FR2953399A1 - SOLID COSMETIC COMPOSITION COMPRISING A POLYESTER AND A SELECTIVE ETHYLENIC COPLYMER - Google Patents

Abstract

The invention relates in particular to a cosmetic composition for the care and / or makeup of keratinous materials comprising at least one fatty phase and containing: (i) at least one ethylenic block copolymer (also called sequenced ethylenic polymer), containing at least a first sequence having a glass transition temperature (Tg) greater than or equal to 40 ° C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least one second block having a glass transition temperature less than or equal to 20 ° C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20 ° C, said first sequence and said second block being interconnected by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second monomers constituting the second block, and said block copolymer having a polydispersity index I greater than 2 and (ii) at least one polyester obtainable by reaction of: a tetraol having from 4 to 10 carbon atoms; a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid having 7 to 11 carbon atoms.

Description

The present invention relates to cosmetic compositions for the care and / or makeup of keratin materials, especially the skin or the lips, comprising a polyester and a block ethylenic polymer.

In particular, the compositions according to the invention are intended to be applied to the lips and the skin, in particular the face. It is preferably care compositions or makeup (lipstick or foundation), in liquid or solid form, for example in the form of sticks, preferably anhydrous.

In the cosmetic field, the development of formulations having both good properties in terms of ease of application on keratinous materials, and whose deposition, in particular on the skin and the lips, has satisfactory properties in terms of holding the skin. Deposition in time and non-sticky, both immediately after application that 2 hours after application, falls under a permanent goal.

It is known from FR 2 917 616, cosmetic compositions containing polyesters associated with conventional volatile oils such as isododecane, to obtain after application to the keratin materials, in particular the lips, a makeup deposit having a good performance. In particular for lipsticks, the makeup has good resistance to the deposition of said lipstick on the lips over time, that is to say the formed deposit retains its integrity and remains homogeneous for 2 hours, and does not tend to weaken or fragment, or accumulate in fine lines on the skin or lips.

These polyesters also make it possible to impart a glossy appearance to the compositions when they are applied to the keratin materials. In particular, a high level of gloss of the deposit is generally sought in the context of a lipstick.

However, these polyesters are very viscous compounds the resulting solid or liquid compositions are generally very catchy (little slippery) in contact with the skin or lips, and therefore difficult to apply, not allowing to obtain a thick and homogeneous deposit. In addition, the deposition formed on the skin and the lips may be sticky. We therefore seek to obtain compositions comprising such polyesters, which are easily applied (good slip) to the skin or the lips, and forming a deposit having good gloss and hold properties in time of the color and gloss of the deposit, and which is comfortable and non-sticky.

The inventors have unexpectedly found that the combination of a polyester as defined below, and a block ethylenic copolymer such as those described in documents EP 1 411 069 and EP 1 882 709 and known to obtain after application on keratin materials, in particular the lips, a makeup deposit with good color and shine retention.

Indeed, these block polymers, like the polyesters, are very viscous and have the disadvantage of being sticky source when present in a composition, which is uncomfortable for the user, which makes the composition catchy and difficult to apply on the skin or lips, and makes the deposit sticky. However, the inventors have discovered that the combination of a polyester and an ethylenic sequenced polymer makes it possible in particular to obtain compositions whose application to the skin and the lips is easy (good sliding) and whose deposit on the skin or lips has a reduced tights. The compositions according to the invention also have good gloss and hold properties of the color and gloss of the deposit formed. Thus the invention relates in particular to a cosmetic composition for the care and / or makeup of keratin materials comprising, in a physiologically acceptable medium, at least one fatty phase and containing: (i) at least one ethylenic block copolymer (also called ethylene polymer) sequenced), containing at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least a second sequence having a glass transition temperature of 20 ° C or less and being issued in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature i nférieure or equal to 20 ° C, said first sequence and said second sequence being interconnected by a random intermediate segment comprising at least one of said first monomers constituting the first sequence and at least one of said second monomers constituting the second sequence, and said block copolymer having a polydispersity index I greater than 2 and (ii) at least one polyester obtainable by reaction of: - a tetraol having from 4 to 10 carbon atoms; - a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid having 7 to 11 carbon atoms.

The invention also relates to a cosmetic process for the care and / or makeup of keratinous materials comprising the application to said keratin materials, and in particular the skin, of a composition according to the invention.

POLYESTERS or POLYCONDENSATS The composition according to the invention comprises at least one polyester (also called polycondensate). A polyester suitable for the invention may be advantageously obtained by reacting a polyol, a polycarboxylic acid, a nonaromatic monocarboxylic acid, and an aromatic monocarboxylic acid.

In particular, a polyester which is suitable for the invention may be preferentially obtained by reaction of: a tetraol having from 4 to 10 carbon atoms; - a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid having 7 to 11 carbon atoms. Advantageously, a polyester of the invention may be obtained by reacting: 10 to 30% by weight of a tetraol having 4 to 10 carbon atoms; 40 to 80% by weight of a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; from 5 to 30% by weight of a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; from 0.1 to 10% by weight of an aromatic monocarboxylic acid having from 7 to 11 carbon atoms, the contents being expressed as percentage by weight relative to the total weight of the polyester. A polyester used according to the invention comprises a tetraol. By tetraol is meant a polyol comprising 4 hydroxyl groups. A tetraol used for the preparation of the polyester is advantageously a hydrocarbon compound, linear, branched and / or cyclic, saturated or unsaturated, comprising from 4 to 10 carbon atoms, and may further comprise one or more oxygen atoms intercalated in the chain (ether function). It is of course possible to use a mixture of such tetraols. A tetraol may in particular be a saturated hydrocarbon compound, linear or branched, comprising 4 to 10 carbon atoms. A tetraol may be chosen from pentaerythritol or tetramethylolmethane, erythritol, diglycerol or ditrimethylolpropane.

Preferably, the tetraol is chosen from pentaerythritol and diglycerol. More preferably still, the tetraol may be pentaerythritol. The content of tetraol, or tetraol mixture, may represent from 10 to 30% by weight, especially 12 to 25% by weight, and more preferably from 14 to 22% by weight relative to the total weight of the polyester.

A polyester used according to the invention also comprises a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms, and in particular 12 to 22 carbon atoms. By saturated monocarboxylic acid is meant a compound of formula RCOOH, wherein R is a saturated hydrocarbon radical, linear or branched, comprising from 8 to 22 carbon atoms, especially from 11 to 21 carbon atoms. It is of course possible to use a mixture of such monocarboxylic acids. Among the saturated monocarboxylic acids which may be used, mention may be made, alone or as a mixture, of nonanoic acid, isononanoic acid or pelargonic acid, decanoic acid or capric acid, lauric acid and tridecanoic acid. or tridecyl acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, and behenic acid. Preferably, lauric acid, myristic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid, behenic acid, and mixtures thereof may be used. Preferentially, isostearic acid or stearic acid is used. When the saturated monocarboxylic acid is liquid at room temperature, it generally leads to a liquid polyester at room temperature. As liquid monocarboxylic acid, mention may be made of nonanoic acid, isononanoic acid and isostearic acid. When the saturated monocarboxylic acid is solid at room temperature, it generally leads to a solid polyester at room temperature. As solid monocarboxylic acid, there may be mentioned decanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid. The content of saturated monocarboxylic acid, or the mixture of said acids, represents from 40 to 80% by weight, in particular from 42 to 75% by weight, or even 45 to 70% by weight, and better still 50 to 65% by weight of the total weight. polyester. The polyester used according to the invention also comprises a cyclic dicarboxylic acid having from 6 to 12 carbon atoms, especially having 8 carbon atoms. The cyclic dicarboxylic acid can be aromatic or nonaromatic. The cyclic dicarboxylic acid is preferably aromatic. It is of course possible to use a mixture of such cyclic dicarboxylic acids.

A cyclic dicarboxylic acid may be chosen from cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid and naphthalene-2 acid. 3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, or mixtures thereof.

Preferably, the cyclic dicarboxylic acid is chosen from phthalic acid, terephthalic acid and isophthalic acid. Phthalic acid can advantageously be used in its anhydride form. Preferably, the cyclic dicarboxylic acid is isophthalic acid.

A cyclic dicarboxylic acid, or a mixture of such diacids, can represent from 5 to 30% by weight, and preferably from 15% to 25% by weight of the total weight of the polyester. A polyester used according to the invention also comprises an aromatic monocarboxylic acid having 7 to 11 carbon atoms. By aromatic monocarboxylic acid is meant a compound of formula R'COOH, in which R 'is an aromatic hydrocarbon radical comprising from 6 to 10 carbon atoms; R 'is in particular a phenyl radical, optionally substituted with 1 to 3 alkyl radicals comprising from 1 to 4 carbon atoms.

It is of course possible to use a mixture of such aromatic monocarboxylic acids. The aromatic monocarboxylic acid may be selected from benzoic acid and 4-tert-butylbenzoic acid. The aromatic monocarboxylic acid is preferably benzoic acid.

Said aromatic monocarboxylic acid, or the mixture of said acids, represents from 0.1 to 10% by weight, in particular from 0.5 to 9.95% by weight, better still from 1 to 9.5% by weight, or even 1, 5 to 8% by weight of the total weight of the polyester.

According to a preferred embodiment, said polyester is obtained by reacting: from 12 to 25% by weight of a tetraol having from 4 to 10 carbon atoms; from 40 to 75% by weight of a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; from 15 to 25% by weight of a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; from 0.5 to 9.95% by weight of an aromatic monocarboxylic acid having from 7 to 11 carbon atoms, the contents being expressed as a percentage by weight relative to the total weight of the polyester. According to another preferred embodiment, said polyester is obtained by reacting: from 14 to 22% by weight of a tetraol having from 4 to 10 carbon atoms; from 45 to 70% by weight of a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; from 15 to 25% by weight of a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; from 1 to 9.5% by weight of an aromatic monocarboxylic acid having from 7 to 11 carbon atoms, the contents being expressed in percentage by weight relative to the total weight of the polyester.

According to another preferred embodiment, said polyester is obtained by reacting: from 14 to 22% by weight of a tetraol having from 4 to 10 carbon atoms; from 50 to 65% by weight of a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; from 15 to 25% by weight of a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; from 1.5 to 8% by weight of aromatic monocarboxylic acid having from 7 to 11 carbon atoms, the contents being expressed in percentage by weight relative to the total weight of the polyester. In a preferred embodiment of the polyester used according to the invention, the aromatic monocarboxylic acid is present in a molar amount less than or equal to that of the linear or branched monocarboxylic saturated acid; in particular the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of linear or branched monocarboxylic saturated acid varies from 0.08 to 0.70. Said weight ratio preferably varies from 0.10 to 0.60, and still more preferably from 0.12 to 0.40. According to one embodiment of the invention, a polyester of the invention may be chosen from benzoic acid / isophthalic acid / isostearic acid / pentaerythritol polyesters, benzoic acid / isophthalic acid / stearic acid / pentaerythritol polyesters, and their mixtures. These monomers are used in particular according to the ranges of monomer concentrations described above. Preferably, the polyester has: an acid number, expressed in mg of potassium hydroxide per gram of polyester, greater than or equal to 1; in particular between 2 and 30, and even better between 2.5 and 15; and / or - a hydroxyl number, expressed in mg of potassium hydroxide per gram of polyester, greater than or equal to 40; in particular between 40 and 120, and even better between 40 and 80.

These acid and hydroxyl numbers can be easily determined by those skilled in the art by the usual analytical methods. Preferably, a polyester of the invention has a weight average molecular weight (Mw) of between 3,000 and 1,000,000, or even between 3,000 and 300,000.

The average molecular weight can be determined by gel permeation chromatography or by light scattering, depending on the solubility of the polymer in question. Preferably, a polyester of the invention has a viscosity, measured at 110 ° C., of between 20 and 4000 mPa.s, in particular between 30 and 3500 mPa.s, even between 40 and 3000 mPa.s and even better between 50 and 4000 mPa.s. and 2500 mPa.s. This viscosity is measured as described below. According to a preferred embodiment, the polyester may be in liquid form at room temperature. A liquid polyester can have a weight average molecular weight (Mw) of from 40,000 to 1,000,000, preferably from 50,000 to 300,000. A liquid polyester can have a viscosity, measured at 110 ° C, of 1000 at 4000 mPa.s, and preferably ranging from 1500 to 3000 mPa.s. In particular, a liquid polyester may be a benzoic acid / isophthalic acid / isostearic acid / pentaerythritol acid polyester, these monomers being in particular present according to the ranges of monomer concentrations described above. According to another embodiment, the polyester may also be in solid form at room temperature. A solid polyester may have a weight average molecular weight (Mw) of from 3,000 to 30,000, preferably from 8,000 to 15,000. The solid polyester may have a viscosity, measured at 80 ° C, of from 20 to 20,000. 1000 mPa.s, and preferably ranging from 50 to 600 mPa.s. In particular, a solid polyester may be a benzoic acid / isophthalic acid / stearic acid / pentaerythritol polyester, these monomers being in particular present according to the ranges of monomer concentrations described above. A polyester of the invention may be prepared according to the synthesis method described in application EP-A-1 870 082. The viscosity of a polyester of the invention may be measured as described below: 80 ° C or 110 ° C of a polyester is measured using a planar cone viscometer type BROOKFIELD CAP 1000+. The adapted cone-plane is determined by the person skilled in the art, on the basis of his knowledge; in particular: - between 50 and 500 mPa.s, one can use a cone 02, - between 500 and 1000 mPa.s: cone 03, - between 1000 and 4000 mPa.s: cone 05, and - between 4000 and 10000 mPa. The amount of polyester, also called polycondensate, present in a composition of the invention may vary from 1 to 60% by weight, preferably from 2 to 50% by weight, especially from 3 to 45% by weight. or from 4 to 35% by weight, and better still from 5 to 30% by weight relative to the total weight of the composition. A polyester that is suitable for the invention can be easily transportable in cosmetic or oily cosmetic media, especially oils, fatty alcohols and / or fatty esters. A polyester of the invention can be prepared easily, in a single synthesis step, and without producing waste, and this at low cost. A polyester suitable for the invention may advantageously be connected (branched) in order to generate a network by entanglement of polymer chains, and thus to obtain the desired properties, in particular in terms of improved behavior, improved gloss, and in terms of solubility. . According to one embodiment, a composition of the invention may comprise at least two polyesters that are distinct from one another.

SEQUENCE-BASED ETHYLENE COPOLYMER The composition according to the present invention contains at least one block ethylenic copolymer (also called sequenced ethylenic polymer), containing at least a first block having a glass transition temperature (Tg) of greater than or equal to 40 ° C. and resulting in all or part of one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least one second sequence having a glass transition temperature less than or equal to 20 ° C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C, first sequence and said second sequence being interconnected by an intermediate segment e statistic comprising at least one of said first monomers constituting the first sequence and at least one of said second constituent monomers of the second sequence, and said block copolymer having a polydispersity index I greater than 2.

The sequenced polymer used according to the invention thus comprises at least a first sequence and at least a second sequence.

By "at least" a sequence is meant one or more sequences. By "sequenced" polymer is meant a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences. By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.

The block ethylenic polymer used according to the invention is prepared exclusively from monofunctional monomers. This means that the sequenced ethylenic polymer used according to the present invention does not contain multifunctional monomers, which make it possible to break the linearity of a polymer in order to obtain a connected or even cross-linked polymer, as a function of the multifunctional monomer content. The polymer used according to the invention also does not contain macromonomers ("macromonomer" means a monofunctional monomer having a pendant group of a polymeric nature, and preferably having a molecular weight greater than 500 g / mol, or a polymer having on one of its ends a polymerizable terminal group (or ethylenically unsaturated)), which are used in the preparation of a graft polymer.

It is specified that in what precedes and what follows the terms "first" and "second" sequences do not condition the order of said sequences (or blocks) in the structure of the polymer.

The first and second sequences of the polymer used in the invention may be advantageously incompatible with each other. By "sequences incompatible with each other" is meant that the mixture formed by a polymer corresponding to the first block and by a polymer corresponding to the second block, is not miscible in the polymerization solvent, predominant in weight, of the sequenced polymer, at ambient temperature (20 ° C.) and atmospheric pressure (105 Pa), for a content of the mixture of said polymers greater than or equal to 5% by weight, relative to the total weight of the mixture of said polymers and of said solvent method of polymerization, it being understood that: i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that ii) each of the polymers corresponding to the first and second blocks has a average molecular weight (in weight or in number) equal to that of the sequenced polymer +/- 15%.

In the case of a mixture of polymerization solvents, assuming two or more solvents present in identical mass proportions, said polymer mixture is immiscible in at least one of them. Of course, in the case of a polymerization carried out in a single solvent, the latter is the majority solvent.

The sequenced polymer according to the invention comprises at least a first sequence and at least a second sequence linked together by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. The intermediate segment (also called intermediate sequence) has a glass transition temperature Tg between the glass transition temperatures of the first and second sequences.

The intermediate segment is a sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer makes it possible to "compatibilize" these blocks. Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.

Preferably, the intermediate sequence is derived essentially from constituent monomers of the first sequence and the second sequence. By "essentially" is meant at least 85%, preferably at least 90%, better at 95% and even better at 100%.

The block polymer according to the invention is advantageously a film-forming ethylenic block polymer. By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.

By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous deposit on a support, in particular on keratin materials.

Preferably, the polymer according to the invention does not comprise silicon atoms in its backbone. By "skeleton" is meant the main chain of the polymer, as opposed to the pendant side chains.

Preferably, the polymer according to the invention is not water-soluble, that is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without modification of pH, with an active ingredient content of at least 1% by weight, at room temperature (20 ° C).

Preferably, the polymer according to the invention is not an elastomer.

By "non-elastomeric polymer" is meant a polymer which, when subjected to a stress aimed at stretching it (for example by 30% relative to its initial length), does not return to a length substantially identical to its length. initial when the constraint stops. More specifically, "non-elastomeric polymer" denotes a polymer having an instantaneous recovery R; <50% and delayed recovery R2h <70% after 30% elongation. Preferably, R; is <30%, and R2h <50%. More specifically, the non-elastomeric nature of the polymer is determined according to the following protocol: A polymer film is prepared by pouring a solution of the polymer into a teflon matrix and then drying for 7 days in a controlled atmosphere at 23 ± 5 ° C. and 50 ± 10% relative humidity.

A film approximately 100 μm thick in which are cut rectangular specimens (for example by punch) of a width of 15 mm and a length of 80 mm are then obtained. This sample is imposed a tensile stress using an apparatus marketed under the reference Zwick, under the same conditions of temperature and humidity as for drying. The specimens are stretched at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (lo) of the specimen. The instantaneous recovery R 1 is determined as follows: the specimen is stretched by 30% (max max), that is to say approximately 0.3 times its initial length ()); the stress is released by imposing a return speed equal to the tensile speed, ie 50 mm / min and the residual elongation of the specimen is measured in percentage, after return to zero load stress (i i).

The instantaneous recovery in% (Ri) is given by the formula below:

Ri = (max max - ii) / Emax) X 100 To determine the delayed recovery, after 2 hours the residual elongation ratio of the specimen is measured in percentage (2 2h), 2 hours after load stress return. nothing. The recovery delayed in% (R2h) is given by the formula below: R2h = (£ max - £ 2h) / Emax) X 100 For information only, a polymer according to one embodiment of the invention preferably has an instantaneous recovery Ri of 10% and a delayed recovery R2h of 30%.

The polydispersity index of the polymer of the invention is greater than 2. Advantageously, the block polymer used in the compositions according to the invention has a polydispersity index I greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still greater than or equal to 2.8, and especially ranging from 2.8 to 6.30. The polydispersity index I of the polymer is equal to the ratio of average weight mass Mw on the average mass number Mn. The weight average (Mw) and number (Mn) molar masses are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). The weight average mass (Mw) of the polymer according to the invention is preferably less than or equal to 300,000, it ranges, for example, from 35,000 to 200,000, and more preferably from 45,000 to 150,000 g / mol. The number average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70,000, it ranges, for example, from 10,000 to 60,000, and more preferably from 12,000 to 50,000 g / mol. Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still or equal to 2.8 and in particular, ranging from 2.8 to 6.

First sequence before a higher Tq or equal to 40 ° C

The sequence having a Tg greater than or equal to 40 ° C has for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example from 50 ° C to 120 ° C, and better still or equal to 60 ° C, for example from 60 ° C to 120 ° C.

The indicated glass transition temperatures of the first and second sequences can be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as Polymer Handbook, 3rd ed, 1989, John Wiley, according to the following relationship, called Fox's Law: 1 / Tg = E (m / Tg), where i is the mass fraction of the monomer i in the considered sequence and Tg; being the glass transition temperature of the homopolymer of the monomer i. Unless otherwise indicated, the Tg values for the first and second sequences in the present application are theoretical Tg.

The difference between the glass transition temperatures of the first and second blocks is generally greater than 10 ° C, preferably greater than 20 ° C, and more preferably greater than 30 ° C.

In the present invention, the expression "comprised between ... and" is intended to denote an interval of values whose mentioned limits are excluded, and "from ... to ..." and "ranging from ... to ... ", an interval of values whose terminals are included. The sequence having a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer. The sequence having a Tg greater than or equal to 40 ° C may be issued in whole or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. This sequence can also be called "rigid sequence". In the case where this sequence is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. This first block may be a homopolymer consisting of a single type of monomer (in which the Tg of the corresponding homopolymer is greater than or equal to 40 ° C.).

In the case where the first block is a copolymer, it may be derived in whole or in part from one or more monomers whose nature and concentration are chosen so that the Tg of the resulting copolymer is greater than or equal to 40%. ° C. The copolymer may for example comprise: monomers which are such that the homopolymers prepared from these monomers have Tg greater than or equal to 40 ° C., for example a Tg ranging from 40 ° C. to 150 ° C., preferably greater than or equal to 50 ° C, for example from 50 ° C to 120 ° C, and more preferably greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C, and monomers which are such that the homopolymers prepared from these monomers have Tg's lower than 40 ° C, chosen from monomers having a Tg of between 20 ° C and 40 ° C and / or monomers having a Tg of less than or equal to at 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably below 15 ° C, in particular ranging from 80 ° C to 15 ° C and better still below 10 ° C, for example ranging from The first monomers whose homopolymers have a glass transition temperature greater than 50 ° C. to 0 ° C. are as described below. or 40 ° C are preferably selected from the following monomers, also called main monomers: - methacrylates of formula CH2 = C (CH3) -000R1 wherein R, represents an unsubstituted alkyl group, linear or branched , containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R, represents a C4 to C12 cycloalkyl group, preferably a C8 to C12 cycloalkyl, such as isobornyl methacrylate, acrylates of formula CH 2 CHCH-OOOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group such as an isobornyl group or a tert-butyl group, the (meth) acrylamides of formula: R 'R 7 CH 2 = C CO N R8 wherein R, and R8, which are identical or different, each represents a hydrogen atom or a linear or branched C12-C12 alkyl group, such as n-butyl, tert-butyl, isopropyl, isohexyl, isooctyl, or isononyl; or R, is H and R8 is 1,1-dimethyl-3-oxobutyl, and R 'is H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide, and mixtures thereof. The first block is advantageously obtained from at least one acrylate monomer of formula CH2 = CH-OO0R2 and at least one methacrylate monomer of formula CH2 = C (CH3) -OO0R2 in which R2 represents a C4 to C12 cycloalkyl group preferably C8 to C12 cycloalkyl, such as isobornyl. The monomers and their proportions are preferably chosen so that the glass transition temperature of the first block is greater than or equal to 40 ° C. According to one embodiment, the first block is obtained from: i) at least one acrylate monomer of formula CH2 = CH-OO0R2 in which R2 represents a C4 to C12 cycloalkyl group, preferably a C8 cycloalkyl group; at C12, such as isobornyl, - ii) and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 to C12 cycloalkyl group, preferably a cycloalkyl group in C8 to 012, such as isobornyl.

According to one embodiment, the first block is obtained from at least one acrylate monomer of formula CH2 = CH-OO0R2 in which R2 represents a C8 to C12 cycloalkyl group, such as isobornyl, and from minus a methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C8 to C12 cycloalkyl group, such as isobornyl. Preferably, R2 and R'2 represent independently or simultaneously an isobornyl group. Preferably, the block copolymer comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acrylic acid.

The first block can be obtained exclusively from said acrylate monomer and said methacrylate monomer. The acrylate monomer and the methacrylate monomer are preferably in mass proposals of between 30:70 and 70:30, preferably between 40:60 and 60:40, in particular of the order of 50:50.

The proportion of the first block is preferably from 20 to 90% by weight of the polymer, more preferably from 30 to 80% and most preferably from 60 to 80%.

According to one embodiment, the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate. Second glass transition temperature sequence less than 20 ° C. The second sequence advantageously has a glass transition temperature Tg of less than or equal to 20 ° C., for example a Tg ranging from -100 ° C. to 20 ° C., preferably less than or equal to 15 ° C., in particular ranging from -80 ° C. C at 15 ° C and better still less than or equal to 10 ° C, for example ranging from -100 ° C to 10 ° C, in particular ranging from 30 ° C to 10 ° C. The second sequence is derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C.

This sequence can also be called "soft sequence".

The monomer having a Tg of less than or equal to 20 ° C (called the second monomer) is preferably chosen from the following monomers:

the acrylates of formula CH2 = CHCOOR3, R3 representing a linear or branched C12-C12 unsubstituted alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms are optionally intercalated; selected from O, N, S,

the methacrylates of formula CH 2 = C (CH 3) -COOR 4, R 4 representing a linear or branched C 6 to C 12 unsubstituted alkyl group in which one or more heteroatoms selected from 0 are optionally intercalated; and S;

vinyl esters of formula R 5 -CO-O-CH =CH 2 where R 5 represents a linear or branched C 4 to C 12 alkyl group; vinyl alcohol and C4 to C12 alcohol ethers; C4 to C12 N-alkyl acrylamides, such as N-octylacrylamide; and mixtures thereof.

The monomers having a Tg of less than or equal to 20 ° C are preferred isobutyl acrylate, 2-ethylhexyl acrylate or mixtures thereof in all proportions.

Each of the first and second sequences may contain, in a minority proportion, at least one constituent monomer of the other sequence. Thus the first sequence may contain at least one constituent monomer of the second sequence and vice versa. Each of the first and / or second sequence may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned above. The nature and amount of this additional monomer (s) are chosen such that the sequence in which they occur has the desired glass transition temperature. This additional monomer is for example chosen from: - monomers containing ethylenic unsaturation (s) comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and salts thereof; methacrylates of formula CH2 = C (CH3) -COOR6 in which R6 represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl group ethyl, propyl or isobutyl, said alkyl group being substituted by one or more substituents selected from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate, methacrylates of the formula CH2 = C (CH3) -COOR9, wherein R9 represents a linear or branched C6-C12 alkyl group in which e (nt) optionally intercalated (s) one or more heteroatoms selected from 0, N and S, said alkyl group being substituted with one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I, F ); the acrylates of formula CH2 = CHCOOR16, wherein R3 represents a linear or branched C12-C12 alkyl group substituted with one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, 1 and F); ), such as 2-hydroxypropyl acrylate and 2-5 hydroxyethyl acrylate, or Rio represents a C1-C12-O-POE (polyoxyethylene) alkyl with a repeat of the oxyethylene unit of 5 to 10 times, for example methoxy-POE, or R8 represents a polyoxyethylenated group comprising from 5 to 10 ethylene oxide units.

In particular, the first block may comprise, as additional monomer: - (meth) acrylic acid, preferably acrylic acid, - tert-butyl acrylate - methacrylates of formula CH 2 = C (CH 3) In which R 1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the (meth) acrylamides of formula: R ' Where R, and R8, which are identical or different, each represents a hydrogen atom or a linear or branched C12-C12 alkyl group, such as a n-butyl, t-butyl, isopropyl or isohexyl group; , isooctyl, or isononyl; or R, is H and R8 is 1,1-dimethyl-3-oxobutyl, and R 'is H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide, and mixtures thereof. The additional monomer can represent 0.5 to 30% by weight of the weight of the polymer. According to one embodiment, the polymer of the invention does not contain any additional monomer. Preferably, the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first block and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block, the first block being 70% by weight of the polymer. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the Tg sequence greater than 40 ° C represents 70% by weight of the polymer, and the acrylic acid represents 5% by weight of the polymer. According to one embodiment, the first sequence does not comprise additional monomer.

According to a preferred embodiment, the second block comprises acrylic acid as additional monomer. In particular, the second block is advantageously obtained from an acrylic acid monomer and from at least one other monomer having a Tg of less than or equal to 20 ° C. According to a preferred embodiment, the invention relates to a cosmetic composition for the makeup and / or care of keratin materials comprising, in a physiologically acceptable medium, at least: a) a copolymer comprising at least one acrylate monomer of formula CH 2 = In which R2 represents a C8 to C12 cycloalkyl group and / or at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C8 to C12 cycloalkyl group, at least a second acrylate monomer of the formula CH 2 = CHCOOR 3, wherein R 3 represents a linear or branched C 1 to C 12 unsubstituted alkyl group, with the exception of the tert-butyl group, and at least one acrylic acid monomer, b) at least one polyester capable of be obtained by reaction of: - a tetraol having from 4 to 10 carbon atoms; - a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid having 7 to 11 carbon atoms.

Preferably, the copolymer used in the compositions according to the invention is obtained from at least one isobornyl methacrylate monomer, at least one isobornyl acrylate monomer, at least one isobutyl acrylate monomer. and at least one acrylic acid monomer. Advantageously, the copolymer used in the invention comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate mixture, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acid. acrylic.

The block copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and especially from 2 to 15% by weight, for example from 3 to 15% by weight, in particular from 4 to 15% by weight, or even from 4 to 15% by weight. 10% by weight of acrylic acid monomers, relative to the total weight of said copolymer. The constituent monomers of the second block and their proportions are chosen so that the glass transition temperature of the second block is less than or equal to 20 ° C.

Intermediate Segment The intermediate segment (also called intermediate sequence) connects the first sequence and the second sequence of the polymer used according to the present invention. The intermediate segment results from the polymerization of: i) the first monomer or monomers, and optionally the additional monomer or monomers, remaining available after their polymerization at a conversion rate of at most 90% to form the first sequence, ii) and the or second monomers, and optionally additional monomer (s) added to the reaction mixture.

The formation of the second sequence is initiated when the first monomers no longer react or become incorporated in the polymer chain either because they are all consumed or because their reactivity no longer allows them to be.

Thus, the intermediate segment comprises the first available monomers, resulting from a conversion rate of these first monomers of less than or equal to 90%, during the introduction of the second monomer or monomers during the synthesis of the polymer.

The intermediate segment of the sequenced polymer is a random polymer (may also be called a statistical sequence). That is to say, it comprises a statistical distribution of the first monomer (s) and second monomer (s) and any additional monomer (s) that may be present.

Thus, the intermediate segment is a statistical sequence, as are the first sequence and the second sequence if they are not homopolymers (i.e., both are formed from at least two different monomers ).

Process for preparing the copolymer: The block ethylenic copolymer according to the invention is prepared by free radical polymerization, according to the techniques well known in this type of polymerization.

The free radical polymerization is carried out in the presence of an initiator whose nature is adapted, in known manner, depending on the desired polymerization temperature and the polymerization solvent. In particular, the initiator may be chosen from peroxide-functional initiators, oxidation-reduction pairs, or other radical polymerization initiators known to those skilled in the art. In particular, as a peroxide-functional initiator, there may be mentioned, for example: a. peroxyesters, such as terbutylperoxyacetate, tertbutylperbenzoate, tertbutylperoxy-2-ethylhexanoate (Akzo Nobel Trigonox 21S), 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox) 141 by Akzo Nobel); b. peroxydicarbonates, such as di-isopropylperoxydicarbonate; c. peroxycetones, such as methyl ethyl ketone peroxide; d. hydroperoxides, such as hydrogen peroxide (H2O2), terbutylhydroperoxide; e. diacyl peroxides, such as acetyl peroxide, benzoyl peroxide; f. dialkyl peroxides, such as di-tert-butyl peroxide; g. inorganic peroxides, such as potassium peroxodisulfate (K2S2O8); As an initiator in the form of a redox couple, mention may be made of the potassium thiosulfate + potassium peroxodisulphate pair, for example.

According to a preferred embodiment, the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms. Preferably, the initiator used is 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane sold under the reference Trigonox® 141 by Akzo Nobel. The block copolymer used according to the invention is prepared by free radical polymerization and not by controlled or living polymerization. In particular, the polymerization of the block ethylenic copolymer is carried out in the absence of control agents, and in particular in the absence of control agent conventionally used in living or controlled polymerization processes such as nitroxides, alkoxyamines dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates, copper catalysts, for example. As previously indicated, the intermediate segment is a statistical sequence, as is the first sequence and the second sequence if they are not homopolymers (i.e., both are formed from at least two different monomers).

The block copolymer may be prepared by free radical polymerization, and in particular by a process comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one glass transition monomer greater than or equal to 40 ° C., less than a glass transition monomer less than or equal to 20 ° C according to the following sequence: - is poured into the reactor, a portion of the polymerization solvent and optionally a portion of the initiator and monomers of the first casting mixture that the the reaction mixture is heated to a reaction temperature of between 60 and 120 ° C., the at least one first monomer with a Tg of greater than or equal to 40 ° C. and, optionally, part of the initiator, which is then poured in a first casting. it is left to react for a time T corresponding to a conversion rate of said monomers of 90% maximum, - then poured into the reactor, in a second casting, at n new polymerization initiator, said at least one second glass transition monomer less than or equal to 20 ° C, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau; the reaction mixture is cooled to room temperature. Preferably, the copolymer may be prepared by free radical polymerization, in particular by a process consisting of mixing, in one and the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one lower glass transition monomer or equal to 20 ° C, at least one acrylate monomer of formula CH2 = CH-OOOR2 in which R2 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R 2 represents a C 4 to C 12 cycloalkyl group, according to the following stage sequence: a portion of the polymerization solvent and optionally a part of the initiator and monomers of the first casting are poured into the reactor, a mixture which is heated to a reaction temperature of between 60 and 120 ° C., the at least one acrylate monomer of formula CH 2 = CH-OOOR 2 and at least one monomer is then poured in a first casting. re methacrylate of formula CH2 = C (CH3) -COOR'2 as monomers of Tg greater than or equal to 40 ° C, and optionally a portion of the initiator which is allowed to react for a duration T corresponding to one conversion rate of said monomers 90% maximum, - then poured into the reactor, in a second casting, again the polymerization initiator, the acrylic acid monomer and said at least one glass transition monomer less than or equal to 20 ° C, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, - the reaction mixture is brought to room temperature.

By polymerization solvent is meant a solvent or a mixture of solvents. In particular, as a polymerization solvent that may be used, mention may be made of: ketones that are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate isopentyl; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes which are liquid at ambient temperature, such as decane, heptane, dodecane, isododecane, cyclohexane and isohexadecane; aromatic cyclic compounds which are liquid at ambient temperature, such as toluene and xylene; aldehydes which are liquid at room temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof. Conventionally, the polymerization solvent is a volatile oil having a flash point of less than 80 ° C. The flash point is measured in particular according to ISO Standard 3679. The polymerization solvent may be chosen in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol, ethanol and aliphatic alkanes. such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

According to another embodiment, the copolymer may be prepared by free radical polymerization according to a preparation process, comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one lower glass transition monomer or equal to 20 ° C, and at least one monomer of Tg greater than or equal to 40 ° C, according to the following step sequence: - is poured into the reactor, a portion of the polymerization solvent and optionally a portion of the initiator and monomers of the first casting, which mixture is heated to a reaction temperature between 60 and 120 ° C, is then poured, in a first casting, said at least one glass transition monomer less than or equal to 20 ° C and optionally a portion of the initiator which is allowed to react for a time T corresponding to a conversion rate of said monomers of 90% maximum, - then poured into the reaction ur, in a second casting, again of the polymerization initiator, said at least one monomer of Tg greater than or equal to 40 ° C, which is allowed to react for a period T 'at the end of which the conversion rate of said monomers reaches a plateau, - the reaction mixture is brought to room temperature.

According to a preferred embodiment, the copolymer can be prepared by free radical polymerization according to a preparation process, comprising mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one monomer of glass transition less than or equal to 20 ° C, at least one monomer of Tg greater than or equal to 40 ° C, and in particular as monomers of Tg greater than or equal to 40 ° C, at least one acrylate monomer of formula CH2 In which R2 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 to C12 cycloalkyl group, in the sequence of C4 to C12; following step: - is poured into the reactor, a portion of the polymerization solvent and optionally a portion of the initiator and the monomers of the first casting mixture that is heated to a reaction temperature; between 60 and 120 ° C., the acrylic acid monomer and the at least one glass transition monomer less than or equal to 20 ° C. and optionally a portion of the initiator which is then added are poured in a first casting. is allowed to react for a time T corresponding to a conversion rate of said monomers of 90% maximum, then poured into the reactor, in a second casting, again the polymerization initiator, said at least one acrylate monomer of formula CH2 = CH-OOOR2 and said at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2, as a monomer of Tg greater than or equal to 40 ° C, which is allowed to react for a time T 'at after which the conversion rate of said monomers reaches a plateau, - the reaction mixture is brought to room temperature. The polymerization temperature is preferably of the order of 90 ° C. The reaction time after the second casting is preferably between 3 and 6 hours.

Block copolymers such as those described above are described in particular in patent applications EP-A-1411069 and EP-A-1882709.

Distillation of the synthesis solvent For the implementation of the block polymer in a composition according to the invention, and when the polymer is prepared in a volatile solvent or a volatile oil having a flash point below 80 ° C., it is advantageous to proceed to a total or partial elimination step of said volatile solvent or oil, in particular if it is desired to formulate a composition in solid form, for example as a stick. It is carried out in particular by distillation, optionally under vacuum, and addition of nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. This technique is known to those skilled in the art and Example 2 described below illustrates this technique.

The distillation of the synthesis solvent (typically isododecane) is preferably carried out with simultaneous addition or in the presence in the mixture before the distillation of a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mole. This step is carried out hot and optionally under vacuum to distil a maximum of isododecane (and more generally of synthetic solvent), if it has been used as a polymerization solvent, or more generally to distill a maximum of volatile oil with a flash point below 80 ° C. The nonvolatile ester oil may also be added partly or wholly to the polymer in the volatile solvent prior to distillation.

The elimination of the volatile oil with a flash point below 80 ° C. (typically isododecane) makes it possible to limit the content thereof in the solution of block copolymer and thus to produce a cosmetic composition containing less than 10% by weight of isododecane (and more generally of volatile solvent) and preferably less than 50% by weight of isododecane (and more generally of volatile solvent), relative to the total weight of the composition.

The composition according to the invention preferably comprises from 0.5 to 40% by weight of block ethylenic copolymer, and advantageously from 1 to 40% by weight, especially from 2 to 30% by weight, or even from 2 to 20% by weight. of active material relative to the total weight of the composition.

Preferably, the polyester and the block ethylenic copolymer are present in a polyconsendate / ethylene block copolymer mass ratio of between 1/50 and 50, preferably between 0.1 and 10, more preferably 1/5 and 5. Oil non-volatile hydrocarbon ester:

The composition according to the invention comprises a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. Advantageously, the first composition of the product according to the invention also comprises a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. The presence of the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol makes it possible to obtain a makeup deposit on keratin materials (in particular the lips) having good properties. The term "oil" means a non-aqueous compound which is liquid at room temperature (25 ° C.) and at atmospheric pressure (760 mmHg). By "non-volatile oil" is meant an oil remaining on the keratin materials at ambient temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 -3 mmHg (0.13 Pa). It is also possible to define a non-volatile oil as having an evaporation rate such that under the conditions defined above, the amount evaporated after 30 minutes is less than 0.07 mg / cm 2. By "hydrocarbon oil" is meant an oil formed essentially, or even constituted, of carbon and hydrogen atoms, and possibly of oxygen, nitrogen, and not containing a silicon atom or of fluorine. By "hydrocarbon ester oil" is meant a hydrocarbon oil comprising at least one ester group. As the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molecular weight of less than 650 g / mol, mention may be made in particular of: fatty acid esters, in particular from 4 to 22 carbon atoms, and especially octanoic acid, heptanoic acid, lanolic acid, oleic acid, lauric acid, stearic acid such as propylene glycol dioctanoate, propylene glycol monoisostearate, neopentyl glycol diheptanoate, synthetic esters such as the oils of formula R, wherein R, represents the residue of a linear or branched fatty acid containing from 4 to 40 carbon atoms and R 2 represents a hydrocarbon chain, in particular branched, containing from 4 to 40 carbon atoms, carbon provided that R, + R2 is 16, such as, for example, purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alcohol benzoate, 2-hexyl ethyl palmitate , the octopotanoate yledodecyl, 2-octyl dodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, 2-octyl dodecyl benzoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethylhexyl palmitate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, 2-octyldodecyl myristate, 2-diethylhexyl succinate; preferably, the preferred synthesis esters R1 COOR2 in which R represents the residue of a linear or branched fatty acid containing from 4 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched chain containing from 4 to 40 carbon atoms. are such that R1 and R2 are 20; hydroxylated esters, such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, glycerine stearate; diethylene glycol diisononanoate; and the pentaerythritol esters; esters of aromatic acids and alcohols comprising 4 to 22 carbon atoms, especially tridecyl trimellitate. According to one embodiment, a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol does not carry a free hydroxyl (OH) group. According to a preferred embodiment, the nonvolatile hydrocarbon ester oil comprises at least 20 carbon atoms with a molar mass of less than 650 g / mol. According to a preferred embodiment, the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms has a molar mass of less than 600 g / mol. The non-volatile hydrocarbon ester oil may in particular comprise a linear or branched hydrocarbon oil having a molar mass of between 100 and 650 g / mol and more particularly between 200 and 600 g / mol. The choice of these non-volatile oils makes it possible to optimize the amount of volatile oil whose flash point is less than or equal to 80 ° C., that is to say, to distil most of the solvent of polymerization (ie isododecane), or essentially all the polymerization solvent (that is to say volatile oil whose flash point is less than or equal to 80 ° C), the latter remaining only as the trace state in the composition. The use of other solvents does not make it possible to eliminate enough volatile oil whose flash point is less than or equal to 80 ° C. During the distillation, the mixture becomes very viscous and non-manipulable and it is no longer possible to continue the distillation. According to a preferred embodiment, the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms (preferably at least 20 carbon atoms) and having a molar mass of less than 650 g / mol is octyledodecyl neopentanoate (especially 2-octyledodecyl neopentanoate). This ester oil makes it possible to distil all of the volatile oil whose flash point is less than or equal to 80 ° C.

The composition according to the invention may comprise from 2 to 80% by weight of non-volatile oil, especially from 5 to 70%, relative to the total weight of the composition. According to a preferred embodiment, the ratio by weight of ethylenic block copolymer relative to the weight of nonvolatile hydrocarbon ester oil is less than 1, preferably less than 0.9, or better still less than 0.8.

Additional nonvolatile oil The composition according to the invention may advantageously comprise at least one other additional nonvolatile oil, different from said hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mole. may be chosen from all cosmetically acceptable oils, in particular mineral, vegetable, and synthetic oils; in particular the hydrocarbon oils and / or silicone and / or fluorinated, volatile or non-volatile and mixtures thereof. For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

The term "fluorinated oil" means an oil comprising at least one fluorine atom. More specifically, the term "hydrocarbon-based oil" is intended to mean an oil formed mainly, or in the main, consisting of carbon and hydrogen atoms, and not containing a silicon or fluorine atom, and possibly comprising one or more selected functions. among the hydroxyl, ester, ether or carboxylic functions.

By way of example of additional nonvolatile hydrocarbon oil, mention may be made of: 1 / linear or branched hydrocarbons of mineral or synthetic origin such as: paraffin oil or its derivatives, petroleum jelly, polybutylenes such as INDOPOL H-100 (molar mass or MW = 965 g / mol), INDOPOL H-300 (MW = 1340 g / mol), INDOPOL H-1500 (MW = 2160 g / mol) marketed or manufactured by the company AMOCO, hydrogenated polyisobutylenes such as Parleam® sold by the company Nippon Oil Fats, PANALANE H-300 E marketed or manufactured by the company AMOCO (MW = 1340 g / mol), Viseal 20000 marketed or manufactured by SYNTEAL (MW = 6000 g / mol), REWOPAL PIB 1000 marketed or manufactured by WITCO (MW = 1000 g / mol), polydecenes and hydrogenated polydecenes such as: PURESYN 10 (MW = 723 g / mol), PURESYN 150 (MW = 9200 g / mol) marketed or manufactured by MOBIL CHEMICALS,

2 / copolymers of vinylpyrrolidone, such as: the vinylpyrrolidone / 1-hexadecene copolymer, ANTARON VU216 sold or manufactured by ISP (MW = 7300 g / mol),

3 / hydrocarbon ester oils having a molar mass greater than 650 g / mol, such as linear fatty acid esters having a total number of carbon ranging from 35 to 70, such as pentaerythrityl tetrapelargonate (MW = 697 g / mol) ), hydroxylated esters such as polyglycerol-2 triisostearate (MW = 965 g / mol), aromatic esters such as tridecyl trimellitate (MW = 757 g / mol), esters of fatty alcohol or C24-C28 branched fatty acids such as those described in application EP-A-0 955 039, and in particular triisoarachidyl citrate (MW = 1033.76 g / mol), pentaerythrityl tetraisonanoate (MW = 697 g / mol) glyceryl triisostearate (MW = 891 g / mol), glyceryl tri-2-tetradecanoate (MW = 1143 g / mol), pentaerythrityl tetraisostearate (MW = 1202 g / mol), polyglyceryl tetraisostearate -2. (MW = 1232 g / mol) or pentaerythrityl tetra decyl 2-tetradecanoate (MW = 1538 g / mol), a polyester resulting from esterification of at least one carboxylic acid (s) triglyceride (s) hydroxylated with an aliphatic monocarboxylic acid and an optionally unsaturated aliphatic dicarboxylic acid, such as succinic acid castor oil and isostearic acid sold under the reference Zénigloss by Zenitech, the esters resulting from the esterification of a polyol and a dimer diacid such as polyglyceryl-2 isostearate copolymer dimerdilinoleate (Hailucent ISDA), dimer esters diol and diacid dimer of the general formula HO-R '- (- 000-R2-COO-R' -) h-OH, wherein: R 'represents a diol dimer residue obtained by hydrogenation of the dilinoleic diacid R2 represents a residue of hydrogenated dilinoleic diacid, and h represents an integer ranging from 1 to 9, in particular the esters of dilinoleic diacids and of dilinoleic diol dimers marketed by the company NIPPON FINE CHEMICAL under the trade name LUSPLAN DD- DA5® and DD-DA7®,

4 / silicone oils such as phenyl silicones (also called phenyl silicone oil) such as Belsil PDM 1000 from Wacker (MW = 9000 g / mol), phenyl trimethicones (such as phenyl trimethicone sold under the trade name DC556 by Dow Corning), phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, non-volatile polydimethylsiloxanes (PDMS), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and / or at the end of a silicone chain groups each having 2 to 24 carbon atoms; 5 / vegetable oils such as sesame oil (MW = 820 g / mol), and mixtures thereof.

Preferably, the composition according to the invention advantageously contains from 1 to 80% by weight, in particular from 5 to 70% by weight, preferably from 10 to 65% by total weight of additional non-volatile oil, relative to to the total weight of the composition.

Oils with a flash point less than or equal to 80 ° C:

According to one embodiment, the composition according to the invention preferably contains less than 10% by weight of volatile oil whose flash point is less than or equal to 80 ° C. This is particularly advantageous when it is desired to produce a composition comprising at least one solid fatty substance such as a wax or a solid fatty substance, in particular to obtain a solid composition. Preferably, the composition according to the invention comprises less than 50% relative to the total weight of the composition or is free of volatile oil whose flash point is less than or equal to 80 ° C., such as isododecane.

In particular, the flash point is measured according to ISO 3679.

For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with keratin materials in less than one hour at ambient temperature and atmospheric pressure (760 mmHg). The volatile organic solvent (s) and the volatile oils of the invention are organic solvents and volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 0 to 13 Pa at 40,000 Pa (10-3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg). These oils may be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof. In particular, as volatile oil whose flash point is less than or equal to 80 ° C., mention may be made of: volatile hydrocarbon-based oils such as hydrocarbon-based oils containing from 8 to 14 carbon atoms, and especially C8-C14 branched alkanes, for example C8-C14 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example the oils sold under the trade names of 'Isopars' or permetyls, and mixtures thereof. Preferably, the volatile solvent is selected from volatile hydrocarbon oils having 8 to 14 carbon atoms and mixtures thereof. As other volatile hydrocarbon oils whose flash point is less than or equal to 80 ° C., mention may also be made of ketones which are liquid at ambient temperature, such as methyl ethyl ketone and acetone; short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alcohols and in particular linear or branched lower monoalcohols having from 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol.

According to one embodiment, the composition according to the invention contains at least one volatile oil whose flash point is greater than 80 ° C., such as isohexadecane.

Solid fatty substances Preferably, the composition according to the invention comprises at least one solid fatty substance chosen from waxes and pasty fatty substances, and their mixture.

Pasty fatty substances For the purposes of the present invention, the term "pasty fatty substance" (also referred to as pasty fatty substance) is intended to mean a lipophilic fat compound with reversible solid / liquid state change, having in the solid state an anisotropic crystalline organization, and having at the temperature of 23 ° C a liquid fraction and a solid fraction. In other words, the starting melting temperature of the pasty compound may be less than 23 ° C. The liquid fraction of the pasty compound measured at 23 ° C. can represent 9 to 97% by weight of the compound. This liquid fraction at 23 ° C is preferably between 15 and 85%, more preferably between 40 and 85% by weight. For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in ISO 11357-3; 1999. The melting point of a paste or a wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the company TA Instruments .

The measurement protocol is as follows: A sample of 5 mg of paste or wax (as the case may be) placed in a crucible is subjected to a first temperature rise from -20 ° C to 100 ° C, at the rate of heating of 10 ° C / minute, then is cooled from 100 ° C to -20 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a heating rate of 5 ° C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the pasty or wax sample is measured as a function of temperature. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature. The liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed at 23 ° C. to the heat of fusion of the pasty compound. The heat of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in crystalline solid form. The pasty compound is said to be in a liquid state when all of its mass is in liquid form. The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a temperature rise of 5 or 10 ° C per minute, according to ISO 11357-3: 1999. The enthalpy of fusion of the pasty compound is the amount of energy required to pass the compound from the solid state to the liquid state. It is expressed in J / g. The heat of fusion consumed at 23 ° C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23 ° C consisting of a liquid fraction and a solid fraction. The liquid fraction of the pasty compound measured at 32 ° C is preferably 30 to 100% by weight of the compound, preferably 50 to 100%, more preferably 60 to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32 ° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 ° C. The liquid fraction of the pasty compound measured at 32 ° C. is equal to the ratio of the enthalpy of fusion consumed at 32 ° C. to the heat of fusion of the pasty compound. The enthalpy of fusion consumed at 32 ° C. is calculated in the same way as the heat of fusion consumed at 23 ° C. The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound can be obtained synthetically from starting materials of plant origin. The pasty compound is advantageously chosen from - lanolin and its derivatives - polyol ethers chosen from pentaerythritol ethers and polyalkylene glycol ethers, fatty alcohol and sugar ethers, and their mixtures, pentaerythritol and polyethylene ether. glycol comprising 5 oxyethylenated units (50E) (CTFA name: PEG-5 Pentaerythrityl Ether), pentaerythritol ether and polypropylene glycol comprising 5 oxypropylene units (5 PO) (CTFA name: PPG-5 Pentaerythrityl Ether), and their mixtures and more particularly the PEG-5 Pentaerythrityl Ether mixture, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name "Lanolide" by the company Vevy, a blend in which the constituents are in a ratio by weight of 46/46/8 : 46% PEG-5 Pentaerythrityl Ether, 46% PPG-5 Pentaerythrityl Ether and 8% soybean oil. the polymeric or non-polymeric silicone compounds or the non-polymeric fluorinated compounds, in particular: homopolymers and copolymers of olefins homopolymers and copolymers of hydrogenated dienes linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C 8 -C 30 alkyl group • Homopolymeric and copolymeric oligomers of vinyl esters having C 8 -C 30 alkyl groups • Homo and copolymer oligomers of vinyl ethers having C 8 -C 30 alkyl groups the liposoluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-C50 diols, the esters, and / or their mixtures. The pasty compound is preferably a polymer, in particular a hydrocarbon polymer.

Among the liposoluble polyethers, copolymers of ethylene oxide and / or of propylene oxide with long-chain C 6 -C 30 alkylene oxides are preferred, more preferably such as the weight ratio of ethylene oxide. and / or propylene oxide with alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, mention will in particular be made of copolymers such as long-chain alkylene oxides are arranged in blocks having an average molecular weight of 1,000 to 10,000, for example a polyoxyethylene / polydodecyl glycol block copolymer such as dodecanediol ethers (22). mol) and polyethylene glycol (45 EO) marketed under the tradename ELFACOS ST9 by Akzo Nobel.

Among the esters, the following are particularly preferred: esters of an oligomeric glycerol, in particular the esters of diglycerol, in particular the condensates of adipic acid and of glycerol, for which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, especially in the image of those marketed under the trademark Softisan 649 by the company Sasol - arachidyl propionate sold under the trademark Waxenol 801 by Alzo; phytosterol esters; triglycerides of fatty acids and their derivatives; non-crosslinked polyesters resulting from the polycondensation between a dicarboxylic acid or a linear polycarboxylic acid or branched C4-050 and a C2-050 diol or polyol, the ester aliphatic esters resulting from the esterification of an aliphatic hydroxycarboxylic acid ester with a carbo acid aliphatic xyl. Preferably, the aliphatic carboxylic acid comprises from 4 to 30 and preferably from 8 to 30 carbon atoms. It is preferably selected from hexanoic acid, heptanoic acid, octanoic acid, 2-ethyl hexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, acid tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexydecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, acid isoarachidic acid, octyldodecanoic acid, henicosanoic acid, docosanoic acid, and mixtures thereof. The aliphatic carboxylic acid is preferably branched. The aliphatic hydroxy carboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid having from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to to 20 hydroxyl groups, preferably 1 to 10 hydroxyl groups and more preferably 1 to 6 hydroxyl groups. The aliphatic hydroxy carboxylic acid ester is chosen from: a) partial or total esters of saturated linear monohydroxylated aliphatic monocarboxylic acids; b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids; c) partial or total esters of saturated monohydroxylated aliphatic polycarboxylic acids; d) partial or total esters of saturated polyhydroxylated aliphatic polycarboxylic acids; e) the partial or total esters of C2 to C16 aliphatic polyols reacted with a mono or polyhydroxylated aliphatic mono or poly carboxylic acid, and mixtures thereof. the diol dimer and diacid dimer esters, if appropriate, esterified on their (their) alcohol (s) or free acid (s) function (s) with acidic radicals or alcohols, especially dimer dilinoleate esters, such esters may in particular be chosen from the following INCI nomenclature esters: bis-behenyl / isostearyl / phytosteryl dimerdilinoleyl dimerdilinoleate (Plandool G), phytosteryl / isosteryl / cetyl / stearyl / behenyl dimerdilinoleate (Plandool H or Plandool S), and their mixtures. the hydrogenated rosinate esters, such as the dilinoleyl dimers of hydrogenated rosinate (Lusplan DD-DHR or DD-DHR from Nippon Fine Chemical), and mixtures thereof.

Advantageously, the pasty compound (s) preferably represents 0.1 to 80%, better still 0.5 to 60%, better still 1 to 30% and better still 1 to 20% by weight relative to the total weight of the composition.

Wax (s) According to a preferred embodiment, the composition according to the invention comprises at least one wax. The wax considered in the context of the present invention is generally a lipophilic compound, solid at room temperature (25 ° C.), with reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C. ° C up to 200 ° C and especially up to 120 ° C.

In particular, the waxes that are suitable for the invention may have a melting point greater than or equal to 45 ° C., and in particular greater than or equal to 55 ° C.

The waxes that may be used in the compositions according to the invention are chosen from waxes, solid, at room temperature of animal, vegetable, mineral or synthetic origin, and mixtures thereof. Illustrative waxes suitable for the invention include hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect wax, rice bran wax, Carnauba wax Candellila wax, Ouricury wax, Alfa wax, berry wax, shellac wax, Japanese wax and sumac wax; montan wax, orange and lemon waxes, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters. There may also be mentioned waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C -C -C fatty chains. Among these, there may be mentioned isomerized jojoba oil such as trans isomerized partially hydrogenated jojoba oil manufactured or marketed by Desert Whale under the trade reference Iso-Jojoba-50®, sunflower oil hydrogenated castor oil, hydrogenated coconut oil, hydrogenated lanolin oil, and di- (1,1,1-trimethylolpropane) tetrastearate sold under the name Hest 2T-4S® by the company HETERENE. Mention may also be made of silicone waxes (C30-45 ALKYL DIMETHICONE) and fluorinated waxes. It is also possible to use the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol sold under the names Phytowax Ricin 16L64® and 22L73® by the company SOPHIM. Such waxes are described in the application FR-A-2792190. As wax, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms) can be used, alone or as a mixture .

Such a wax is especially sold under the names "Kester Wax K 82 P®", "Hydroxypolyester K 82 P®" and "Kester Wax K 80 P®" by the company Koster Keunen. As micro-waxes that can be used in the compositions according to the invention, mention may be made in particular of carnauba micro-waxes such as that marketed under the name MicroCare 350® by the company Micro Powders, and synthetic wax waxes such as that marketed. under the name MicroEase 114S® by MICRO POWDERS, micro waxes consisting of a mixture of carnauba wax and polyethylene wax such as those marketed under the names Micro Care 300® and 310® by the company MICRO POWDERS , micro waxes consisting of a mixture of carnauba wax and synthetic wax such as that marketed under the name Micro Care 325® by the company Micro Powders, polyethylene micro waxes such as those sold under the names Micropoly 200® , 220®, 220L® and 250S® by MICRO POWDERS and polytetrafluoroethyl micro waxes lene such as those sold under the names Microslip 519® and 519 L® by the company Micro Powders. The composition according to the invention may comprise a wax content ranging from 0.1 to 30% by weight relative to the total weight of the composition, in particular it may contain from 0.5 to 20% by weight, more particularly from 1 to 15%.

Additional Filmoqene Polymer The composition may comprise, in addition to the copolymer described above, an additional polymer such as a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous deposit on a support, in particular on keratin materials. Among the film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers of radical type, polymers of natural origin and mixtures thereof. As film-forming polymer, mention may in particular be made of acrylic polymers, polyurethanes, polyamides, polyureas and cellulose polymers, such as nitrocellulose. The polymer may be associated with one or more auxiliary film-forming agents. Such a film-forming agent may be chosen from all the compounds known to those skilled in the art as being capable of fulfilling the desired function, and in particular be chosen from plasticizers and coalescing agents.

Lipophilic Gelling Agents According to one embodiment, the composition according to the invention may comprise at least one gelling agent. The gelling agents that may be used in the compositions according to the invention may be organic or inorganic, polymeric or molecular lipophilic gelling agents. As inorganic lipophilic gelling agents, there may be mentioned optionally modified clays, such as hectorites modified with a C 10 -C 22 ammonium chloride, such as hectorite modified with di-stearyl dimethyl ammonium chloride such as, for example that marketed under the name Bentone 38V® by the company ELEMENTIS. It is also possible to mention the optionally hydrophobic fumed silica surface with a particle size of less than 1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8th edition, 2000). They are, for example, sold under the references Aerosil R812® by the company Degussa, CAB-O-SIL TS-530® by the company Cabot, dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treatment of fumed silica in the presence of polydimethylsiloxane. or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by the company DEGUSSA, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by CABOT.

Among the lipophilic gelling agents that can be used in the compositions according to the invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates, in particular such as those sold under the names Rheopearl TL® or Rheopearl KL. ® by the company CHIBA FLOUR. Dyestuff The composition according to the invention may further comprise a dyestuff chosen from dyes, pigments, pearlescent agents and flakes well known to those skilled in the art. The dyestuffs may be present in the composition, in a content ranging from 0.01% to 50% by weight, relative to the weight of the composition, preferably from 0.01% to 30% by weight. By pigments, it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition. By nacres, it is necessary to understand particles of any iridescent form, in particular produced by certain molluscs in their shell or else synthesized. The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxides, and oxides of zinc, iron (black, yellow or red) or chromium, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder.

Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum. Mention may also be made of effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being covered or not with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and their mixtures. The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated with, inter alia, blue. ferric oxide or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It is also possible to use interferential pigments, in particular liquid crystal or multilayer pigments. The dyes may for example be chosen from water-soluble dyes, such as beet juice or methylene blue, for example.

Charges The composition according to the invention may also comprise one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight. By fillers, it is necessary to include particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or the texture of the composition. The fillers can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem), poly-13-alanine and polyethylene, tetrafluoroethylene polymer powders (Teflon® ), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industrie), copolymers of acrylic acid (Polytrap®). Dow Corning Company), precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metallic soaps organic carboxylic acid derivatives having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

According to a particular embodiment, said composition further comprises at least 5% by weight, preferably at least 10% by weight, or even at least 13% by weight of pulverulent phase (pigments, fillers) relative to the total weight of said composition.

ADDITIVES A cosmetic composition according to the invention may also comprise any additive usually used in the field concerned, for example chosen from gums, anionic, cationic, amphoteric or nonionic surfactants, silicone surfactants, gums, resins, dispersing agents, semi-crystalline polymers, antioxidants, essential oils, preservatives, perfumes, neutralizers, antiseptics, UV protective agents, cosmetic active agents, such as vitamins, moisturizing agents, emollients, and mixtures thereof.

It falls within the routine operations of those skilled in the art to adjust the nature and amount of the additives present in the compositions according to the invention, so that the desired cosmetic properties and stability properties of these they are not affected. The composition according to the invention may be in liquid or solid form.

By solid cosmetic compositions is meant compositions whose hardness at 20 ° C and at atmospheric pressure (760 mm Hg) is greater than or equal to 30 Nm-1 when measured according to the protocol described below.

Protocol for Measuring Hardness: The hardness of the composition is measured according to the following protocol: The lipstick stick is stored at 20 ° C. for 24 hours before measuring the hardness. The hardness can be measured at 20 ° C. by the so-called "butter-cutting thread" method, which consists in transversely cutting a stick of product, preferably cylindrical of revolution, with the aid of a rigid tungsten wire. 250 μm diameter by moving the wire relative to the stick at a speed of 100 mm / min. The hardness of the samples of compositions of the invention, expressed in Nm-1, is measured by means of a DFGS2 dynamometer marketed by INDELCO-CHATILLON. The measurement is repeated three times and averaged. The average of the three values read using the dynamometer mentioned above, denoted Y, is given in 25 grams. This average is converted to Newton and divided by L which represents the highest dimension traversed by the wire. In the case of a cylindrical stick, L is equal to the diameter (in meters). The hardness is converted to Nm-1 by the equation below: (Yx 10-3 x 9.8) / L For a measurement at a different temperature, the stick is kept at this new temperature for 24 hours before the measurement.

The composition according to the invention is in solid form. By "solid" is meant a composition whose hardness measured according to the preceding protocol is greater than or equal to 30 Nm-1 at the temperature of 20 ° C and at atmospheric pressure (760 mmHg).

According to this measurement method, the composition according to the invention preferably has a hardness at 20 ° C and at atmospheric pressure greater than or equal to 40 Nm-1, preferably greater than 50 Nm-1.

Preferably, the composition according to the invention has in particular a hardness at 20 ° C of less than 500 Nm-1 in particular less than 400 Nm-1, preferably less than 300 Nm-1.

PHYSIOLOGICALLY ACCEPTABLE MEDIUM By "physiologically acceptable medium" is meant a medium that is particularly suitable for applying a composition of the invention to the skin. The physiologically acceptable medium is generally adapted to the nature of the medium to which the composition is to be applied, as well as to the appearance under which the composition is to be packaged. A composition of the invention may be anhydrous or in the form of a dispersion or emulsion. An emulsion may have an oily or aqueous continuous phase. Such an emulsion may be, for example, an inverse emulsion (W / O) or a direct emulsion (O / W), or a multiple emulsion (W / O / W or H / E / H). In the case of emulsions, inverse emulsions (W / O) are preferred.

Preferably, the composition according to the invention comprises less than 3%, or better, less than 1% water by weight relative to the total weight of the composition. More preferably the composition is completely anhydrous. By anhydrous is meant in particular that the water is preferably not deliberately added to the composition but may be present in trace amounts in the various compounds used in the composition. Those skilled in the art may choose the appropriate dosage form, and its method of preparation, on the basis of his general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support and on the other hand, the intended application of the composition. A composition according to the invention may, in particular, be in the form of a care or make-up composition, in particular for making up the skin, the lips or the eyelashes. According to a first preferred embodiment, the composition according to the invention is a lipstick. According to a second preferred embodiment, the composition according to the invention is a foundation.

The invention also relates to a cosmetic process for the care or makeup of keratinous substances, in particular the skin and / or the lips, comprising the application to said keratin materials, and in particular the skin and / or the lips of a composition as defined previously.

The present invention is presented in more detail in the examples described hereinafter which are only provided by way of illustration of the invention and should not be interpreted as limiting the invention. EXAMPLES Example 1 Preparation of a Copolymer of Poly (Isobornyl Acrylate / Disobornyl Methacrylate / Isobutyl Acrylate / Acrylic Acid) 300 g of isododecane are introduced into a 1-liter reactor, then the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C in 1 hour.

105 g of isobornyl methacrylate, 105 g of isobornyl acrylate and 1.8 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox®) are then added at 90 ° C. and over 1 hour. 141 by Akzo Nobel). The mixture is maintained for 1 hour at 90 ° C. 75 g of isobutyl acrylate, 15 g of acrylic acid and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-di are then introduced into the above mixture, still at 90 ° C. and over 30 minutes. methyl hexane. The mixture is kept at 90 ° C. for 3 hours, then the mixture is cooled. A 50% solution of copolymer active material in isododecane is obtained.

A copolymer is obtained comprising a first poly (isobornyl acrylate / isobornyl methacrylate) block or block having a Tg of 128 ° C., a second poly (isobutyl acrylate / acrylic acid) block having a Tg of -9 ° C. C and an intermediate block which is a random copolymer of isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate / acrylic acid. The Tg of the copolymer is 74 ° C. This is theoretical Tg calculated by Fox law.

EXAMPLE 2 Distillation of the Synthesis Solvent (Isododecane) by Adding Octyldodecyl Neopentanoate The solution obtained in Example 1 is heated to 130 ° C. under a vacuum of 100 mbar in order to evaporate the isododecane while simultaneously adding the neopentanoate. octyldodecyl. The entirety of the isododecane was substituted by as much octyldodecyl neopentanoate by weight.

The use of octyldodecyl neopentanoate makes it possible to evaporate all of the isododecane, this latter possibly remaining only in the state of residual traces. There is thus obtained a 50% solids copolymer solution in 50% octyldodecyl neopentanoate. Examples 3 to 6: Liquid Lipstick:

A liquid lipstick composition 3 according to the invention comprising a sequenced ethylenic polymer and a polyester and three comparative compositions 4,5 and 6 which are not part of the invention comprising respectively only a sequenced ethylene polymer and only a polyester. Compositions 3-6 comprise the following ingredients (percentages by weight): COMPOUNDS Composition Composition Composition Composition 3 according to Comparative Comparative Comparative Invention Pha PENTAERYTHRITYL 18.93 18.93 18.93 18.93 TETRAISOSTEARATE (PRISORINE 3631 commercial ref CRODA) 20 Pha TRIDECYL 13.77 13.77 13.77 13.77 se B TRIMELLITATE (LIPO CHEMICALS commercial ref LIPONATE TDTM) ISOPROPYLPARABE 0.61 0.61 0.61 0.61 N ( and) ISOBUTYLPARABEN (and) BUTYLPARABEN (ISP LIQUAPAR OIL ref) BHT 0.06 0.06 0.06 0.06 DIISOSTEARYL 13.14 13.14 13.14 MALATE (commercial ref. SCHERCEMOL DISM from LUBRIZOL) POLYBUTENE (ref 15,50 15,50 15,50 15,50 commercial: INDOPOL H 100 from INEOS) Pentaerythritol 20 / 21,22 - 33,62 27,42 benzoic acid 4 / isostearic acid 56 / isophthalic acid 20 (such as prepared in Example 2 of EP-A-1870082) Poly (Methacrylate 12.40 33.62 - - isobornyl-co-isobornyl acrylate-isobutyl co-acrylate acrylic acid) 50% active ingredient in 50% octyldodecyl neopentanoate as prepared according to example 2 above octyldodecyl - - - 6.20 neopentanoate Pha RED 7 0.24 0.24 0.24 0 OXIDES 0.31 0.31 0.31 0.31 TITANIUM DIOXIDE 0.16 0.16 0.16 0.16 Pha SILICA DIMETHYL 3.36 3.36 3.36 3.36 se D SILYLATE (commercial ref.) AEROSIL R 972 of 10 EVONIK DEGUSSA Pha Perfume 0.31 0.31 0.31 0.31 se E TOTAL 100.00 100.00 100.00 100.00 Process of preparation: The compositions 3 to 6 are obtained according to the following protocol: Firstly, the phase C pigments are milled in part of the phase A to the tri-roll mill. The pigmented mash is then added to the ingredients of phase B. The whole is heated to 80 ° C with stirring under Rayneri. The silica is added to the mixture maintained at 80 ° C and stirred to homogenize well. Then allowed to cool to room temperature and the juice is then packaged in a boil with an applicator. Composition Evaluation Composition 3 according to the invention At the application on the lips: very soft, very glossy, slightly sticky. After 2 hours: good brightness, very little sticky deposit. Composition 4 comparative A application on the lips: very sticky, bright, quite eye-catching. After 2h: good gloss, very sticky deposit. Comparative composition With application to the lips: very sticky, glossy, very eye-catching, medium-homogeneous deposit. After 2h: good gloss, very sticky deposit. Composition 6 comparative application to the lips: deposit quite bright, deposit little sticky.

After 2 hours, poor gloss performance, very little sticky deposit. Evaluation: The compositions 3, 4, 5 and 6 were applied to the lips.

The three compositions 3, 4, 5 have good deposition behavior over time, as well as a good level of gloss and shine, especially 2 hours after application. With the compositions 3 and 4, a homogeneous deposit is obtained, whereas with the composition 5, the deposit obtained is less homogeneous. Comparative compositions 4 and 5 are very acccueilous and difficult to apply, unlike composition 3 according to the invention. In addition, the deposits made with the comparative compositions 4 and 5 are very sticky on the lips. On the other hand, the deposit made with the composition 3 according to the invention is only slightly tacky. The composition 6 is only slightly tacky, immediately at the application or 2 hours after the application, but has a poor resistance to the color and gloss of the deposit on the lips, in particular with respect to the composition 1 according to the invention.

All of these results show that the combination of a polyester with a block ethylenic copolymer makes it possible to obtain cosmetic compositions, in particular anhydrous lipstick type, having good sliding properties on application, comfort , shine, hold and non-stickiness.

Claims (15)

REVENDICATIONS1. Cosmetic care and / or makeup composition for keratin materials comprising, in a physiologically acceptable medium, at least one fatty phase and containing: (i) at least one block ethylenic copolymer (also called sequenced ethylenic polymer), containing at least a first a sequence having a glass transition temperature (Tg) greater than or equal to 40 ° C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a transition temperature vitreous temperature greater than or equal to 40 ° C, and at least one second block having a glass transition temperature of less than or equal to 20 ° C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C, said first sequence and said second sequence being connected to each other by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second monomers constituting the second block, and said block copolymer having a higher polydispersity index I at 2 and (ii) at least one polyester obtainable by reaction of: - a tetraol having from 4 to 10 carbon atoms; - a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms; a cyclic dicarboxylic acid having from 6 to 12 carbon atoms; and an aromatic monocarboxylic acid having 7 to 11 carbon atoms. 2. Composition according to the preceding claim, characterized in that the one or more first monomers of the block copolymer, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, are chosen. among: - methacrylates of formula CH2 = C (CH3) -OOOR1 in which R1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, a C4 to C12 cycloalkyl group; in which R 2 represents a C 4 to C 12 cycloalkyl group, the (meth) acrylamides of formula: ## STR1 ## in which R 1 and R 8, which are identical or different, each represent a hydrogen atom; hydrogen or a linear or branched C 1 -C 12 alkyl group, or R 1 represents H and R 8 represents a 1,1-dimethyl-3-oxobutyl group, and R 'denotes H or methyl. and in that the second monomer or monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C., are chosen from: acrylates of formula CH 2 = CHCOOR 3, R 3 represents a linear or branched C 1 to C 12 unsubstituted alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms chosen from O, N, S are optionally intercalated; methacrylates of formula CH2 = C (CH3) -COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group in which one or more heteroatoms selected from among 0, N and (or) are optionally intercalated; S; vinyl esters of formula R 5 -CO-O-CH =CH 2 where R 5 represents a linear or branched C 4 to C 12 alkyl group; vinyl alcohol and C4 to C12 alcohol ethers; C4 to C12 N-alkyl acrylamides, such as N-octylacrylamide; and mixtures thereof. 3. Composition according to any one of the preceding claims, characterized in that said block copolymer is such that the first block is obtained from at least one acrylate monomer of formula CH2 = CH-OO0R2 in which R2 represents a cycloalkyl group C4 to C12 and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C4 to C12 cycloalkyl group, andthe second block is obtained from at least one second monomer such as the homopolymer obtained has a glass transition temperature of less than or equal to 20 ° C, and an additional monomer of acrylic acid type. 4. Composition according to the preceding claim, characterized in that R2 and R'2 represent independently or simultaneously an isobornyl group. 5. Composition according to any one of the preceding claims, characterized in that said copolymer comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate, from 10 to 30% by weight of isobutyl acrylate and from 2 to 30% by weight of isobutyl acrylate and from 2 to 30% by weight of isobutyl acrylate. 10% by weight of acrylic acid. 6. Composition according to any one of the preceding claims, characterized in that it comprises from 0.5 to 40% by weight of block copolymer active material, and advantageously from 1 to 40% by weight, in particular from 2 to 30% by weight. % by weight, or even 2 to 20% by weight of copolymer active material relative to the total weight of the composition. 7. Composition according to one of the preceding claims, characterized in that the said (s) polyester (s) is / are likely to be obtained (s) by reaction: - from 10 to 30% by weight of a tetraol having from 4 to 10 carbon atoms, in particular selected from diglycerol and pentaerythritol; from 40 to 80% by weight of a saturated monocarboxylic acid, linear or branched, having from 9 to 23 carbon atoms, in particular chosen from stearic acid and isostearic acid; from 5 to 30% by weight of a cyolic dicarboxylic acid having from 6 to 12 carbon atoms, in particular from an isophthalic acid, from 0.1 to 10% by weight of an aromatic monocarboxylic acid having from 7 to at 11 carbon atoms, in particular selected from benzoic acid and 4-tert-butyl benzoic acid, and the contents being expressed as a percentage by weight relative to the total weight of the polyester. 8. Composition according to any one of the preceding claims, characterized in that the said polyester (s) is / are chosen from among the polyesters of benzoic acid / isophthalic acid / isostearic acid / pentaerythritol , benzoic acid / isophthalic acid / stearic acid / pentaerythritol polyesters, and mixtures thereof. 9. Composition according to any one of the preceding claims, characterized in that the polyester and the block ethylenic copolymer are present in a mass ratio polyconsendat / ethylenic block copolymer between 1/50 and 50, preferably between 0.1 and 10. , more preferably 1/5 and 5. 10 10. Composition according to any one of the preceding claims, characterized in that it comprises from 1 to 60% by weight of polyester, in particular from 2 to 50% by weight, and more particularly from 3 to 45% by weight, from 4 to 35% by weight, and more preferably from 5 to 30% by weight of polyester relative to the total weight of the composition. 11. Composition according to any one of the preceding claims, characterized in that it comprises at least one non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. 12. Composition according to any one of the preceding claims, characterized in that it comprises at least one solid fatty substance selected from waxes and pasty fatty substances, and mixtures thereof. 13. Composition according to any one of the preceding claims, characterized in that it is anhydrous. 14. Composition according to any one of the preceding claims, characterized in that it is free of volatile oil whose flash point is less than or equal to 80 ° C. 15. A cosmetic process for the care and / or makeup of keratin materials, comprising the application to said materials of at least one layer of a composition as defined according to any one of claims 1 to 14.