaconic, maleic, fumaric acids or carrying a carboxylic acid anhydride group such as maleic anhydride, and their mixtures.

 . When Y is a non-polar monomer it may be an ester of the branched or cyclic linear (meth) acrylate type, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted by an alkyl group. in C1 to C10, such as [alpha] - methylstyrene, a macromonomer of the polyorganosiloxane type with vinyl unsaturation.

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By "alkyl" is meant in the sense of the invention a saturated group in particular C8 to C24, unless expressly mentioned.

ss) 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 semi-crystalline polymers with a crystallizable side chain are homopolymers of alkyl (meth) acrylate or of alkyl (meth) acrylamide with an alkyl group as defined above, and in particular in C14-C24, copolymers of these monomers with a hydrophilic monomer preferably of a different nature from (meth) acrylic acid such as N-vinylpyrrolidone or hydroxyethyl (meth) acrylate and their mixtures.

 B) Polymers carrying at least one crystallizable block in the backbone These are also polymers which are soluble or dispersible in the liquid fatty phase by heating above their melting point Pf. These polymers are in particular block copolymers consisting of at least two sequences of different chemical nature, one of which is crystallizable.

- The polymers defined in US Pat. No. 5,156,911 can be used, - Block copolymers of olefin or of cycloolefin with a crystallizable chain such as those resulting from the block polymerization of: cyclobutene, cyclohexene, cyclooctene, norbornene (i.e. bicyclo (2,2,1) heptene-2), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethyl norbornene , 5-ethylidene-norbornene, 5-phenyl-norbonene, 5-benzylnorbornene, 5-vinyl norbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8a-octahydronaphthalene, dicyclopentadiene or their mixtures,. with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-
1-pentene, 1-octene, 1-decene, 1-eicosene or their mixtures,. and in particular the copoly (ethylene / norbornene) blocks and the terpolymers (ethylene / propylene / ethylidene-norbornene), blocks. It is also possible to use those resulting from the block copolymerization of at least 2 α-olefins in C2-C16 and better in C2-C12 such as those mentioned above and in particular the block bipolymers of ethylene and 1-octene.

 - The copolymers can be copolymers having at least one crystallizable block, the rest of the copolymer being amorphous (at room temperature). These copolymers can, moreover, have two crystallizable blocks of different chemical nature. The preferred copolymers are those which have both at room temperature a crystallizable block and an amorphous block which is both hydrophobic and lipophilic, distributed sequentially; mention may, for example, be made of polymers having one of the crystallizable blocks and one of the following amorphous blocks:. Sequence crystallizable by nature: a) polyester such as poly (alkylene terephthalate), b) polyolefin such as polyethylenes or polypropylenes.

 . Amorphous and lipophilic sequence such as: amorphous polyolefins or copoly (olefin) such as poly (isobutylene), hydrogenated polybutadiene, hydrogenated poly (isoprene).

 As examples of such copolymers with crystallizable block and with amorphous block, there may be mentioned: a) poly (# - caprolactone) -b-poly (butadiene) block copolymers, preferably used hydrogenated, such as those described in article D6 "Melting behavior of poly (-

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 caprolactone) -block-polybutadiene copolymers "from S. Nojima, Macromolecules, 32.3727-3734 (1999).

 P) block copolymers poly (butyleneterephthalate) -b-poly (isoprene) hydrogenated block or multiblock, cited in article D7 "Study of morphological and mechanical properties of PP / PBT" by B. Boutevin et al., Polymer Bulletin, 34, 117-123 (1995). y) poly (ethylene) -b-copoly (ethylene / propylene) block copolymers cited in articles D8 "Morphology of semi-crystalline block copolymers of ethylene- (ethylene-altpropylene)" by P. Rangarajan et al., Macromolecules, 26,4640-4645 (1993) and D9 "Polymer agregates with crystalline cores: the system poly (ethylene) -poly (ethylenepropylene)" P. Richter et al., Macromolecules, 30,1053-1068 (1997).

8) the poly (ethylene) -b-poly (ethylethylene) block copolymers mentioned in general article D10 "Crystallization in block copolymers" by I.W. Hamley, Advances in Polymer Science, vol 148, 113-137 (1999).

The semi-crystalline polymers of the composition of the invention may or may not be crosslinked in part as long as the crosslinking rate does not hinder their dissolution or dispersion in the liquid fatty phase by heating above their melting temperature. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It can also be a physical crosslinking which can then be due either to the establishment of hydrogen or dipolar type bonds between groups carried by the polymer such as for example the dipolar interactions between carboxylate ionomers, these interactions being in small quantity and carried by the polymer backbone; or a phase separation between the crystallizable blocks and the amorphous blocks, carried by the polymer.

 Preferably, the semi-crystalline polymers of the composition according to the invention are non-crosslinked.

 As a particular example of a structuring semi-crystalline polymer which can be used in the composition according to the invention, mention may be made of the Intelimer products 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 carry crystallizable side chains and have the above formula X.

Mixture of semi-crystalline polymer with high melting point and semi-crystalline polymer with low melting point
In the following description, the semi-crystalline polymer (s) having a melting point Pf2 lower than 50 C will be called "low melting point polymers" and the crystalline or semi-crystalline compound (s) having a melting point Pf1 greater than or equal to 50 C will be referred to as "high melting point compounds". According to the invention, the melting point can be measured in particular by any known method and in particular with a differential scanning calorimeter (DSC).

 The composition advantageously contains a mixture of a polymer chosen from polymers with a low melting point having a melting temperature below 50 C, and a polymer chosen from polymers with a high melting point having a melting temperature at least equal to 50 C.

 According to the invention, the semi-crystalline compound (s) with a high melting point are advantageously polymers having a melting temperature Pf1 such that 50 C <Pf1

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 # 150 C, better 55 C Pf1 # 150 C, and preferably 60 C Pf1 # 130 C and polymers with a low melting point advantageously have a melting temperature Pf2 such that 30 C Pf2 <50 C, and better 35 C Pf2 45 C. This melting temperature is a first order state change temperature.

In general, polymers with a low melting point have a melting point Pf2 at least equal to the temperature of the keratinous support which is to receive the composition according to the invention.

As compound with high melting point which can be used in the invention, mention may be made of high melting point waxes such as certain polyethylene waxes such as Epolene N-14 sold by Eastman Chemical Co., Carnauba waxes and certain microcrystalline waxes like those sold by Tisco under the brand "Tisco wax 88", as well as semi-crystalline polymers with high melting point. Preferably, the high melting compound is a second organic solid semi-crystalline polymer with high melting point. It is however possible to use, as a compound with a high melting point, crystalline polymers, solid at room temperature and having a melting temperature above 50 ° C., random polymers comprising controlled crystallization, as described in document EP-A- 0 951 897 and more specifically the commercial products Engage 8 401 and Engage 8 402 from Dupont de Nemours, with a melting temperature of 51 C and 64 C respectively and which are random ethylene / 1-octene bipolymers. i) The semi-crystalline polymers whose melting point is less than 50 ° C. are in particular those described in examples 3,4, 5,7, 9 of patent US-A-5,156,911 with a COOH group, resulting from the copolymerization of acrylic acid and C5 to C16 alkyl (meth) acrylate with a melting temperature ranging from 20 C to 35 C and more particularly of the copolymerization:. of acrylic acid, hexadecylacrylate and isodecylacrylate in a 1/16/3 ratio,. of acrylic acid and pentadecylacrylate in a ratio 1/19,. acrylic acid, hexadecylacrylate, ethylacrylate in a ratio 2.5 / 76.5 / 20,. of acrylic acid, hexadecylacrylate and methylacrylate in a 5/85/10 ratio,. acrylic acid, polyoctadecylmethacrylate in a ratio 2.5 / 97.5.

 One can also use the polymer Structure 0 from National Starch such as that described in the document US-A-5,736,125 with a melting point of 44 C as well as semi-crystalline polymers with crystallizable pendant chains comprising fluorinated groups as described in examples 1,4, 6,7 and 8 of document WO-A-01/19333.

 It is also possible to use the semi-crystalline polymers of low melting point obtained by copolymerization of stearyl acrylate and acrylic acid or NVP as described in document US-A-5,519,063 or EP-A-550,745 and more especially those described in Examples 1 and 2, below, of polymer preparation. ii) The semi-crystalline polymers having a melting point greater than or equal to 50 C are in particular the Intelimer described in the brochure "Intelimer polymers", Landec IP22 (Rev. 4-97) with a melting temperature of 56 C, which is a viscous product at room temperature, waterproof, non-sticky.

 It is also possible to use the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and acrylic acid or NVP, as described in the

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 documents US-A-5,519,063 and EP-A-055 0745 and more particularly those described in Examples 3 and 4, below, of polymer preparation.

Preferably, the semi-crystalline polymers with a low melting point and / or those with a high melting point do not contain a carboxylic group.

According to the invention and advantageously, the compound with high melting point (crystalline or semi-crystalline) and that with low melting point are in a weight ratio ranging from 10/90 to 90/10 and better still 40 / 60 to 60/40, more preferably in a weight ratio close to 50/50.

Advantageously, the weight ratio of semi-crystalline polymer with organic structure relative to the liquid fatty phase is from 0.20 to 0.60 and better still from 0.25 to 0.50, obtaining a hard stick which disintegrates at skin or lip contact and in particular of hardness ranging from 100 to 350 gf.

The gelation of the fatty phase is adjustable according to the nature of the polymer (s) and their respective concentrations and can be such that a rigid structure is obtained in the form of a stick or a stick.

The level of each polymer is chosen according to the hardness of the desired composition and according to the particular application envisaged. The respective amounts of polymer may be such that they enable a disintegrable solid to be obtained, in particular having a hardness ranging from 100 to 350 gf. This hardness can be measured by the so-called "butter cutting wire" method, which consists of cutting a stick of lipstick 12.7 mm in diameter and measuring the hardness at 20 C, using a dynamometer.
DFGHS 2 from the company Indelco-Chatillon moving at a speed of 100mm / minute.

 It is expressed as the shear force (expressed in gram-force) necessary to cut a stick under these conditions.

 This hardness is such that the composition is self-supporting and can disintegrate easily to form a satisfactory deposit on the skin and the lips. In addition, with this hardness, the composition of the invention in cast form, in particular in stick form, withstands impact well.

 Preferably, the composition of the invention is in the form of a solid stick, of hardness ranging from 100 gf to 350 gf, measured according to the "butter cutting wire" method. It is however possible to use an amount of semi-crystalline polymer such that the composition is in the form of a flexible paste which can be applied with the finger or with the aid of an applicator on keratin materials.

 In practice, the total amount of semi-crystalline polymer (s) represents from 0.1 to 80% of the total weight of the composition and better still from 0.5 to 40% and even better still from 3 to 30%. Preferably, it represents from 15% to 25% by weight of the composition.

 The sticks or sticks according to the invention make it possible, after application, to obtain a glossy deposit, uniform in color, non-sticky, with good coverage (that is to say that the skin or the lips do not appear under the makeup).

Polyester oil
The oil comprising at least two functions ester a fatty substance liquid at room temperature (25 C) and atmospheric pressure (760 mm Hg). It is preferably chosen from:

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 - hydrocarbon oils with a high triglyceride content consisting of fatty acid esters (C4 to C24) and glycerol, the fatty acids of which can have varied chain lengths, the latter being linear or branched, saturated or unsaturated; these oils are in particular glyceryl triheptanoate, glyceryl trioctanoate; oils of wheat germ, corn, sunflower, shea, castor, sweet almonds, macadamia, apricot, soy, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grape or blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, bancoulier, passionflower, muscat rose; or the triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; - di-isostearyl malate; tri-isocetyl citrate; tridecyl trimellitate - polyol esters, such as propylene glycol dioctanoate, neopentylglycol diheptanoate, diethylene glycol diisononanoate.

- pentaerythritol esters, such as pentaerythrityl tetraisostearate.

- and their mixtures.

The polyester oil preferably represents 5 to 30%, preferably 10 to 20% by weight of the composition.

The weight ratio of polyester oil relative to the semi-crystalline polymer is advantageously between 0.2 and 1.1, preferably between 0.4 and 0.9.

The liquid fatty phase By “liquid fatty phase”, in the sense of the request, one understands a fatty phase liquid at ambient temperature (25 C) and atmospheric pressure (760 mm of Hg), composed of one or more fatty fatty liquids room temperature, also called oils, compatible with each other. This fatty phase is macroscopically homogeneous.

Advantageously, the liquid fatty phase, structured by the semi-crystalline polymers, constitutes the continuous phase of the composition. This fatty phase can contain one or more non-polar oils or a mixture of non-polar oil (s) and polar oil (s), different from the polyester oil described above.

The apolar oils according to the invention are in particular silicone oils such as polydimethylsiloxanes (PDMS), linear or cyclic, liquid at room temperature; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, pendant and / or at the end of the silicone chain, groups having 2 to 24 carbon atoms, liquid at room temperature; phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates, liquids; linear or branched hydrocarbons or fluorocarbons of synthetic or mineral origin, liquids, such as paraffin oils and their derivatives, petrolatum, polydecenes, hydrogenated polyisobutene such as Parlam sold by the company Nippon Oil Fats, squalane; their mixtures. Preferably, the nonpolar oils used are nonpolar oils of the hydrocarbon type, liquids, of mineral or synthetic origin, chosen in particular from Parleam oil (hydrogenated isoparaffin), isoparaffins, squalane and their mixtures.

 Advantageously, the liquid fatty phase contains at least one polar oil and at least one slightly polar oil, such as isononyl isononanonoate.

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In particular, the polar oils of the invention are: - hydrocarbon vegetable oils with a high triglyceride content consisting of fatty acid esters (C8 to C24) and glycerol, the fatty acids of which can have various chain lengths , the latter may be linear or branched, saturated or unsaturated; these oils are in particular the oils of wheat germ, corn, sunflower, shea, castor, sweet almonds, macadamia, apricot, soy, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grape or blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, and nutmeg , passionflower, muscat rose; or the triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; - synthetic oils of formula R5COOR6 in which R5 represents the remainder of a linear or branched higher fatty acid containing from 7 to 40 carbon atoms and R6 represents a branched hydrocarbon chain containing from 3 to 40 carbon atoms such as for example l 'Purcellin oil (ketostearyl octanoate), isononyl isononanoate, C12 to C15 alcohol benzoate; - synthetic esters and ethers such as isopropyl myristate, ethyl 2-hexyl palmitate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, hydroxylated esters such as isostearyl lactate, malate of di-isostearyl; and pentaerythritol esters; - fatty acids having from 12 to 22 carbon atoms such as oleic, linoleic or linolenic acid; - their mixtures.

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

The coloring matter
Advantageously, the composition contains a coloring material which can be chosen from lipophilic dyes, hydrophilic dyes, pigments and nacres usually used in cosmetic or dermatological compositions, and mixtures thereof. This coloring material is generally present in an amount of 0.01 to 50% (in dry matter) of the total weight of the composition, preferably from 5 to 30% (if present).

The liposoluble dyes are for example Sudan red, D & C Red 17, D & C
Green 6, (3-carotene, soybean oil, Sudan brown, D & C Yellow 11, D & C Violet
2, D & C orange 5, quinoline yellow, annatto. They can represent from 0 to 20% of the weight of the composition and better still from 0.01 to 6% (if present). The water-soluble dyes are for example beet juice, methylene blue and can represent up to
6% of the total weight of the composition.

 The pigments can be white or colored, mineral and / or organic, coated or not.

Mention may be made, among the mineral pigments, of titanium or zinc dioxide, optionally surface-treated, zirconium or cerium oxides, as well as iron or chromium oxides, manganese violet, ultramarine blue, l hydrate of chromium and ferric blue. Among the organic pigments, mention may be made of carbon black, pigments of the D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum (such as D & C red 27, 21 , 7, D & C yellow 5, 6, FD &
C blue n 1). The pigments can represent from 0 to 40% (0.01 to 40%) in particular of
0.5 to 35% and better still 2 to 25% of the total weight of the composition (if present).

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 Conventional waxes, in the sense of demand, are those generally used in the cosmetic and dermatological fields; they are in particular of natural origin such as beeswax, Candellila, Ouricoury, Japan, cork fibers or sugar cane, paraffin waxes, lignite, microcrystalline waxes of melting point> 50 C, lanolin wax, Montan wax, ozokerites, hydrogenated oils such as hydrogenated jojoba oil, but also of synthetic origin such as polyethylene waxes resulting from the polymerization of ethylene and the waxes obtained by synthesis of FischerTropsch at melting point> 50 C, fatty acid esters and concrete glycerides at 50 C, silicone waxes such as alkyl, alkoxy and / or poly (di) methylsiloxane esters at 50 C.

Advantageously, the composition of the invention contains little or no "mattifying" fillers and in particular less than 5% of mattifying filler. This is particularly the case when it is desired to obtain a shiny deposit on keratin materials such as the lips, the eyelashes and the hair. On the contrary, for a foundation, this type of filler can be used. A mattifying filler is generally a filler which absorbs sweat and / or sebum from the skin such as silicas, talcs, clays, kaolins, polyamide powders (Nylon @).

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

The subject of the invention is also a cosmetic process for caring for, making up or treating keratin materials of human beings and in particular of the skin, facial lips and integuments of human beings, comprising the application to keratin materials of the composition, in particular cosmetic, as defined above.

 Another subject of the invention is the use of an oil comprising at least two ester functions, in a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose temperature melting point is greater than or equal to 30 C, and b) a coloring matter, the liquid fatty phase, the coloring matter, the polyester oil and the polymer forming a physiologically acceptable medium.

 Another subject of the invention is the use of a sufficient quantity of a polyester oil, in a cosmetic composition containing a physiologically acceptable medium comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with structure organic, the melting point of which is greater than or equal to 30 C, and b) a coloring material, as stabilizing agent for said composition, said composition depositing on the keratin materials, and in particular the lips, a shiny and comfortable film.

 Another subject of the invention is the use of a polyester oil in a makeup composition containing a physiologically acceptable medium comprising at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, to obtain a cosmetic composition. stable.

 The invention is illustrated in more detail in the following examples. The quantities are given in percentage by mass.

1) Examples of manufacturing semi-crystalline polymers
Example 1 Homopolymer with a Melting Point of 48 C

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 120 g of Parleam are introduced into a reactor with a central agitation with an anchor, a condenser and a thermometer, which are heated from room temperature to 80 ° C. in 45 min. At 80 ° C., the following mixture Ci is introduced over 2 hours: 40 g of cyclohexane + 4 g of Trigonox 141 [2.5 bis (2-ethyl hexanoyl peroxy) - 2.5 dimethyl hexane].

30 min after the start of the pouring of the mixture C1, the mixture C2, consisting of: 200 g of stearyl acrylate + 400 g of cyclohexane, is introduced in 1 h 30 min.

At the end of the two flows, the mixture is left to act for an additional 3 hours at 80 ° C. and then all of the cyclohexane present in the reaction medium is distilled at atmospheric pressure.

The polymer is then obtained at 60% by weight of active material in the Parléam.

Its weight average molecular weight is around 20,000-30,000 and its melting temperature Tf is 48 C, measured by D.S.C.

Example 2: Copolymer with a melting point of 48 ° C. The same procedure is applied as in example 1, except that a mixture of 10 g of N-Vinyl Pyrrolidone and 190 g of stearyl acrylate is used.

The polymer obtained is 60% by weight of active material in Parleam, its weight average molecular weight is 43,000-53,000 and its Tf is 48 C.

Example 3: Homopolymer with a melting point of 58 C The same procedure is applied as in Example 1, except that behenyl acrylate is used in place of stearyl acrylate. The polymer obtained is 60% by weight of active material in Parléam. Its weight average molecular mass is 17,000-27,000 and its Tf is 58 C.

Example 4 Copolymer of Melting Point of 58 C
The same procedure is applied as in Example 2, except that behenyl acrylate is used in place of stearyl acrylate. The polymer obtained is
60% by weight of active ingredient in Parléam. Its weight average molecular mass is 23,500-33,500 and its Tf is 58 C.

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II) Examples of composition Example 5: Lipstick formula
Percentage by weight Octyldodecanol 14.5 Diisostearyl malate 9.5 Polyhydroxystearic acid 2 Hydrogenated coco-glycerides 2 Low melting point polymer according to example 1 11 High melting point polymer according to example 3 11 Pigments 9 Filler 1 Nacre 3 Isononanoate d 'isononyle qs 100 Example 6: Lipstick formula Low melting point polymer according to Example 1 11% Low melting point polymer according to Example 3 11% Pigments 8.66% Isoparaffin hydrogenated 49.34% Solsperse 21000 2 % Di-isostearylmalate 14.8% nylon 3% perfume 0.2% This Lipstick formula, which contains 14.8% di-isostearylmalate which is a polyester type oil, is stable for 2 months at 47 C
Counter Example of Example 6
Low melting point polymer according to Example 1 11%
Low melting point polymer according to Example 3 11%
Pigments 8.66%
Hydrogenated isoparaffin 49.34%
Solsperse 21000 2%
Isononyl isononanoate 14.8% nylon 3% 0.2% perfume
This lipstick formula has a very slight shrinkage after 2 months at 47 ° C as well as traces of streaks on the appearance of the sticks.

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Example 7 Low melting point polymer according to Example 1 11% Low melting point polymer according to Example 3 11%
Pigments 8.66% Hydrogenated isoparaffin 9.34% Solsperse 21000 2% Octyldodecanol 10% Di-isostearyl malate 20% squalane 22.80% Peanut propionate 2% nylon 3% perfume 0.2% This Lipstick formula presents very good thermal stability

Claims (34)

 CLAIMS 1. Make-up composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting point is greater than or equal to 30 C, b) a coloring matter and c) an oil comprising at least two ester functions, the liquid fatty phase, the coloring matter, the polyester oil and the polymer forming a physiologically acceptable medium. 2. Composition according to claim 1, characterized in that the polyester oil is chosen from - hydrocarbon oils with a high triglyceride content consisting of fatty acid esters (C4 to C24) and glycerol whose fatty acids can have varied chain lengths, which can be linear or branched, saturated or unsaturated; these oils are in particular glyceryl triheptanoate, glyceryl trioctanoate; oils of wheat germ, corn, sunflower, shea, castor, sweet almonds, macadamia, apricot, soy, rapeseed, cotton, alfalfa, poppy, pumpkin, sesame, squash, avocado, hazelnut, grape or blackcurrant seed, evening primrose, millet, barley, quinoa, olive, rye, safflower, bancoulier, passionflower, muscat rose; or the triglycerides of caprylic / capric acids such as those sold by the company Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel; - di-isostearyl malate; tri-isocetyl citrate; tridecyl trimellitate - polyol esters, such as propylene glycol dioctanoate, neopentylglycol diheptanoate, diethylene glycol diisononanoate. - pentaerythritol esters, such as pentaerythrityl tetraisostearate. - and their mixtures.  3. Composition according to claim 1, characterized in that the polyester oil is chosen from di-isostearyl malate, tri-isocetyl citrate, tridecyl trimellitate, glyceryl triheptanoate and mixtures thereof.  4. Composition according to one of the preceding claims, characterized in that the polyester oil represents 5 to 30% by weight of the composition.  5. Composition according to one of the preceding claims, in which the polyester oil represents 10 to 20% by weight of the composition.  6. Composition according to one of the preceding claims, characterized in that the weight ratio of polyester oil relative to the semi-crystalline polymer is between 0.2 and 1.1, preferably between 0.4 and 0.9.  7. Composition according to any one of the preceding claims, in which the semi-crystalline polymer has a weight-average molecular mass ranging from 5,000 to 1 000,000, preferably 10,000 to 800,000, preferably 15,000 to 500,000. <Desc / Clms Page number 17> 8. Composition according to any one of the preceding claims, characterized in that the semi-crystalline polymer is soluble in the liquid fatty phase at a temperature above its melting temperature. 9. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer has a melting temperature higher than the temperature of the keratinous support intended to receive said composition. 10. Composition according to the preceding claim, characterized in that the support intended to receive the composition is the skin or the lips. 11. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from: - block copolymers of polyolefins with controlled crystallization, - aliphatic or aromatic polyester polycondensates and aliphatic / aromatic copolyesters, - homo- or co-polymers carrying at least one crystallizable side chain, - mixtures thereof. 12. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers and copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers carrying the chain (s ) hydrophobic crystallizable side (s). 13. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers and copolymers resulting from the polymerization of at least one monomer with crystallizable chain (s) of formula X:

 #M # with M representing an atom of the polymer backbone 1 S representing a spacer S C representing a crystallizable group C and their mixtures, with S-C representing an alkyl chain containing at least 11 carbon atoms, optionally fluorinated or perfluorinated. 14. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from polymers resulting from the polymerization of at least one monomer chosen from acrylic, methacrylic, crotonic, itaconic, maleic acid, maleic anhydride and mixtures thereof. 15. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is chosen from homopolymers and copolymers resulting from the polymerization of at least one monomer with a crystallizable chain chosen from alkyl (meth) acrylates C14-C24 saturated, C11C15 perfluoroalkyl (meth) acrylates, C14 to C24 N alkyl (meth) acrylamides with or without fluorine atom, vinyl esters with C14 to C24 alkyl or perfluoroalkyl chains, vinyl ethers with C14 to C24 alkyl or perfluoroalkyl chains, C14 to C24 alpha-olefins, para-alkyl styrenes with an alkyl group containing from 12 to 24 carbon atoms, their mixtures. 16. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymers are homopolymers of alkyl (meth) acrylate or <Desc / Clms Page number 18>  of (meth) acrylamide with a C14 to C24 alkyl group, copolymers of these monomers with a hydrophilic monomer.  17. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymers are copolymers of alkyl (meth) acrylate or of alkyl. (Meth) acrylamide with a C14 to C24 alkyl group with a monomer different in nature from (meth) acrylic acid such as N-vinylpyrolidone or hydroxyethyl (meth) acrylate, and mixtures thereof.  18. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer (s) represent from 0.1 to 80% of the total weight of the composition and better still from 0.5 to 40% and even better still from 3 to 30%, preferably from 15% to 25% by weight of the composition.  19. Composition according to one of the preceding claims, characterized in that the composition contains a mixture of a polymer chosen from polymers with a low melting point having a melting temperature below 50 C, and a polymer chosen from polymers with a high melting point having a melting temperature of at least 50 C.  20. Composition according to the preceding claim, characterized in that the polymer with a high melting point has a melting temperature Pf1 such that 55 C # Pf1 # 150 C and preferably 60 C <Pf1 # 130 C.  21. Composition according to claim 21 or 22, characterized in that the polymer with low melting point has a melting temperature Pf2 such that 30 C # Pf2 <50 C.  22. Composition according to one of the preceding claims, characterized in that the semi-crystalline polymer is a mixture of a polymer with low melting point having a melting temperature below 50 C, and a polymer with high point with a melting temperature of at least 50 C, in a weight ratio between 90/10 and 10/90, preferably between 40/60 and 60/40, more preferably in a weight ratio close to 50/50.  23. Composition according to one of the preceding claims, characterized in that the fatty phase contains at least one polar oil, and a slightly polar oil.  24. Composition according to one of the preceding claims, characterized in that the weight ratio of the semi-crystalline polymer and of the liquid fatty phase is between 0.20 and 0.60, preferably between 0.25 and 0.50.  25. Composition according to one of the preceding claims, characterized in that it contains less than 10%, by weight, of wax and / or less than 5% by weight of mattifying filler, relative to the total weight of the composition.  26. Composition according to one of the preceding claims, characterized in that the composition is in anhydrous form.  27. Composition according to any one of the preceding claims, characterized in that it is in cast form.  28. Composition according to any one of the preceding claims, characterized in that it is in the form of mascara, eyeliner, foundation, rouge à <Desc / Clms Page number 19>  lips, deodorant, body makeup product, eyeshadow or blush, concealer. 29. Composition according to claim 28, characterized in that it is in the form of a solid stick, of hardness ranging from 100 to 350 gf. 30. Lipstick comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting temperature Pf1 is such as 55 C Pf1 # 150 C, and at least one semi-crystalline polymer with an organic structure whose melting point Pf2 is such that 30 C <Pf2 <50 C b) a coloring matter and c) a polyester oil. 31. Cosmetic make-up method comprising the application to keratin materials of the composition according to one of claims 1 to 30. 32. Cosmetic use of a polyester oil, in a makeup composition comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure whose melting point is greater than or equal to 30 C, b ) a coloring matter, the liquid fatty phase, the coloring matter, the polyester oil and the polymer forming a physiologically acceptable medium. 33. Cosmetic use of a sufficient amount of a polyester oil, in a cosmetic composition containing a physiologically acceptable medium comprising a) at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, the temperature of which fusion is greater than or equal to 30 C, and b) a coloring material, as thermal stabilizing agent for said composition, said composition depositing on the keratin materials, and in particular the lips, a shiny and comfortable film.  34. Cosmetic use of a polyester oil in a makeup composition containing a physiologically acceptable medium comprising at least one liquid fatty phase structured by at least one semi-crystalline polymer with organic structure, in order to obtain a stable composition.