FR2946874A1 - Composition for cosmetic method comprises ethylenic block copolymer having first and second blocks of specific glass transition temperatures, nonvolatile hydrocarbon ester oil of specific molar mass and specific amount of volatile oil - Google Patents

Abstract

Composition (C1) comprises: in medium, ethylenic block copolymer comprising first block(s) having glass transition temperature (Tg) of >= 40[deg] C, resulting from first monomer that forms homopolymer with Tg of >= 40[deg] C, and second block(s) having Tg of = 20[deg] C, resulting from second monomer that forms homopolymer with Tg of = 20[deg] C, connected by segment having the monomer(s), and block copolymer has polydispersity index of greater than 2; nonvolatile hydrocarbon ester oil(s) having molar mass of less than 650 g/mol; and volatile oil having flash point of = 80[deg] C (less than 10 wt.%). A composition (C1) comprises: in a physiological medium, at least, one ethylenic block copolymer comprising at least one first block having a glass transition temperature (Tg) of >= 40[deg] C and resulting, in whole or in part, from at least one first monomer which is such that a homopolymer prepared from these monomers has a Tg of >= 40[deg] C, and at least one second block having a Tg of = 20[deg] C and resulting, in whole or in part, from at least one second monomer which is such that a homopolymer prepared from these monomers has a Tg of = 20[deg] C, the first block and the second block are connected to one another via a random intermediate segment comprising at least one of the first constituent monomers of the first block and at least one of the second constituent monomers of the second block, and the block copolymer has a polydispersity index (I) of greater than 2; and at least one nonvolatile hydrocarbon ester oil comprising >= 16 carbon atoms and having a molar mass of less than 650 g/mol; where the composition comprises volatile oil having a flash point of = 80[deg] C (less than 10 wt.%). An independent claim is included for cosmetic method involving: application of the composition (C1) to a keratinous substance.

Description

The present invention relates to a cosmetic composition for makeup and / or care of the skin or lips. In the field of cosmetics, the development of formulations having both good properties in terms of application and comfort, and satisfactory properties in terms of comfort, brightness, hold, especially the holding of the shine and color is a permanent goal. It is known from EP 1 621 229 lipstick compositions comprising a so-called tackifying hydrocarbon resin, such as hydrogenated indene / methylstyrene / styrene copolymers sold under the name REGALITE by the company Eastman Chemical in order to obtain a brilliant deposit on the lips. However, stick-type solid compositions containing these resins are generally hard and therefore difficult to apply to the skin or the lips; they are unctuous and disintegrate poorly on the skin or lips and lead to the formation of a thin deposit. The deposit is not thick enough, it deteriorates more quickly over time (especially after 1 hour) and thus has a poor performance, thereby inducing a poor performance of the color and brightness of the deposit. Moreover, the deposit formed on the skin and the lips is not very comfortable because of the hard nature of the resin and the fineness of the deposit.

Consequently, there remains to this day a need for a composition for makeup and / or care of the lips, making it possible to obtain a thick and homogeneous deposit which is easily deposited on the lips, and exhibiting a holding of the color and the satisfactory brightness, on application and over time, especially 1 hour after application. The inventors have discovered that such a composition could be obtained by combining with a hydrocarbon resin a particular ethylenic block copolymer. Such a composition applied to the skin and / or the lips, makes it possible to obtain a deposit (in particular of make-up) creamy, thick and homogeneous, having good properties of comfort (absence of feeling of tightness, dryness), and holding Thus, according to a first aspect, the present invention relates to a solid cosmetic composition comprising, in a physiologically acceptable medium, at least: a) a block ethylenic copolymer, 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 sequence having a glass transition temperature of less than or equal to 20 ° C and resulting from t otality or in part of 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 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 constituent monomers of the second block, and said block copolymer having a polydispersity index I of greater than 2, and b) a block of weight number average molecular weight less than or equal to 10000 g / mol chosen from rosin, rosin derivatives, hydrocarbon resins and mixtures thereof, c) at least one solid fatty substance.

The invention also relates, in another aspect, to a cosmetic process for making up the skin or the lips, comprising applying to the skin or the lips a composition as defined above. Finally, the subject of the invention is the use of a composition as described above for obtaining a make-up of the skin or of the lips having comfort and / or gloss and / or gloss-holding properties, and / or of color keeping. Tackifying Resin The composition according to the invention comprises at least one resin chosen from rosin, rosin derivatives, hydrocarbon resins and mixtures thereof. The resin used in the composition according to the invention (also called tackifying resin) preferably has a number average molecular weight of less than or equal to 10,000 g / mol, in particular ranging from 250 to 10,000 g / mol, preferably less than or equal to at 5,000 g / mol, in particular ranging from 250 to 5,000 g / mol, better still, less than or equal to 2,000 g / mol, especially ranging from 250 to 2,000 g / mol and even more preferably less than or equal to 1,000 g / mol mol especially ranging from 250 to 1000 g / mol. The number average molecular weights (Mn) were determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). The resin of the composition according to the invention is advantageously a so-called tackifying resin. Such resins are especially described in the Handbook of Pressure Sensitive Adhesive, edited by Donatas Satas, 3rd ed., 1989, p. 609-619. The resin of the composition according to the invention is chosen from rosin, rosin derivatives, hydrocarbon resins and mixtures thereof. Rosin is a mixture comprising mainly organic acids called rosin acids (mainly abietic and pimaric type acids). There are three types of rosin: rosin ("gum rosin") obtained by incision on live trees, wood rosin ("wood rosin") which is extracted from stumps or pine wood, and tall ("tall oil rosin") which is obtained from a by-product from the production of paper. The rosin derivatives may be derived in particular from the polymerization, hydrogenation and / or esterification (for example with polyhydric alcohols such as ethylene glycol, glycerol, pentaerythritol) of rosin acids. There may be mentioned, for example, the rosin esters marketed under the reference FORAL 85, PENTALYN H and STAYBELITE ESTER 10 by the company HERCULES; SYLVATAC 95 and ZONESTER 85 by ARIZONA CHEMICAL or UNIREZ 3013 by UNION CAMP.

The hydrocarbon resins are chosen from low molecular weight polymers which can be classified, according to the type of monomer they comprise, as: - indene hydrocarbon resins such as the resins resulting from the polymerization in majority proportion of monomer indene and in proportion minority of monomer selected from styrene, methylindene, methylstyrene and mixtures thereof. These resins may optionally be hydrogenated. These resins may have a molecular weight ranging from 290 to 1150 g / mol. As examples of indene resins, mention may be made of those sold under the reference ESCOREZ 7105 by Exxon Chem., NEVCHEM 100 and NEVEX 100 by Neville Chem., NORSOLENE S105 by Sartomer, PICCO 6100 by Hercules and RESINALL. by the company Resinall Corp., or the hydrogenated indene / methylstyrene / styrene copolymers sold under the name REGALITE by the company Eastman Chemical, in particular REGALITE R 1100, REGALITE R 1090, REGALITE R-7100, REGALITE R1010 HYDROCARBON RESIN, REGALITE R1125 HYDROCARBON RESIN. aliphatic pentanediene resins such as those resulting from the polymerization mainly of 1,3-pentanediene monomers (trans or cis piperylene) and of a minor monomer chosen from isoprene, butene, 2-methyl-2-butene, pentene, 1,4-pentanediene and mixtures thereof. These resins may have a molecular weight ranging from 1000 to 2500 g / mol. Such resins of 1,3-pentanediene are sold, for example, under the references PICCOTAC 95 by the company Eastman Chemical, ESCOREZ 1304 by the company Exxon Chemicals, NEVTAC 100 by the company Neville Chem. or WINGTACK 95 by the company Goodyear; mixed pentanediene and indene resins, which result from the polymerization of a mixture of pentanediene and indene monomers such as those described above, for example the resins marketed under the reference ESCOREZ 2101 by the Exxon Chemicals., NEVPENE 9500 by Neville Chem., HERCOTAC 1148 by Hercules., Norsolene A 100 by Sartomer, WINGTACK 86, WINGTACK EXTRA and WINGTACK PLUS by Goodyear, - diene dimer resins from cyclopentanediene such as those resulting from the polymerization of the first monomer chosen from indene and styrene, and the second monomer chosen from cyclopentanediene dimers such as dicyclopentanediene, methyldicyclopentanediene, the other dimers of pentanediene, and mixtures thereof. These resins generally have a molecular weight ranging from 500 to 800 g / mol, such as for example those sold under the reference BETAPRENE BR 100 by Arizona Chemical Co., NEVILLE LX-685-125 and NEVILLE LX-1000 by the company Neville Chem., PICCODIENE 2215 by Hercules, PETRO-REZ 200 by Lawter or RESINALL 760 by Resinall Corp. ; the diene resins of the dimers of isoprene, such as the terpenic resins resulting from the polymerization of at least one monomer chosen from α-pine, (3-pinene, limonene, and mixtures thereof, these resins may have a weight These resins are sold, for example, under the name PICCOLYTE A115 and S125 by the company Hercules, ZONAREZ 7100 or ZONATAC 105 LITE by the company ARIZONA Chem, the hydrogenated C6-C20 polyolefins, such as those marketed under the names EASTOTAC H-142W, EASTOTAC H-142R, and EASTOTAC H-100W by Eastman Chemical Co.

According to a preferred embodiment, the resin is chosen from indene hydrocarbon resins, in particular hydrogenated indene / methylstyrene / styrene copolymers sold under the name REGALITE by the company Eastman Chemical, such as REGALITE R 1100, REGALITE R 1090, REGALITE R -7100, REGALITE R1010 HYDROCARBON RESIN, REGALITE R1125 HYDROCARBON RESIN.

The tackifying resin may be present in the composition according to the invention in a content ranging from 0.1 to 45% by weight, relative to the total weight of the composition, preferably ranging from 0.5 to 30% by weight, more preferably ranging from 1 to 15% by weight. Preferably, the weight ratio resin of average molecular weight less than or equal to 10000 g / mol / block ethylenic copolymer is between 1/20 and 20/1, preferably between 1/10 and 10/1, or better between 1/5 and 5/1.

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 mono-functional 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 (by macromonomer is meant a mono-functional monomer having a pendant group of polymeric nature, and preferably having a molecular weight greater than 500 g / mol, or a polymer comprising 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 (25 ° 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, in the case of 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%, more preferably 95%, and most preferably 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 (25 ° 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 ° C. and 50 + 10% relative humidity. A film approximately 100 m thick in which are cut rectangular specimens (for example with a punch) of a width of 15 mm and a length of 80 mm are then obtained. This sample is subjected to tensile stress with the aid of 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 (Io) of the specimen. The instantaneous recovery R 1 is determined as follows: - the specimen is stretched 30% (cmax), that is to say about 0.3 times its length - the stress is released by imposing an equal speed of return at the tensile speed, ie 50 mm / min and the residual elongation of the test piece is measured in percentage, after return to zero load stress (ci). The instantaneous recovery in% (R1) is given by the following formula: ## EQU1 ## To determine the delayed recovery, the rate of residual elongation of the specimen in percentage (e2h), 2 hours after return to the zero load stress. The delayed recovery in% (R2h) is given by the formula below:

R2 h (Emax - E2h) / Emax) X 100 For purely indicative purposes, a polymer according to one embodiment of the invention preferably has an instantaneous recovery R; 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 or equal to 2.8 and in particular ranging from 2.8 to 6. The polydispersity index I of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn. The weight average (Mw) and number (Mn) molar masses were 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, 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 500,000 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 2.8 and in particular, ranging from 2.8 to 6. First sequence having a T2 greater than 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 ranging from 50 ° C. to 120 ° C., and better greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C.

The indicated glass transition temperatures of the first and second sequences may 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, 3 '. ed, 1989, John Wiley, according to the following relationship, known as Fox's Law:

1 / Tg = E / Tg;), where Mi 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 sequences is generally greater than 10 ° C, preferably greater than 20 ° C, and more preferably greater than 30 ° C.

In the present invention, it is meant by the expression comprised between ... and ..., an interval of values whose mentioned terminals 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 of 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 10 40 ° C. This sequence can also be called a 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 sequence 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 such 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 -50 ° C to 0 ° C to, as described below.

The first monomers whose homopolymers have a glass transition temperature greater than or equal to 40 ° C. are preferably chosen from the following monomers, also called main monomers: methacrylates of formula CH 2 = C (CH 3) COOR 1 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, or R 1 represents a C 4 to C 10 cycloalkyl group, preferably a C 8 to C 14 cycloalkyl ring; , such as isobornyl methacrylate, - acrylates of formula CH2 = CH-COOR2 in which R2 represents a C4-C12 cycloalkyl group such as an isobornyl group or a tert-butyl group, - (meth) acrylamides of formula : R 'R7

Where R7 and R8, which are identical or different, each represent a hydrogen atom or a linear or branched C1-C15 alkyl group, such as a n-butyl, t-butyl, isopropyl, isohexyl or isooctyl group, or isononyl; or R7 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 CH 2 CHCH-COOR 2 and at least one methacrylate monomer of formula CH 2 CC (CH 3) -COOR 2 in which R 2 represents a C 4 to C 10 cycloalkyl group. preferably a C -C 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 CH 2 CHCH-COOR 2 in which R 2 represents a C 4 to C 14 cycloalkyl group, preferably a C 8 cycloalkyl group C12, such as isobornyl, ii) and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C4 to C14 cycloalkyl group, preferably a group C 8 to C 12 cycloalkyl, such as isobornyl.

According to one embodiment, the first block is obtained from at least one acrylate monomer of formula CH2 = CH-COOR2 in which R2 represents a C8-C12 cycloalkyl group, such as isobornyl, and from minus a methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C8-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 isobornyl methacrylate / 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 below 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 a flexible 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:

acrylates of formula CH2 = CHCOOR3, R3 representing a linear or branched C1-C18 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 14 unsubstituted alkyl group in which one or more heteroatoms chosen from 0 are optionally intercalated; N 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 14 alkyl group; vinyl alcohol and C 4 to C 14 alcohol ethers; C 4 to C 14 alkyl acrylamides, such as N-octyl acrylamide, and mixtures thereof.

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 are located 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) -OOR6 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-C18 alkyl group, wherein or optionally interspersed with one or more heteroatoms selected from O, 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 CH 2 = CHCOOR 10, R 10 representing a linear or branched C 1 -C 14 alkyl group substituted with one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or Rio represents a C1-C12-O-POE (polyoxyethylene) alkyl with repeating 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) -COOR1 wherein R1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group; - (meth) acrylamides of formula: R 'R7

Wherein R7 and R8, which are identical or different, each represents a hydrogen atom or a linear or branched C1-C15 alkyl group, such as a n-butyl, t-butyl, isopropyl, isohexyl or isooctyl group; , or isononyl; or R7 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 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 solid cosmetic composition for the makeup and / or care of keratin materials comprising, in a physiologically acceptable medium, at least one copolymer comprising at least one acrylate monomer of formula CH 2 = CH- COOR2 wherein R2 represents a C8-C10 cycloalkyl group and / or at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C8-C15 cycloalkyl group, at least one second acrylate monomer of formula CH 2 = CHCOOR 3, in which R 3 represents a linear or branched C 1 to C 14 unsubstituted alkyl group, with the exception of the tert-butyl group, and at least one acrylic acid monomer, at least one resin of number average molecular weight less than or equal to 10000 g / mol chosen from rosin, rosin derivatives, hydrocarbon resins and mixtures thereof, and at least one solid fatty substance.

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 acrylic acid.

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, based on 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 and second sequences 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 additional monomer (s), remaining available after their polymerization at a conversion rate of at most 90% to form the first sequence, ii) and second monomer (s) 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 into 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, it comprises a statistical distribution of the first monomer (s) and second monomer (s) as well as any additional monomer (s) present.

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

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. is chosen from organic peroxides comprising from 8 to 30 carbon atoms, the initiator used is preferably 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane sold under the reference TrigonoX 141 by the company 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, alcohols xyamines, 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 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 a portion of the initiator is then poured in a first casting. that 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 of the polymerization initiator, said at least one second glass transition monomer less than or equal to 20 ° 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 cooled to room temperature. Preferably, the copolymer may be prepared by free radical polymerization, in particular by a process comprising mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one lower glass transition monomer. or at 20 ° C, at least one acrylate monomer of formula CH2 = CH-COOR2 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, according to the following stage sequence: a portion of the polymerization solvent and possibly a part of the initiator and monomers of the first casting, which mixture is poured into the reactor, are poured into the reactor; the reaction mixture is heated to a reaction temperature of between 60 and 120 ° C., the at least one acrylate monomer of formula CH 2 = CH-COOR 2 and at least one of my omere methacrylate of formula CH2 = C (CH3) -COOR'2 as monomers of Tg greater than or equal to 40 ° C, and optionally a part of the initiator which is allowed to react for a duration T corresponding to a 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 room 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 Wherein R2 represents a C4 to C10 cycloalkyl group, and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R'2 represents a C4 to Ciz cycloalkyl group, in the sequence of 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-COOR2 and said at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2, as monomer of Tg greater than or equal to 40 ° C, which is allowed to react for a period 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.

The synthetic solvent used for the polymerization of the film-forming copolymer is generally chosen from volatile oils whose flash point is less than 80 ° C., such as isododecane, for example. According to a preferred embodiment of the invention, the composition contains a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, preferably octyldodecylneopentanoate.

In particular, the block copolymer can be used in the composition in the presence of this ester oil, especially during the synthesis of this block copolymer, it is thus possible to proceed by distillation of the synthesis solvent, optionally under vacuum. And addition of the nonvolatile hydrocarbon ester oil.

This distillation 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) can be carried out with simultaneous addition or in the presence in the mixture before the distillation of a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650. g / mol. 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 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.

Non-volatile hydrocarbon ester oil:

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 comfort properties (No feeling of tightness or dryness and gloss.) By oil is meant a non-aqueous compound, liquid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg). 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.

Hydrocarbon oil is understood to mean an oil formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and not containing silicon or fluorine atoms. By hydrocarbon ester oil is meant a hydrocarbon oil comprising at least one ester group.

As non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass 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 in particular octanoic acid, heptanoic acid, lanolic acid, oleic acid, lauric acid, stearic acid such as propylene glycol dioctanoate, propylene glycol monoisostearate, neopentyl glycol diheptanoate, esters as R1000R2 oils in which RI represents the residue of a linear or branched fatty acid having from 4 to 40 carbon atoms and R2 represents a particularly branched hydrocarbon chain containing from 4 to 40 carbon atoms provided that RI R 2 is 16, for example purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alcohol benzoate, ethyl 2-hexyl palmitate, octyl neopentanoate dodecyl, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, 2-octyldodecyl 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 R10OOR2 synthetic esters in which R1 represents the residue of a linear or branched fatty acid comprising from 4 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched hydrocarbon chain containing from 4 to 40 carbon atoms, are such that R1 and R2 is 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 at a molecular weight 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.

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, and in particular of nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol , 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 non-volatile hydrocarbon ester oil is less than 1, preferably less than 0.75, or better still less than 0.5, and especially greater at 0.1.

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 consisting mainly of carbon and hydrogen atoms and not containing a silicon or fluorine atom, and possibly comprising one or more functions chosen from 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, petrolatum, 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, 25 - hydrogenated polyisobutylenes such as Parléam marketed by the company NIPPON OIL FATS, PANALANE H-300 E marketed or manufactured by the company AMOCO (MW = 1340 g / mol), the VISEAL 20000 marketed or manufactured by the company SYNTEAL (MW = 6000 g / mol), REWOPAL PIB 1000 marketed or manufactured by WITCO (MW = 1000 g / mol), 30 - polydecenes and hydrogenated polydecenes such as: PURESYN 10 (MW = 723 g / mol), PURESYN 150 (MW = 9200 g / mol) marketed or manufactured by MOBIL CHEMICAL S, 2 / vinylpyrrolidone / 1-hexadecene copolymers, such as for example that sold under the name ANTARON VU216 (also called Ganex V216) by the company ISP (MW = 7300 g / mol), 3 / the hydrocarbon ester oil having a mass molar 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 polyglyceryl-2 triisostearate (MW = 965 g / mol), aromatic esters such as tridecyl trimellitate (MW = 757 g / mol), esters of fatty alcohol or branched C24-C28 fatty acids, those described in application EP-AO 955 039, and in particular triisoarachidyl citrate (MW = 1033.76 g / mol), pentaerythrityl tetraisonanoate (MW = 697 g / mol), glyceryl triisostearate (MM = 891 g / mol), glyceryl 2-decyl tetradecanoate (MW = 1143 g / mol), pentaerythritis tetraisostearate tyl (MW = 1202 g / mol), polyglyceryl -2 tetraisostearate (MW = 1232 g / mol) or pentaerythrityl tetra decyl tetradecanoate (MW = 1538 g / mol), a polyester resulting from the 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 castor oil of succinic acid 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 the polyglyceryl-2 isostearate copolymer dimerdilinoleate (Hailucent ISDA), the esters of diol dimer and diacid dimer compound 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 diacid residue hydrogenated dilinoleic, and h represents a varian integer t 1 to 9, in particular the esters of dilinoleic diacids and of dilinoleic diol dimers marketed by 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 (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, during and / or at the end of the silicone chain, groups each having from 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, by weight. relative to the total weight of the composition.

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

According to a preferred embodiment, the composition contains less than 10% by weight of volatile oil whose flash point is less than or equal to 80 ° C., or better still less than 5% relative to the total weight of the composition or else is free of volatile oil whose flash point is less than or equal to 80 ° C, such as isododecane. The flash point is measured in particular 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 room 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 room temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular from 0.degree. , 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. at 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 C 8 -C 14 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 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 the standard 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 mixtures thereof. pentaerythritol ether and polyethylene 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- Pentaerythrityl Ether), and mixtures thereof, and more especially the PEG-5 Pentaerythrityl Ether mixture, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name Lanolide by the company Vevy, a mixture in which the constituents are in a ratio by weight 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 6 -C 30 alkyl group • homopolymers and copolymers of vinyl esters having C 6 -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; pentaerythritol esters; non-crosslinked polyesters resulting from the polycondensation between a dicarboxylic acid or a linear or branched C 4 -C 50 polycarboxylic acid and a C2-050 diol or polyol, the ester aliphatic esters resulting from the esterification of a hydroxycarboxylic acid ester Aliphatic acid with an aliphatic carboxylic acid. 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, isoarachidic acid, octyldodecanoic acid, henicosanoic acid, docosanoic acid, and mixtures thereof. The aliphatic carboxylic acid is preferably branched. The aliphatic hydroxycarboxylic 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 more preferably from 12 to 28 carbon atoms, and from 1 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 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 C8-C32 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, hydrogenated 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 application FR-A-2792190.

As wax, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms), alone or in admixture, can be used. Such a wax is in particular 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 micro-waxes such as that marketed under the name MicroEase 114S by the company MICRO POWDERS, the micro waxes consisting of a mixture of carnauba wax and polyethylene wax such as those sold 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 sold under the name Micro Care 325 by the company Micro Powders, the polyethylene micro-waxes such as those sold under the names Micropoly 200, 220, 220L and 250S by the company MICRO POWDERS and micro-waxes of polytetrafluoroethylene such those marketed 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%.

The solid composition according to the invention has, at ambient temperature (20 ° C.) and at atmospheric pressure (760 mmHg), a hardness greater than 30 Nm ', preferably greater than 40 Nm'. 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 cutting a product stick, preferably cylindrical of revolution, transversely, using a rigid tungsten wire of diameter 250. m 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 ', is measured by means of a DFGS2 dynamometer marketed by INDELCOCHATILLON. 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 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 'by the equation below: (Yx 10-3 x9.8) / L For a measurement at a different temperature, the stick is kept at this new temperature for 24 hours before the measurement. According to this measurement method, the composition according to the invention has a hardness at 20 ° C greater than or equal to 30 Nm ', preferably greater than 40 Nm', preferably greater than 50 Nm '.

Preferably, the composition according to the invention has in particular a hardness at 20 ° C. of less than 500 Nm ', in particular less than 400 Nm', preferably less than 300 Nm '. In particular, a composition whose hardness is greater than 30 Nm 'is a so-called solid composition at ambient temperature (20 ° C.) and at atmospheric pressure (760 mmHg).

Physiologically Acceptable Medium Physiologically acceptable medium means a medium compatible with keratin materials, such as oils or organic solvents commonly used in cosmetic compositions. The physiologically acceptable medium of the composition according to the invention may also comprise one or more organic solvents or solid, physiologically acceptable fatty substances (acceptable tolerance, toxicology and touch).

Additional Filmo2ene 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" is intended to mean 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 can be used in the composition of the present invention, mention may be made of synthetic polymers, of free radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. As film-forming polymer, there may be mentioned in particular acrylic polymers, polyurethanes, polyesters, polyamides, polyureas, 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 C10 to C22 ammonium chloride, such as hectorite modified with di-stearyl-dimethyl ammonium chloride such as, for example, sold under the name Bentone 38V by the company ELEMENTIS.

It is also possible to mention fumed silica optionally treated hydrophobic surface whose particle size is less than 1 m. 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 obtained in particular by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as silica dimethyl silylate according to the CTFA (8th edition, 2000). They are for example marketed under the Aerosil R972 references, and Aerosil R974 by the DEGUSSA company, 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 coloring material selected from water-soluble dyes, and pulverulent dyestuffs such as pigments, nacres, 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. Examples of inorganic pigments are titanium dioxide, optionally surface-treated, zirconium or cerium oxides, and oxides of zinc, iron (black, yellow or red) or chromium, violet 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, pigments of the D & C type, and lacquers based on carmine of cochineal, barium, strontium, calcium or aluminum.5 Mention may also be made of effect pigments such particles comprising an organic or inorganic substrate, natural or synthetic, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being coated or not covered with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide, and mixtures thereof. 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. Water-soluble dyes are, for example, beet juice, methylene blue. 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 are meant any colorless or white, mineral or synthetic particles of any form, insoluble in the medium of the composition regardless of the temperature at which the composition is made. These fillers serve in particular to modify the rheology or the texture of the composition. The fillers can be mineral or organic in any form, 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 (3-alanine and polyethylene), tetrafluoroethylene polymer powders (Teflon), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene / acrylonitrile chloride such as Expancel (Nobel Industrie), copolymers of acrylic acid (Polytrap from Dow Corning) ), precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads from Maprecos), glass or ceramic microcapsules, metal soaps derived from acids organic carboxylic compounds having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

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. The composition according to the invention may be intended for caring for and / or making up keratin materials, in particular the lips and the skin, in particular the lips.

Preferably, the composition according to the invention is in solid form, in stick form or cast in a dish for example. The examples which follow illustrate the invention in a nonlimiting manner. The quantities are expressed as a percentage by mass.

EXAMPLES Example 1: Preparation of a Pole Copolymer (Isobornyl Acrylate / Disobornyl Methacrylate / Isobutyl Acrylate / Acrylic Acid) 300 g of isododecane are introduced into a 1 liter reactor, and the temperature is then raised 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 141) are then added at 90 ° C. and over 1 hour. from Akzo Nobel). The mixture is maintained for 1 h 30 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-dimethylhexane are then introduced into the above mixture, still at 90 ° C. and over 30 minutes. . The mixture is kept at 90 ° C. for 3 hours, then the mixture is cooled. There is thus obtained a solution containing 50% of dry matter of copolymer in 50% of isododecane comprising a first poly (isobornyl acrylate / isobornyl methacrylate) block or block having a Tg of 128 ° C., a second poly ( isobutyl acrylate / acrylic acid) having a Tg of -9 ° 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 is 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 and 4: Lipsticks made of a stick A lipstick composition 4 according to the invention was prepared and a comparative composition 3 not forming part of the invention, comprising the following ingredients (amounts in percent by weight): Materials first (INCI name Composition 3 Composition 4 US) comparative according to the invention (outside the invention) Phase A NEOPENTANOATE 17,31 7,42 OCTYLDODECYL POLYISOBUTENE HYDROGEN 6.53 6,53 (PARLEAM from NOF Corporation) VinylPyrrolidone / HEXADECENE 8 , 21 8.21 COPOLYMER (Antaron V216 from ISP) Phase B ISOHEXADECANE 18.30 18.30 COPOLYMER 7.91 7.91 STYRENE / METHYL STYRENE / HYDROGEN INDENE (REGALITE R1100 from EASTMAN CHEMICAL) Poly (isobornyl methacrylate) 9.89 isobornyl acrylate-isobutyl co-acrylate co-acrylic acid) 50% active ingredient in 50% octyldodecyl neopentanoates according to Example 2 above Phase C COPOLYMER VinylPyrrolidone 1, 98 1.98 / EICOSENE (Antaron V220F from ISP) POLY WAX ETHYLENE 10.88 10.88 (Performalene 500-L from New Phase Technologies) Phase D Iron Oxides 3.39 3.39 Blue Dye 1.04 1.04 Titanium Dioxide 1.41 1.41 Red Dye 2.06 2.06 Phase E TRIMETHYLSILOXYPHENYL 20.97 20.97 DIMETHICONE (BELSIL 1000 from Wacker) Total: 100 100 The compositions 3 and 4 are obtained according to the following protocol: First, the fillers and pigments of the D phase are milled to the mill tri-cylinder in a part of the oily phase. The remaining fat-soluble ingredients are then mixed at a temperature of the order of 100 ° C. The ground material or the pre-dispersed actives are then added to the oily phase. Finally, the composition is poured into a mold for obtaining sticks 12.7 mm in diameter and the whole is allowed to cool in a freezer for about an hour.

During the application to the lips of each of the two compositions 3 and 4, the lipstick of composition 4 according to the invention, compared with the comparative composition 3 not containing a block copolymer, is more creamy on application. and the formed deposit is thicker and more comfortable. In addition, the hour after application, it is observed that the deposition on the lips made with the composition 4 remains thicker and more comfortable and has a better hold of the gloss and color than that achieved with the composition 3.

Claims (24)

REVENDICATIONS1. A solid cosmetic composition for the makeup and / or care of keratin materials comprising, in a physiologically acceptable medium, at least: a) a block ethylenic copolymer (also called sequenced ethylenic polymer), containing at least a first sequence having a transition temperature vitreous (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 the 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 constituent monomers of the second block, and said block copolymer having a polydispersity index I greater than 2, and at least b) at least one resin of average molecular weight less than or equal to 10000 g / mol selected from rosin, rosin derivatives, hydrocarbon resins and mixtures thereof, c) at least one solid fatty substance. 2. Composition according to the preceding claim, characterized in that it comprises less than 5% by weight of volatile oil whose flash point is less than or equal to 80 ° C. 3. Composition according to any one of the preceding claims, characterized in that it does not comprise volatile oil whose flash point is less than or equal to 80 ° C. 4. Composition according to any one of the preceding claims, characterized in that the said first monomer or monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C., are chosen from: methacrylates of formula CH2 = C (CH3) -COOR1 in which R1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, a C4 to C14 cycloalkyl group, and acrylates; of formula CH 2 = CH-COOR 2 in which R 2 represents a C 4 to C 12 cycloalkyl group, the (meth) acrylamides of formula: ## STR1 ## in which R 7 and R 8, which are identical or different, each represent a hydrogen atom; hydrogen or a linear or branched C1-C15 alkyl group, or R7 represents H and R8 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 -C 14 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 Ciz unsubstituted alkyl group in which one or more heteroatoms chosen from 0, N and S are optionally intercalated; ; 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. 5. Composition according to any one of the preceding claims, characterized in that said block copolymer is such that said first block is obtained from at least one acrylate monomer of formula CH2 = CH-000R2 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, and said second block is obtained from at least a second monomer glass transition temperature less than or equal to 20 ° C and additional monomer. 6. Composition according to the preceding claim, characterized in that said additional monomer is acrylic acid. 7. A solid cosmetic composition for the makeup and / or care of keratin materials comprising, in a physiologically acceptable medium, at least one copolymer comprising at least one acrylate monomer of formula CH 2 CHCH-COOR 2 in which R 2 represents a C 8 cycloalkyl group at C12 and / or at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 wherein R'2 represents a C8-C12 cycloalkyl group, at least one second acrylate monomer of formula CH2 = CHCOOR3, wherein R3 represents a linear or branched C1-C12 unsubstituted alkyl group, with the exception of the t-butyl group, and at least one acrylic acid monomer, said composition further comprising at least one resin having a number average molecular weight of less than or equal to at 10,000 g / mol chosen from rosin, rosin derivatives, hydrocarbon resins and mixtures thereof, and at least one solid fatty substance. 8. Composition according to any one of claims 5 to 7, characterized in that R2 and R'2 represent independently or simultaneously an isobornyl group. 25 9. Composition according to any one of the preceding claims, characterized in that said copolymer 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. 10. 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 10% by weight of acrylic acid. 11. 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, especially 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. 12. Composition according to any one of the preceding claims, characterized in that said resin is an indene hydrocarbon resin derived from the polymerization of indene monomer and monomer selected from styrene, methylindene, methylstyrene and mixtures thereof. 13. Composition according to the preceding claim, characterized in that the indene hydrocarbon resin is hydrogenated. 14. Composition according to any one of the preceding claims, characterized in that the resin is an indene resin chosen from hydrogenated indene / methylstyrene / styrene copolymers. 15. Composition according to any one of the preceding claims, characterized in that the resin is present in a content ranging from 0.1 to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.3 to 20% by weight, more preferably from 0.5 to 15% by weight. 16. 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. 17. Composition according to the preceding claim, characterized in that said non-volatile hydrocarbon oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol is octyldodecyl neopentanoate. 18. Cosmetic composition according to any one of the preceding claims, characterized in that the mass ratio between said block copolymer and the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. , is less than 1. 19. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises less than 10% by weight of volatile oil whose flash point is less than or equal to 80 ° C, relative to the total weight of the composition. . 20. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises less than 3% water, or better still less than 1% or is completely anhydrous. 21. Cosmetic composition according to any one of the preceding claims, characterized in that it further comprises at least one volatile oil whose flash point is greater than 80 ° C. 22. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises at least one wax. 23. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises at least one pasty fatty substance, and or an additional nonvolatile oil, and / or a filler and / or a coloring matter. 24. A cosmetic process for the makeup of keratin materials comprising applying to said keratin materials, and in particular the lips or the skin, a composition as defined in any one of the preceding claims.