FR2951641A1 - COSMETIC COMPOSITION COMPRISING A SEQUENCE POLYMER AND A SILICONE RESIN - Google Patents

Abstract

Cosmetic composition comprises at least one: (a) ethylene block copolymer containing at least one first block and at least one second block; (b) a silicone resin; and (c) a non volatile hydrocarbon ester oil comprising at least 16C and having a molecular weight of less than 650 g/mole, where the composition comprises 0-10 wt.% of a volatile oil having a flashpoint of = 80[deg] C. Cosmetic composition comprises at least one: (a) ethylene block copolymer (as ethylene block polymer) containing at least one first block having a glass transition temperature (Tg) of >= 40[deg] C, and which is obtained by one or more first monomers, which are homopolymer prepared from the monomers having a glass transition temperature of >= 40[deg] C, and at least one second block with a glass transition temperature of = 20[deg] C and obtained from all or part of one or more second monomers, which are homopolymer prepared from the monomers having a glass transition temperature of = 20[deg] C, where the first block and the second block are interconnected between these by a statistical intermediate segment comprising at least one of the first constitutive monomers of the first block and at least one of the second constitutive monomers of the second block, and the block copolymer has a polydispersity index of greater than 2; (b) a silicone resin; and (c) a non volatile hydrocarbon ester oil comprising at least 16C and having a molecular weight of less than 650 g/mol, where the composition comprises 0-10 wt.% of a volatile oil having a flashpoint of = 80[deg] C. Independent claims are included for: (1) a cosmetic process for make up and/or care of keratin material comprising: applying the composition on the keratin material, preferably lips or skin; or applying at least one first composition comprising at least one silicone resin, in a medium, and at least one second composition comprising at least one ethylene block polymer, non volatile hydrocarbon ester oil in a medium, where the second composition comprises 0-10 wt.% of the volatile oil; and (2) a product for makeup and/or care of keratin material comprising the first composition and the second composition, where the compositions are packaged separately in independent compartments or containers.

Description

The present invention relates to a cosmetic composition for makeup and / or care of keratin materials, in particular skin or lips, comprising a block polymer and a silicone resin. In the cosmetic field, the development of formulations with both good properties in terms of application and comfort, and satisfactory properties in terms of comfort, brightness, hold, especially withstand time, falls under a permanent goal. It is known documents EP 1 411 069 and EP 1 882 709, cosmetic compositions containing ethylenic block polymers known to obtain after application on keratin materials, including the lips, a makeup deposit having good performance. In particular for lipsticks, the makeup has a good hold time deposit of said lipstick on the lips. However, such block polymers are carried in volatile oils whose flash point is below 80 ° C (these may for example be used as a polymerization solvent for the film-forming polymer), such as idododecane. However, these volatile oils adversely affect the brightness of the makeup deposit obtained and give the composition discomfort sensations on application to the lips or skin. Indeed, the presence of a high content (that is to say greater than 10%) in volatile oil whose flash point is below 80 ° C causes a sensation of dryness and tightness on the lips or the skin. skin (feeling of discomfort). In addition, the presence of this volatile oil involves constraints in terms of the preparation process, in particular for the preparation of lipsticks comprising solid fatty substances such as waxes having a high melting point (in particular greater than or equal to 45 ° C), for which it is necessary to heat to a temperature generally higher than that of the flash point of the volatile oil. Furthermore, these compositions containing a volatile oil must be packaged in a sealed packaging to prevent evaporation of the solvent (that is to say volatile oil) from the composition during storage. This constraint of the sealed package represents an additional manufacturing cost. To overcome these problems with volatile oils, the solution is to use a non-volatile oil. However, the presence of the latter causes a loss of in terms of behavior over time of the deposition of makeup formed on the skin or lips. In particular, the formed deposit has a tendency to become fragile or fragmented, and to accumulate in the fine lines on the skin or the contour of the lips from 1 hour after application, while it is desired that it retains its integrity and remains homogeneous, especially for a period of 2 or 3 hours, or even for 4 or 6 hours. In particular, the formed deposit tends to become fragile on contact with the fat, especially during a meal, or in contact with saliva. It has been envisaged to compensate for the loss of strength of the composition by adding a hydrocarbon resin of the styrene / methyl styrene / indene hydrogenated copolymer type (such as, for example, Regalite from EASTMAN CHEMICAL) to the composition. However, the presence of such a resin makes it possible to improve the gloss resistance of the deposit formed on the skin or the lips, but the deposition behavior over time remains insufficient, since fragmentation and a loss of homogeneity are observed. deposit after 2 hours and therefore a loss of makeup color.

There is therefore a need to have a cosmetic composition containing a sequential film-forming polymer making it possible to obtain a deposit on the lips or the skin having good properties of resistance over time and improved comfort in the presence of non-volatile oil, and not having the constraints of manufacturing process and packaging mentioned above.

The inventors have discovered that such a composition can be obtained by combining the block polymer with a silicone resin in the presence of non-volatile oil, and with a zero or low content of volatile oil whose flash point is less than 80 ° C. . Such a composition applied to keratin materials, in particular the skin or the lips, makes it possible to obtain a deposit (in particular of make-up) having, when it is applied to the skin or the lips, good comfort properties (absence of sensation tingly, dryness), gloss, and whose deposition exhibits satisfactory behavior (no embrittlement or fragmentation of the deposit which remains homogeneous), especially for a period of 2 or 3 hours, or even for 4 or 6 hours. hours.

When the composition is a stick, there are also good sliding properties, good disintegration, to form a homogeneous and thick deposit on the skin or lips.

Furthermore, the silicone resin is compatible with the block ethylenic polymers and makes it possible to obtain a composition and a deposit on the skin or the homogeneous lips. On the other hand, the crosslinked organopolysiloxane elastomers, such as those sold under the names KSG by Shin Etsu, are incompatible with these block polymers: when they are associated with them, they lead to the production of a composition having the formation grains, lumps and / or a phase shift of the composition.

Thus, according to a first aspect, the present invention relates to a cosmetic composition comprising, in a physiologically acceptable medium, at least: a) a block ethylenic copolymer containing at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ° C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least 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 sequence being connected together a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second monomers constituting the second block, and said block copolymer having a polydispersity index I greater than 2; b) a silicone resin c) a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molecular weight of less than 650 g / mol, said composition comprising from 0 to 10% by weight of volatile oil having a flash point of less than or equal to equal to 80 ° C, relative to the total weight of the composition.

In the context of the present invention, the term "keratin materials" includes skin, lips, nails, hair, eyelashes and eyebrows.

The subject of the invention is also, according to another aspect, a cosmetic process for making up keratin materials, in particular skin or lips, comprising the application to keratin materials, in particular to the skin or the lips of a composition as defined previously. The invention finally relates to the use of a composition as described above to obtain a makeup of keratinous materials having comfort properties and / or deposition behavior over time.

An object of the present invention is also a makeup and / or care product for keratinous materials comprising at least a first composition comprising, in a physiologically acceptable medium, at least one silicone resin and at least one second composition comprising, in a physiologically acceptable medium, at least: a) a block ethylenic polymer, b) a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, said second composition comprising from 0 to 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, said compositions being packaged separately in separate compartments or containers. The product of the invention may be in particular a makeup product for the skin, or the lips. By makeup product is meant a product containing a coloring agent for depositing a color on a keratin material (especially the skin or the lips) by the application to the keratinous material of products such as lipsticks, make-up, eye-liners, foundations or self-tanners.

The product according to the invention comprises at least two cosmetically acceptable compositions packaged separately or together in one and the same packaging article or in at least two separate packaging articles. Preferably, these compositions are packaged separately and advantageously in separate packaging articles. The invention also relates to a makeup kit containing a cosmetic product as defined above, wherein the different compositions are packaged separately and are advantageously accompanied by appropriate application means. These means may be brushes, brushes, pens, pencils, felts, feathers, sponges, tubes and / or foam tips.

An object of the present invention is also a cosmetic process for making up and / or caring for keratin materials, comprising applying to said keratinous materials: at least one first composition comprising, in a physiologically acceptable medium, at least one silicone resin and a second composition comprising, in a physiologically acceptable medium, at least: a) a block ethylenic polymer, b) a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / moles, said second composition comprising from 0 to 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.

The first composition of the product according to the invention may constitute a base layer applied to the keratin material and the second composition a top layer. It is possible to apply under the first layer an under layer having the constitution or not of the second layer. In particular the basecoat is a lipstick, a foundation, a mascara, a lip gloss, an eyeliner, a body make-up product, and the top layer (or "top coat") a care product or protection.

The invention also relates to a process for making up and / or caring for keratin materials, in particular the skin and / or the lips, comprising applying to the keratin materials a cosmetic product as defined above.

The subject of the invention is also a cosmetic process for the care or makeup of keratinous tracts, which consists in applying to the skin, the lips and / or the integuments a first layer of a first composition containing a silicone resin, and then to apply, on all or part of the first layer, a second layer of a second composition comprising at least a) a sequenced ethylenic polymer, b) a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, said second composition comprising from 0 to 10% by weight of volatile oil whose flash point is less than or equal to 80 ° C, relative to the total weight of the second composition.

SILICONE RESIN The composition according to the invention, or the first composition of the product according to the invention, comprises at least one silicone resin.

More generally, the term "resin" means a compound whose structure is three-dimensional. The term "silicone resins" is also referred to as "silicone resins" or "siloxane resins". Thus, within the meaning of the present invention, a polydimethylsiloxane is not a silicone resin.

The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known under the name of "MDTQ", the resin being described according to the different monomeric siloxane units that it comprises, each of the letters "MDTQ" characterizing a type of unit.

The letter "M" represents the mono functional unit of formula R 1 R 2 R 3 SiO 2, the silicon atom being connected to a single oxygen atom in the polymer comprising this unit.

The letter "D" signifies a Difunctional unit R1R2SiO212 in which the silicon atom is connected to two oxygen atoms. The letter "T" represents a trifunctional unit of formula R1 SiO312.

Such resins are described for example in "Encyclopedia of Polymer Science and Enginnering, vol. 15, John and Wiley and Sons, New York, (1989), p. 265-270, 10 and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 5,082,706, US 5,319,040, US 5,302, 685 and US 4,935,484. In the units M, D and T defined above, R 1, namely R 1 and R 2, represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group. Finally, the letter "Q" signifies a tetrafunctional SiO412 unit in which the silicon atom is bonded to four oxygen atoms themselves linked to the rest of the polymer.

Various silicone resins of different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical R, the length of the chain polymer, the degree of branching and the size of the pendant chains.

As silicone resins which can be used in the compositions according to the invention, silicone resins of the MQ, T type or MQT type can be used, for example.

MQ resins: As an example of silicone resins of MQ type, mention may be made of alkylsiloxysilicates of formula [(R 1) 3 SiO 2] X (SiO 4 12) y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the group R1 represents a radical as defined above, and preferably is an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group.

Examples of solid silicone resins of the MQ type of trimethylsiloxysilicate type that may be mentioned are those sold under the reference SR1000 by the company General Electric, under the reference TMS 803 by the company Wacker, under the name "KF-7312J" by the company Shin -Etsu, "DC 749", "DC 593" by Dow Corning. As silicone resins comprising MQ siloxysilicate units, mention may also be made of phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate (Silshine 151 sold by General Electric). The preparation of such resins is described in particular in US5817302.

T-resins: By way of example of T-type silicone resins, there may be mentioned polysilsesquioxanes of formula (RSiO312) X (T units) in which x is greater than 100 and such that the R group is an alkyl group having 1 to 10 carbon atoms, said polysilsesquioxanes may further comprise Si-OH end groups. Preferably, it is possible to use the polymethylsilsesquioxane resins in which R represents a methyl group, for instance those marketed: by the company Wacker under the reference Resin MK such as Belsil PMS MK: polymer comprising repeating units CH3SiO312 (T units) , which may also comprise up to 1% by weight of units (CH 3) 2 SiO 2 12 (D units) and having an average molecular weight of approximately 10,000 g / mol, or - by SHIN-ETSU under the references KR-220L which are composed of T units of formula CH3SiO312 and have Si-OH end groups (silanol), under the reference KR-242A which comprise 98% of T units and 2% of dimethyl D units and have Si end groups -OH or also under the reference KR-251 comprising 88% of T units and 12% of dimethyl D units and have Si-OH end groups.

MQT Resins: As a resin comprising MQT units, those known from US 5,110,890 are particularly known. A preferred form of MQT type resins are MQT-propyl resins (also called MQTPr). Such resins that can be used in the compositions according to the invention are in particular those described and prepared in application WO 2005/075542, the content of which is incorporated herein by reference. The MQ-T-propyl resin preferably comprises the units: R 1, R 2 and R 3 independently represent a hydrocarbon radical (especially alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having 1 to 8 carbon atoms or a phenyl group, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d = 1, and a, b, c and d being mole fractions, provided that more than 40 mol% of the R 3 groups of the siloxane resin are propyl groups. Preferably the siloxane resin comprises the units: (i) (R13SiO1 / 2) a (iii) (R3 SiO3 / 2) c and (iv) (51O4 / 2) d with R1 and R3 independently representing an alkyl group having 1 to 8 carbon atoms, where R1 is preferably methyl and R3 is (i) (R13SiOii2) a (ii) (R22S1O2 / 2) b (iii) (R3 SiO3 / 2) c and (iv) (S1O4 / 2) d preferably with a propyl group, a being between 0.05 and 0.5, preferably between 0.15 and 0.4, c being greater than zero, preferably between 0.15 and 0. , 4, d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55, a + b + c + d = 1 and a, b where c and d are mole fractions, provided that more than 40 mol% of the R 3 groups of the siloxane resin are propyl groups.

The siloxane resins that can be used according to the invention can be obtained by a process comprising the reaction of: A) an MQ resin comprising at least 80 mol% of units (R13SiO2) a and (SiO4 / 2) d R1 representing a grouping alkyl having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, a and d being greater than zero, the ratio a / d being between 0.5 and 1.5; and B) a propyl resin T comprising at least 80 mol% of units (R 3 SiO 3 12) wherein R 3 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, c being greater than zero, with the proviso that at least 40 mol% of the R3 groups are propyl groups, where the A / B mass ratio is between 95: 5 and 15:85, preferably the weight ratio A / B is 30:70.

Advantageously, the mass ratio A / B is between 95: 5 and 15:85. Preferably, the ratio A / B is less than or equal to 70:30. These preferred ratios have been found to provide comfortable deposits due to the absence of percolation of rigid MQ resin particles in the deposit.

Thus, preferably, the silicone resin is chosen from the group comprising: a) a resin of MQ type, in particular chosen from (i) alkylsiloxysilicates, which may be trimethylsiloxysilicates, of formula [(R 1) 3 SiO 2] X (SiO 4 12) in which x and y are integers ranging from 50 to 80, and such that the group R 1 represents a hydrocarbon radical having 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or a hydroxyl group, and preferably is an alkyl group having from 1 to 8 carbon atoms, preferably a methyl group, and (ii) phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate, and / or b) a type T resin, especially chosen from polysilsesquixanes of formula (RSiO312) X, wherein x is greater than 100 and the group R is an alkyl group having 1 to 10 carbon atoms, for example a methyl group, said polysilsesquioxanes being moreover include Si-OH end groups, and / or c) a MQT type resin, especially of the MQT-propyl type, which may comprise the units (i) (R13SiOli2) a, (ii) (R22SiO2 / 2) b, (iii ) (R3SiO312) c and (iv) SiO4 / 2) d, with R1, R2 and R3 independently representing a hydrocarbon radical, especially alkyl, having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or else a hydroxyl group and preferably an alkyl radical having 1 to 8 carbon atoms or a phenyl group, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero, d being between 0.05 and 0.6, a + b + c + d = 1, a, b, c and d being mole fractions, provided that more than 40 mol% of the R 3 groups of the siloxane resin are propyl groups.

Preferably, the silicone resin is present in the composition according to the invention in a total resin solids content ranging from 1% to 40% by weight relative to the total weight of the composition, preferably ranging from 2% to 30% by weight, and more preferably from 3% to 25% by weight.

Preferably, the silicone resin and the block ethylenic copolymer are present in the composition according to the invention in contents such that the weight ratio silicone resin / ethylenic block copolymer is between 1/20 and 20/1, preferably between 1 / 10 and 10/1, or better between 1/5 and 5/1.

ETHYLENIC COPOLYMER SEQUENCE The composition according to the present invention, or the second composition of the product according to the invention, contains at least one ethylenic block copolymer (also called sequenced ethylenic polymer), containing at least a first sequence having a glass transition temperature (Tg ) greater than or equal to 40 ° C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of not less than 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 temperature of glass transition 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 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 ("macromonomer" means a mono-functional monomer having a pendant group of a polymeric nature, and preferably having a molecular mass greater than 500 g / mol, or a polymer having on one of its ends a polymerizable terminal group (or ethylenically unsaturated)), which are used in the preparation of a graft polymer.

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

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

Preferably, the polymer according to the invention is not an elastomer. By "non-elastomeric polymer" is meant a polymer which, when subjected to a stress aimed at stretching it (for example by 30% relative to its initial length), does not return to a length substantially identical to its length. initial when the constraint stops. More specifically, "non-elastomeric polymer" denotes a polymer having an instantaneous recovery R; <50% and delayed recovery R2h <70% after 30% elongation. Preferably, R; is <30%, and R2h <50%. More specifically, the non-elastomeric nature of the polymer is determined according to the following protocol: A polymer film is prepared by pouring a solution of the polymer into a Teflon matrix and then drying for 7 days in a controlled atmosphere at 23 ± 5 ° C. and 50 + 10% relative humidity. A film approximately 100 μm thick in which are cut rectangular specimens (for example by punch) of a width of 15 mm and a length of 80 mm are then obtained. This sample is 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 by 30% (cmax), that is to say about 0.3 times its initial length (Io); the stress is released by imposing a return speed equal to the tensile speed, ie 50 mm / min and the residual elongation of the specimen is measured in percentage, after return to zero load stress (ci). The instantaneous recovery in% (R;) is given by the formula below:

Ri ù (Emax - Ci) / Emax) X 100 To determine the delayed recovery, after 2 hours the residual elongation ratio of the specimen is measured 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 (Mw) of the polymer according to the invention is preferably less than or equal to 300,000, it ranges, for example, from 35,000 to 200,000, and more preferably from 45,000 to 150,000 g / mol. The number average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70,000, it ranges, for example, from 10,000 to 60,000, and more preferably from 12,000 to 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 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 blocks may be theoretical T g determined from the theoretical T g 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, the expression "comprised between ... and ..." is intended to mean an interval of values whose mentioned limits are excluded, and "from ... to ..." and "ranging from ... to ... ", an interval of values whose terminals are included. The sequence having a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer.

The sequence having a Tg 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 "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, ranging for example from 50 ° C to 120 ° C, and better still greater than or equal to 60 ° C, ranging 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 CI-I2 = C (C13) -COOR11 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 or R8 represents a C4 to C12 cycloalkyl group, preferably a cycloalkyl group C8 to C12, such as isobornyl methacrylate, - acrylates of formula CH2 = CH-COOR12 in which R12 represents a C4-C12 cycloalkyl group such as an isobornyl group or a tert-butyl group,

the (meth) acrylamides of formula: wherein R7 and R8, which may be identical or different, each represent a hydrogen atom or a linear or branched C1-C12 alkyl group, such as a group n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl; or R7 is H and R8 is 1,1-dimethyl-3-oxo-butyl, and R 'is H or methyl. Examples of monomers include N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide, and mixtures thereof. The first block is advantageously obtained from at least one acrylate monomer of formula CH2 = CH-COOR12 and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR12 in which R12 represents a C4 to C12 cycloalkyl group preferably C 6 to C 12 cycloalkyl, such as isobornyl. The monomers and their proportions are preferably chosen so that the glass transition temperature of the first block is greater than or equal to 40 ° C. According to one embodiment, the first block is obtained from: i) at least one acrylate monomer of formula CH2 = CH-COOR12 in which R12 represents a C4 to C12 cycloalkyl group, preferably a C8 cycloalkyl group at C12, such as isobornyl, - ii) and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'12 wherein R'12 represents a C4 to C12 cycloalkyl group, preferably a cycloalkyl group C 8 to C 12, such as isobornyl.

According to one embodiment, the first block is obtained from at least one acrylate monomer of formula CH2 = CH-COOR12 in which R12 represents a C8 to C12 cycloalkyl group, such as isobornyl, and from minus a methacrylate monomer of formula CH2 = C (CH3) -COOR'12 wherein R'12 represents a C8-C12 cycloalkyl group, such as isobornyl. Preferably, Rte and R '12 independently or simultaneously represent an isobornyl group.

Preferably, the block copolymer comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acrylic acid.

The first block can be obtained exclusively from said acrylate monomer and said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are preferably in mass proposals of between 30:70 and 70:30, preferably between 40:60 and 60:40, in particular of the order of 50:50. The proportion of the first block is preferably from 20 to 90% by weight of the polymer, more preferably from 30 to 80% and even more preferably from 60 to 80%. According to one embodiment, the first block is obtained by polymerization of the isobornyl methacrylate and isobornylaclylate.

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 "soft sequence".

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

the acrylates of formula CH2 = CHCOOR13, R13 representing a linear or branched C1-C12 unsubstituted alkyl group, with the exception of the tert-butyl group, in which is optionally intercalated one or more heteroatoms chosen from O, N, S,

methacrylates of formula CH2 = C (CH3) -COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group in which (or) one or more heteroatoms selected from 0 are optionally intercalated; and S;

vinyl esters of formula R5-CO-O-C1-1 = CI-I2 where R5 represents a linear or branched C4-C12 alkyl group; C4 to C12 alcohol and vinyl alcohol ethers; C4 to C12 N-alkyl acrylamides, such as N-octylacrylamide, and mixtures thereof.

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

Each of the first and second sequences may contain, in a minority proportion, at least one constituent monomer of the other sequence. Thus the first sequence may contain at least one constituent monomer of the second sequence and vice versa. Each of the first and / or second sequence may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned above. The nature and amount of this additional monomer (s) are chosen such that the sequence in which they 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) -COOR6 wherein R6 represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl group; , 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, 1, F ), such as trifluoroethyl methacrylate, methacrylates of the formula CH2 = C (CH3) -COOR9, wherein R9 represents a linear or branched C6-C12 alkyl group in which there is (optionally) ercalé (s) one or more heteroatoms selected from 0, N and S, said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, 1, F); the acrylates of formula CI-12 = CHCOOR10, Rio representing a linear or branched C1-C12 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 a repeat of the oxyethylene unit of 5 to 10 times, for example methoxy -POE, or R8 represents a polyoxyethylenated group comprising from 5 to 10 ethylene oxide units. In particular, the first block may comprise, as additional monomer: - (meth) acrylic acid, preferably acrylic acid, - tert-butyl acrylate - methacrylates of formula CH 2 = C (CH 3) In which R 1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, the (meth) acrylamides of formula: R R 7 CH 2 = C CO N R 8, wherein R 7 and R 8, which may be identical or different, each represent a hydrogen atom or a linear or branched C 1 -C 12 alkyl group, such as a n-butyl, t-butyl, isopropyl or isohexyl group; , isooctyl, or isononyl; or R7 is H and R8 is 1,1-dimethyl-3-oxobutyl, and R 'is 1-1 or methyl. As examples of monomers, there may be mentioned 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 mode of implementation, 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 representing % 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 at least one other monomer having a Tg of less than or equal to 20 ° C.

According to a preferred embodiment, the invention relates to a cosmetic composition for the makeup and / or care of keratin materials comprising, in a physiologically acceptable medium, at least: a) a copolymer comprising at least one acrylate monomer of formula CH 2 = CH-COOR12 in which R12 represents a C8 to C12 cycloalkyl group and / or at least one methacrylate monomer of formula C1-I2 = C (CH3) -COOR '12 in which R' 12 represents a C8 to C12 cycloalkyl group, at least a second acrylate monomer of formula CH2 = CHCOOR13, in which R13 represents a C1-C12 unsubstituted alkyl group, linear or branched, with the exception of the tert-butyl group, and at least one acrylic acid monomer, b) a resin silicone, c) a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, said composition comprising from 0 to 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.

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 4 to 10% by weight of acrylic acid monomers, relative to the total weight of said copolymer. The constituent monomers of the second block and their proportions are chosen so that the glass transition temperature of the second block is less than or equal to 20 ° C.

Intermediate segment

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

The formation of the second sequence is initiated when the first monomers no longer react or become incorporated in the polymer chain either because they are all consumed or because their reactivity no longer allows them to be. Thus, the intermediate segment comprises the first available monomers, resulting from a conversion rate of these first monomers of less than or equal to 90%, during the introduction of the second monomer or monomers during the synthesis of the polymer.

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

Thus, the intermediate segment is a random sequence, as are the first sequence and the second sequence 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 a known manner, as a function of the desired polymerization temperature and of the polymerization solvent. In particular, the initiator may be chosen from peroxide-functional initiators, oxidation-reduction pairs, or other radical polymerization initiators known to those skilled in the art. In particular, as a peroxide-functional initiator, there may be mentioned, for example: a. peroxyesters, such as terbutylperoxyacetate, tertbutylperbenzoate, tertbutylperoxy-2-ethylhexanoate (Akzo Nobel Trigonox 21S), 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox) 141 by Akzo Nobel); b. peroxydicarbonates, such as di-isopropylperoxydicarbonate; c. peroxycetones, such as methyl ethyl ketone peroxide; d. hydroperoxides, such as hydrogen peroxide (H2O2), terbutylhydroperoxide; e. diacyl peroxides, such as acetyl peroxide, benzoyl peroxide; f. dialkyl peroxides, such as di-tert-butyl peroxide; g. Inorganic peroxides, such as potassium peroxodisulfate (K2S2O8); As an initiator in the form of a redox couple, mention may be made of the potassium thiosulfate + potassium peroxodisulphate pair, for example. According to a preferred embodiment, the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms. Preferably, the initiator used is 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane sold under the reference Trigonox® 141 by Akzo Nobel. The block copolymer used according to the invention is prepared by free radical polymerization and not by controlled or living polymerization. In particular, the polymerization of the block ethylenic copolymer is carried out in the absence of control agents, and in particular in the absence of control agent conventionally used in living or controlled polymerization processes such as nitroxides, alkoxyamines dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates, copper catalysts, for example. As previously indicated, the intermediate segment is a statistical sequence, as is the first sequence and the second sequence if they are not homopolymers (i.e., both are formed from at least two different monomers). The block copolymer may be prepared by free radical polymerization, and in particular by a process comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one glass transition monomer greater than or equal to 40 ° C. at least one glass transition monomer less than or equal to 20 ° C in 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 when 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. is then poured in a first casting and optionally part 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 reactor, in a second color again, said polymerization initiator, said at least one second vitreous 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 tray, - the reaction mixture is brought to room temperature. Preferably, the copolymer may be prepared by free radical polymerization, in particular by a process comprising mixing, in one and the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer or at least one lower glass transition monomer. or at 20 ° C, at least one acrylate monomer of formula CH2 = CH-COOR12 in which R12 represents a C4 to C12 cycloalkyl group, and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'12 in which R'12 represents a C4 to C12 cycloalkyl group, according to the following stage sequence: a part of the polymerization solvent and possibly a portion of the initiator and monomers of the first casting, are added to the reactor; which is heated to a reaction temperature of between 60 and 120 ° C, is then poured, in a first casting, said at least one acrylate monomer of formula CH2 = CH-COOR12 and said at least methacrylate monomer of formula CH2 = C (CH3) -COOR'12 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 of said monomers of up to 90% is 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 can 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, 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, 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 liquid at room temperature such as toluene and xylene; Aldehydes which are liquid at room temperature, such as benzaldehyde, 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 15 • 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 of 60 to 120 ° C., the at least one lower glass transition monomer is then poured in a first casting. or at 20 ° 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 of 90% maximum, in the reactor, in a second casting, again 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 rate When the conversion of said monomers reaches a plateau, the reaction mixture is brought back to ambient 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 vitreous transition monomer 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 CH 2 = CH-COOR 12 in which R 12 represents a C 4 to C 12 cycloalkyl group, and at least one methacrylate monomer of formula CH 2 CC (CH 3) -COOR' 2 in which R '12 represents a C 4 to C 12 cycloalkyl group, according to the sequence 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 temperature of between 60 and 120 ° C., the acrylic acid monomer and the at least one glass transition monomer of less than or equal to 20 ° C. are then poured in a first casting and, if appropriate, part of the initiator which the 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-COOR12 and said at least one methacrylate monomer of formula CH2 = C (CH3) -COOR '12, as a monomer of Tg greater than or equal to 40 ° C, which is allowed to react for a period of time At the end of which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought back to ambient 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-1 882 709. Distillation of the synthetic solvent For the implementation of the sequenced polymer in a composition according to the invention and when the polymer is prepared in a volatile solvent or a volatile oil having a flash point below 80 ° C, it is necessary to proceed to a step of total or partial removal of said solvent or volatile oil. The process is carried out in particular by distillation, optionally under vacuum, and addition of nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. volatile compound comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. This technique is known to those skilled in the art and Example 2 described below illustrates this technique.

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

The elimination of volatile oil with a flash point of less than 80 ° C. (conventionally isododecane) makes it possible to limit the content thereof in the solution of block copolymer and thus to produce a cosmetic composition containing less than 10% by weight of isododecane (and more generally of volatile solvent) and preferably less than 5% by weight of isododecane (and more generally of volatile solvent), relative to the total weight of the composition.

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

Non-volatile hydrocarbon ester oil:

The composition according to the invention, or the second composition of the product according to the invention, comprises a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol.

Advantageously, the first composition of the product according to the invention also comprises a nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol. The presence of the non-volatile 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 make-up deposit on keratin materials (in particular the lips) having good comfort (no feeling of tightness or dryness and shine.) By "oil" is meant a non-aqueous compound, liquid at room temperature (25 ° C) and atmospheric pressure (760 mmHg). By "non-volatile oil" is meant an oil remaining on the keratin materials at ambient temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 -3 mmHg (0.13 Pa). It is also possible to define a non-volatile oil as having an evaporation rate such that under the conditions defined above, the amount evaporated after 30 minutes is less than 0.07 mg / cm 2. By "hydrocarbon oil" is meant an oil formed essentially, or even constituted, of carbon and hydrogen atoms, and possibly of oxygen, nitrogen, and not containing a silicon atom or fluorine. 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 molecular weight of less than 650 g / mol, mention may be made in particular of: fatty acid esters, in particular from 4 to 22 carbon atoms, and including octanoic acid, heptanoic acid, lanolic acid, oleic acid, lauric acid, stearic acid such as propylene glycol dioctanoate, propylene glycol monoisostearate, neopentyl glycol diheptanoate, synthetic esters such as the oils of formula R1000R2 in which RI represents the residue of a linear or branched fatty acid containing from 4 to 40 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched hydrocarbon chain containing from 4 to 40 carbon atoms, provided that that RI + R2 is 16, such as, for example, purcellin oil (cetostearyl octanoate), isononyl isononanoate, C12-C15 alcohol benzoate, ethyl 2-hexyl palmitate, neopentanoate d o cetyledodecyl, 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 synthesis esters R.sub.1COOR.sub.2 in which R.sub.1 represents the residue of a linear or branched fatty acid containing from 4 to 40 carbon atoms and R.sub.2 represents a particularly branched hydrocarbon-based 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 with a molar mass of less than 650 g / mol. According to a preferred embodiment, the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms has a molar mass of less than 600 g / mol. The non-volatile hydrocarbon ester oil may in particular comprise a linear or branched hydrocarbon oil having a molar mass of between 100 and 650 g / mol and more particularly between 200 and 600 g / mol.

The choice of these nonvolatile oils makes it possible to optimize the amount of volatile oil whose flash point is less than or equal to 80 ° C evaporated, that is to say to distil most of the polymerization solvent ( as isododecane), or essentially all the polymerization solvent (that is to say volatile oil whose flash point is less than or equal to 80 ° C), the latter remaining only at the trace state in the composition. The use of other solvents does not make it possible to eliminate enough volatile oil whose flash point is less than or equal to 80 ° C. During the distillation, the mixture becomes very viscous and non-manipulable and it is no longer possible to continue the distillation. According to a preferred embodiment, the nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms (preferably at least 20 carbon atoms) and having a molar mass of less than 650 g / mol is octyledodecyl neopentanoate (especially 2-octyledodecyl neopentanoate). This ester oil makes it possible to distil all of the volatile oil whose flash point is less than or equal to 80 ° C.

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

Additional nonvolatile oil The composition according to the invention (or the first and / or the second composition of the product according to the invention) may advantageously comprise at least one other additional nonvolatile oil, different from said hydrocarbon ester oil comprising at least 16 atoms. of carbon and having a molar mass of less than 650 g / mol, this additional oil can be chosen from all cosmetically acceptable oils, especially mineral, vegetable, synthetic oils; in particular the hydrocarbon oils and / or silicone and / or fluorinated, volatile or non-volatile and mixtures thereof.

For the purposes of the present invention, the term "silicone oil" means an oil comprising at least one silicon atom, and in particular at least one Si-O group. The term "fluorinated oil" means an oil comprising at least one fluorine atom.

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

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

2 / copolymers of vinylpyrrolidone such as: the vinylpyrrolidone / 1-hexadecene, Antaron Vù216 marketed or manufactured by the company ISP (MW = 7300 g / mol), 3 / the hydrocarbon ester oil having a molar mass greater than 650 g mole, such as linear fatty acid esters having a total carbon number ranging from 35 to 70 such as pentaerythrityl tetrapelargonate (MW = 697 g / mol), hydroxylated esters such as polyglycerol triisostearate; 2 (MW = 965 g / mol), aromatic esters such as tridecyl trimellitate (MW = 757 g / mol), esters of fatty alcohol or branched C24-C28 fatty acids such as 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 (MW = 891 g / mol ), tri-decyl-2 glyceryl tetradecanoate (MW = 1143 g / mol), pentaerythrityl tetraisostearate e (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 acid, and h represents an integer varying from e 1 to 9, in particular the esters of dilinoleic diacids and of dilinoleic diol dimers marketed by the company Nippon Fine Chemical under the trade name LUSPLAN DD-DA5® and DD-DA7®, 4 / silicone oils such as phenyl silicones (also called phenyl silicone oil) as BELSIL PDM 1000 from the company Wacker (MW = 9000 g / mol), the trimethicones phenyl (such as phenyl trimethicone sold under the trade name DC556 by Dow Corning), phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, polydimethylsiloxanes (PDMSs), polydimethylsiloxanes comprising alkyl or alkoxy groups, pendant and / or end of a silicone chain, these groups each containing 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, relative to to the total weight of the composition.

Oils whose flash point is less than or equal to 80 ° C. The composition according to the invention (or the second composition of the product according to the invention) contains less than 10% by weight of volatile oil whose flash point is less than or equal to 80 ° C. Preferably, the composition according to the invention (or the second composition of the product according to the invention) comprises less than 5% relative to the total weight of the composition or is free of volatile oil whose flash point is lower or equal to 80 ° C, such as isododecane. In particular, the flash point is measured according to ISO 3679.

For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with keratin materials in less than one hour at ambient temperature and atmospheric pressure (760 mmHg). The volatile organic solvent (s) and the volatile oils of the invention are organic solvents and volatile cosmetic oils which are liquid at ambient temperature and have a non-zero vapor pressure at ambient temperature and atmospheric pressure, in particular ranging from 0 to 13 Pa at 40,000 Pa (10-3 to 300 mm Hg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg). These oils may be hydrocarbon oils, silicone oils, fluorinated oils, or mixtures thereof.

In particular, as volatile oil whose flash point is less than or equal to 80 ° C., mention may be made of: volatile hydrocarbon-based oils such as hydrocarbon-based oils containing from 8 to 14 carbon atoms, and especially C8-C14 branched alkanes, for example 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 (or the first and / or second composition of the product according to the invention) preferably comprises at least one solid fatty substance chosen from waxes and pasty fatty substances, and their mixture.

Pasty fats The composition according to the invention (or the first and / or the second composition of the product according to the invention) preferably comprises at least one pasty fatty substance. For the purposes of the present invention, the term "pasty fatty substance" (also referred to as pasty fatty substance) is understood to mean a lipophilic fat compound with a reversible solid / liquid state change, having in the solid state an anisotropic crystalline organization and comprising at least one the temperature of 23 ° C a liquid fraction and a solid fraction.

In other words, the starting melting temperature of the pasty compound may be less than 23 ° C. The liquid fraction of the pasty compound measured at 23 ° C. can represent 9 to 97% by weight of the compound. This liquid fraction at 23 ° C is preferably between 15 and 85%, more preferably between 40 and 85% by weight.

For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in ISO 11357-3; 1999. The melting point of a paste or a wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name "MDSC 2920" by the company TA Instruments .

The measurement protocol is as follows: A sample of 5 mg of paste or wax (as the case may be) placed in a crucible is subjected to a first temperature rise from -20 ° C to 100 ° C, at the rate of heating of 10 ° C / minute, then is cooled from 100 ° C to -20 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise from -20 ° C to 100 ° C at a heating rate of 5 ° C / minute. During the second temperature rise, the variation of the power difference absorbed by the empty crucible and the crucible containing the pasty or wax sample is measured as a function of temperature. The melting point of the compound is the value of the temperature corresponding to the peak apex of the curve representing the variation of the difference in power absorbed as a function of the temperature. The liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed at 23 ° C. to the heat of fusion of the pasty compound. The heat of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in crystalline solid form. The pasty compound is said to be in a liquid state when all of its mass is in liquid form. The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a temperature rise of 5 or 10 ° C per minute, according to ISO 11357-3: 1999.

The enthalpy of fusion of the pasty compound is the amount of energy required to pass the compound from the solid state to the liquid state. It is expressed in J / g. The heat of fusion consumed at 23 ° C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23 ° C consisting of a liquid fraction and a solid fraction. The liquid fraction of the pasty compound measured at 32 ° C is preferably 30 to 100% by weight of the compound, preferably 50 to 100%, more preferably 60 to 100% by weight of the compound. When the liquid fraction of the pasty compound measured at 32 ° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 ° C. The liquid fraction of the pasty compound measured at 32 ° C. is equal to the ratio of the enthalpy of fusion consumed at 32 ° C. to the heat of fusion of the pasty compound. The enthalpy of fusion consumed at 32 ° C. is calculated in the same way as the heat of fusion consumed at 23 ° C.

The pasty compound is preferably chosen from synthetic compounds and compounds of plant origin. A pasty compound can be obtained synthetically from starting materials of plant origin. The pasty compound is advantageously chosen from - lanolin and its derivatives - polyol ethers chosen from pentaerythritol ethers and polyalkylene glycol ethers, fatty alcohol and sugar ethers, and 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- 5 Pentaerythrityl Ether), and mixtures thereof, and more particularly the PEG-5 Pentaerythrityl Ether mixture, PPG-5 Pentaerythrityl Ether and soybean oil, sold under the name "Lanolide" by the company Vevy, a 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 8 -C 30 alkyl groups • Homo and copolymer oligomers of vinyl ethers having C 8 -C 30 alkyl groups the liposoluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-C50 diols, the esters, and / or their mixtures. The pasty compound is preferably a polymer, in particular a hydrocarbon polymer.

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

Among the esters, the following are particularly preferred: esters of an oligomeric glycerol, in particular the esters of diglycerol, in particular the condensates of adipic acid and of glycerol, for which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, especially in the image of those marketed under the trademark Softisan 649 by the company Sasol - arachidyl propionate sold under the trademark Waxenol 801 by Alzo, - phytosterol esters, - fatty acid triglycerides and their derivatives, - pentaerythritol esters, - non-crosslinked polyesters resulting from the polycondensation between a dicarboxylic acid or a C 4 -C 50 linear or branched 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, acid isoarachidic acid, octyldodecanoic acid, henicosanoic acid, docosanoic acid, and mixtures thereof. The aliphatic carboxylic acid is preferably branched. The aliphatic hydroxy carboxylic acid ester is advantageously derived from a hydroxylated aliphatic carboxylic acid having from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to to 20 hydroxyl groups, preferably 1 to 10 hydroxyl groups and more preferably 1 to 6 hydroxyl groups. The aliphatic hydroxy carboxylic acid ester is chosen from: a) partial or total esters of saturated linear monohydroxylated aliphatic monocarboxylic acids; b) partial or total esters of unsaturated monohydroxylated aliphatic monocarboxylic acids; c) partial or total esters of saturated monohydroxylated aliphatic polycarboxylic acids; d) partial or total esters of saturated polyhydroxylated aliphatic polycarboxylic acids; e) the partial or total esters of C2 to C16 aliphatic polyols reacted with a mono or polyhydroxylated aliphatic mono or poly carboxylic acid, and mixtures thereof. the diol dimer and diacid dimer esters, if appropriate, esterified on their (their) alcohol (s) or free acid (s) function (s) with acidic radicals or alcohols, especially dimer dilinoleate esters, such esters may in particular be chosen from the following INCI nomenclature esters: bis-behenyl / isostearyl / phytosteryl dimerdilinoleyl dimerdilinoleate (Plandool G), phytosteryl / isosteryl / cetyl / stearyl / behenyl dimerdilinoleate (Plandool H or Plandool S), and their mixtures. the hydrogenated rosinate esters, such as the dilinoleyl dimers of hydrogenated rosinate (Lusplan DD-DHR or DD-DHR from Nippon Fine Chemical), and mixtures thereof.

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

Wax (s) According to a preferred embodiment, the composition according to the invention (or the first and / or the second composition of the product 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 (20 ° 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®, 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 the wax, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising from 20 to 40 carbon atoms), alone or in admixture, can be used. Such a wax is especially sold under the names "Kester Wax K 82 P®", "Hydroxypolyester K 82 P®" and "Kester Wax K 80 P®" by the company Koster Keunen.

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

According to a first embodiment, the composition according to the invention is liquid at ambient temperature (20 ° C.). According to a second preferred embodiment, the composition according to the invention is solid, and preferably has, at ambient temperature (20 ° C.) and at atmospheric pressure (760 mmHg), a hardness greater than 30 Nm ', Preferably, the composition according to the invention preferably comprises at least one solid fatty substance, such as a wax or a pasty fatty substance.

Protocol for Measuring Hardness: The hardness of the composition is measured according to the following protocol: The lipstick stick is stored at 20 ° C. for 24 hours before measuring the hardness. The hardness can be measured at 20 ° C. by the so-called "butter-cutting thread" method, which consists in transversely cutting a stick of product, preferably cylindrical of revolution, with the aid of a rigid tungsten wire. 250 μm diameter by moving the wire relative to the stick at a speed of 100 mm / min.

The hardness of the samples of compositions of the invention, expressed in Nm ', is measured by means of a DFGS2 dynamometer marketed by INDELCO-CHATILLON. The measurement is repeated three times and averaged. The average of the three values read using the dynamometer mentioned above, denoted Y, is given in 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 Nr -1 by the following equation: (Yx 10-3 x 9.8) / L For a measurement at a different temperature, the stick is kept at this new temperature for 24 hours before the measurement. According to this measurement method, the composition according to the invention has a hardness at 20 ° C of greater than or equal to 30 Nm ', preferably greater than 40 Nr -1, preferably greater than 50 Nm'. Preferably, the composition according to the invention has in particular a hardness at 20 ° C. of less than 500 Nr -1, in particular less than 400 Nm 2, preferably less than 300 Nm 3. In particular, a composition having a hardness greater than 30 Nr -1 is a so-called "solid" composition at room temperature (20 ° C) and atmospheric pressure (760 mm Hg).

Physiologically Acceptable Medium The term "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" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous deposition 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 the film-forming polymer, mention may in particular be made of acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulose polymers, such as nitrocellulose. The polymer may be associated with one or more auxiliary film-forming agents. Such a film-forming agent may be chosen from all the compounds known to those skilled in the art as being capable of fulfilling the desired function, and in particular be chosen from plasticizers and coalescing agents.

Lipophilic Gelling Agents According to one embodiment, the composition according to the invention (or the first and / or the second composition of the product 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 the mineral lipophilic gelling agent, 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, that marketed 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 micron. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8th edition, 2000). They are, for example, sold under the references Aerosil R812® by the company Degussa, CAB-O-SIL TS-530® by the company Cabot, dimethylsilyloxyl or polydimethylsiloxane groups, which are especially obtained by treatment of fumed silica in the presence of polydimethylsiloxane. or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (8th edition, 2000). They are for example marketed under the references Aerosil R972®, and Aerosil R974® by the company DEGUSSA, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by CABOT.

Among the lipophilic gelling agents that can be used in the compositions according to the invention, mention may also be made of dextrin and fatty acid esters, such as dextrin palmitates, in particular such as those sold under the names Rheopearl TL® or Rheopearl KL. ® by the company CHIBA FLOUR.

Dyestuff The composition according to the invention (or the first and / or the second composition of the product according to the invention) may further comprise a dyestuff chosen 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 include particles of any iridescent form, in particular produced by certain molluscs in their shell or else synthesized. The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxides, and oxides of zinc, iron (black, yellow or red) or chromium, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder.

Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum. Mention may also be made of effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being covered or not with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and their mixtures. The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated with, inter alia, blue. ferric oxide or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It is also possible to use interferential pigments, in particular liquid crystal or multilayer pigments. The water-soluble dyes are, for example, beet juice, methylene blue. Charges The composition according to the invention (or the first and / or the second composition of the product according to the invention) may also comprise one or more fillers, especially in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably from 0.01% to 30% by weight. By fillers, it is necessary to include particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or the texture of the composition.

The fillers can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem), poly- (3-alanine and polyethylene), tetrafluoroethylene polymer powders (Teflon ®), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industrie), copolymers of acrylic acid (Polytrap® from Dow Corning), precipitated calcium carbonate, magnesium carbonate and hydrocyanate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, soaps metal derivatives of organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 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 the care and / or makeup of keratin materials, in particular the lips and the skin, such as a lipstick, a mascara, an eyeliner or a foundation. The composition according to the invention may also be in the form of a liquid gloss. 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 was introduced into a 1 liter reactor, and then the temperature was increased to from room temperature (20 ° 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) were then added at 90 ° C. and over 1 hour. ® 141 from Akzo Nobel). The mixture was 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 were then added to the above mixture, still at 90 ° C. and over 30 minutes. -diméthylhexane. The mixture was kept at 90 ° C. for 3 hours and then cooled. There was thus obtained a solution containing 50% by weight of copolymer 20 in 50% of isododecane comprising a first poly (isobornyl acrylate / isobornyl methacrylate) block or block having a Tg of 128 ° C., a second block 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 to evaporate the isododecane while simultaneously adding the octyldodecyl neopentanoate. The entirety of the isododecane was substituted by as much octyldodecyl neopentanoate by weight.

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

Examples 3 and 4: Sticky lip wheels A lipstick composition 4 according to the invention comprising a silicone resin and a sequenced ethylenic polymer and a comparative composition 3 not forming part of the invention in which the resin was prepared. silicone (SR 1000 from Momentive Performance Materials), of Example 3 was replaced weight for weight by a hydrocarbon resin (REGALITE R1100 from Eastman Chemical). Compositions 3 and 4 comprise the following ingredients (amounts in percent by weight): Raw materials (INCI name and Composition 3 Composition 4 commercial reference) comparative according to the invention (outside the invention) Phase A NEOPENTANOATE 7.42 7.42 D ' OCTYLDODECYL POLYISOBUTENE HYDROGEN 6.53 6.53 (PARLEAM from NOF Corporation) Copolymer 8.21 8.21 VinylPyrrolidone / Hexadecene (Antaron V216 from ISP) Phase B ISOHEXADECANE 18.30 18.30 COPOLYMER 7.91 - STYRENE / METHYL STYRENE / HYDROGEN INDENE (REGALITE R1 100 from EASTMAN CHEMICAL) TRIMETHYLSILOXYSILICATE 7.91 (SR 1000 from MOMENTIVE PERFORMANCE MATERIALS) Poly (isobornyl methacrylate-co- 9.89 9.89 isobornyl acrylate-co-acrylate isobutyl-co-acrylic acid) at 50% active ingredient in 50% octyldodecyl neopentanoate according to Example 2 above Phase C COPOLYMER VinylPyrrolidone 1.98 1.98 / EICOSENE (Antaron V220F from ISP) WAX POLYETHYLENE 10.88 10.88 (Performalene 500-L from New Phase Te chnologies) 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 at Wacker) Total: 100 100 Hardness 115.7 Nm '110 Nm' The compositions 3 and 4 are obtained according to the following protocol: Firstly, the fillers and pigments of the phase D are milled with the grinding mill -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 making it possible to obtain sticks 12.7 mm in diameter and the whole is left to cool in a freezer for about an hour. The hardness of the compositions 3 and 4 is measured according to the protocol described above. Compositions 3 and 4 were applied in half-lips to be compared. Composition 3 was applied to the upper and lower left half-lip, and composition 4 was applied to the upper and lower right half-lip.

The composition 4 according to the invention, when applied to the lips is more creamy and forms a thicker and more comfortable deposit, compared with the composition 3 not forming part of the invention. In addition, it is observed that the deposit on the lips made with the composition 4 has a better behavior in time than that produced with the composition 3, in particular, 2 hours after application to the lips, the makeup deposit remains more homogeneous on the lips, by more homogeneous means, we mean that the deposit does not become fragile and does not fragment. As a result, the distribution of the color of the deposit remains more uniform.

Examples 5 and 6: Lipstick product comprising 2 distinct compositions (basecoat / topcoat):

Basecoat: Raw materials (INCI name and Composition 5 of Basecoat (solid) commercial reference) Phase A OCTYLDODECYL 7.00 NEOPENTANOATE ref ELEFAC I-205 from BERNEL CHEMICAL (ALZO) POLYISOBUTENE HYDROGEN 5.00 (PARLEAM from NOF Corporation) Copolymer 10 , 00 VinylPyrrolidone / Hexadecene (Antaron V216 from ISP) Phase B ISOHEXADECANE 23.00 Poly (isobornyl methacrylate-co-10.00 isobornyl acrylate-co-isobutyl acrylate-co-acrylic acid) at 50% of active material in 50% of octyldodecyl neopentanoate according to Example 2 above Phase C COPOLYMER VinylPyrrolidone 2.00 / EICOSENE (Antaron V220F from ISP) WAX POLYETHYLENE 12.00 (Performalene 500-L from New Phase Technologies) Phase D IRON OXIDES 3.43 BLUE 1 LAKE 1.05 TITANIUM DIOXIDE 1.44 RED 28 LAKE RED 28 AL 2.08 LAKE Phase E TRIMETHYLSILOXYPHENYL 23.00 DIMETHICONE (ref BEL SIL PDM 1000 FROM WACKER) TOTAL 100.00 Composition of basecoat 5 is prepared according to the protocol described in the previous example in on compositions 3 and 4.

Topcoat (liquid composition): Raw materials (INCI name Composition 6 of and commercial reference) Topcoat TRIMETHYLSILOXYSILICATE 25 ref SR 1000 of MOMENTIVE PERFORMANCE MATERIALS ISODODECANE 40 BENTONE GEL ISD V of 20 ELEMENTIS POLYETHYLENE 5 PERFORMALENE 400 from NEW PHASE TECHNOLOGIES Nacre 10 Mode of operation: The MQ resin and the bentone gel are dispersed in isododecane. Then the wax is added and the whole is heated at 80 ° C. with Rayneri stirring, until this wax has completely dissolved and until the mixture is homogeneous. The mother-of-pearl is then added to the mixture. The mixture is allowed to cool to room temperature.

The basecoat composition is applied to the lips. After 15 minutes of waiting, a layer of the composition 6 of topcoat is applied using an applicator (preferably a brush) on the lips. A comfortable, homogeneous makeup result with a good level of hold is obtained.

Examples 7 and 8: Lipstick product comprising 2 distinct compositions (basecoat / topcoat):

Basecoat Raw Materials (INCI name and reference Composition 7 of commercial) Basecoat TRIMETHYLSILOXYSILICATE ref SR 1000 of 25 MOMENTIVE PERFORMANCE MATERIALS ISODODECANE 40.8 BE, NTONE GEL ISD V of ELEME.N'TIS 20 POLYETHYLENE PERFORMALENE 400 of NEW 6 PHASE IRON OXIDE TECHNOLOGIES 3.50 BLUE 1 LAKE 1.10 TITANIUM DIOXIDE 1.50 RED 28 LAKE 2.10 RED 28 AI, LAKE Total: 100 Procedure: MQ resin and bentone gel are dispersed in isododecane. The wax is then added and the whole is heated to 80 ° C. with Rayneri stirring until the wax is completely dissolved and until the mixture is homogeneous. The pigments are then added to the mixture. The mixture is allowed to cool to room temperature. 10 Topcoat: Raw materials (INCI name and Composition 8 of Basecoat commercial reference) (solid) Phase A OCTYLDODECYL 7.00 NEOPENTANOATE ref ELEFAC I-205 from BERNEL CHEMICAL (ALZO) POLYISOBUTENE HYDROGEN 5.00 (PARLEAM from NOF Corporation) Copolymer 10.00 VinylPyrrolidone / Hexadecene (Antaron V216 from ISP) Phase B ISOHEXADECANE 23.00 Poly (isobornyl methacrylate-co-10.00 isobornyl acrylate-co-isobutyl acrylate-co-acrylic acid) at 50 % of active material in 50% of octyldodecyl neopentanoate according to Example 2 above Phase C COPOLYMER VinylPyrrolidone 2.00 / EICOSENE (Antaron V220F from ISP) POLYETHYLENE WAX 12.00 (Performalene 500-L from New Phase Technologies Phase D Nacres 8 Phase E TRIMETHYLSILOXYPHENYL 23.00 DIMETHICONE (ref BEL SIL WACKER PDM 1000) TOTAL 100.00 The composition of Topcoat 8 is prepared according to the protocol described in the preceding example for compositions 3 and 4.

The composition 7 of basecoat is applied to the lips using an applicator (preferably a brush). Then a layer of topcoat composition 8 is applied to the lips. We obtain a comfortable makeup result, homogeneous and 10 having a good level of behavior. 58

Claims (15)

REVENDICATIONS1. 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 block having a glass transition temperature (Tg) greater than or equal to 40 ° C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least 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 seq. uence 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 greater than 2, and b) a silicone resin, c )a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, said composition comprising from 0 to 10% by weight of volatile oil of which the flash point is less than or equal to 80 ° C, relative to the total weight of the composition. 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, or in that it is oil-free. volatile whose flash point is less than or equal to 80 ° C. 3. Composition according to any one of the preceding claims, characterized in that the said first 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 CI-12 = C (CH 3) -000 R 11 in which R 11 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, a C 4 to C 12 cycloalkyl group, the acrylates of formula CH 2 CHCH-COOR 12 in which R 12 represents a C 4 to C 12 cycloalkyl group, the (meth) acrylamides of formula: R 'R 7 CH 2 CC CO N R 8 where R 7 and R 8, which are identical or different, represent each a hydrogen atom or a linear or branched C1-C12 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 CH2 = CHCOOR13, R13 representing a linear or branched C1-C12 unsubstituted alkyl group, with the exception of the tert-butyl group, in which is (are) optionally intercalated one or more heteroatoms chosen from O, N, S, methacrylates of formula CH 2 CC (Cl 3) -COOR 4, R 4 representing a linear or branched C 6 to C 12 unsubstituted alkyl group in which one or more heteroatoms chosen from O, 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. 4. 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-COOR12 in which Rt2 represents a C4 cycloalkyl group at C12 and at least one methacrylate monomer of formula CH2 = C (CH3) -COOR'2 in which R't2 represents a C4 to C12 cycloalkyl group, and said second block being obtained from at least a second monomer glass transition temperature less than or equal to 20 ° C and additional monomer. 5. Cosmetic composition for the make-up and / or care of keratin materials comprising, in a physiologically acceptable medium, at least a) a copolymer comprising at least one acrylate monomer of formula CH2 = CH-COOR12 in which R12 represents a C8 cycloalkyl group at C12 and / or at least one methacrylate monomer of formula CH2 = C (CH3) -OOOR '12 in which R' 12 represents a C8 to C12 cycloalkyl group, at least a second acrylate monomer of formula C1-I2 = CHCOOR13, in which R13 represents a linear or branched C1-C12 unsubstituted alkyl group, with the exception of the tert-butyl group, and at least one acrylic acid monomer, b) a silicone resin, c) a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molecular weight of less than 650 g / mol; said composition comprising from 0 to 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. 6. Composition according to any one of claims 4 to 5, characterized in that R12 and R'12 represent independently or simultaneously an isobornyl group. 7. 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 acrylate monomer. isobutyl and at least one acrylic acid monomer. 8. Composition according to any one of the preceding claims, characterized in that it comprises from 0.5 to 40% by weight of active ingredient of block copolymer, and advantageously from 1 to 40% by weight, in particular from 2 to 30% by weight, or even 2 to 20% by weight of copolymer active material relative to the total weight of the composition. 9. Composition according to any one of the preceding claims, characterized in that said silicone resin is chosen from the group comprising: a) a resin of MQ type, in particular chosen from (i) alkylsiloxysilicates, which may be trimethylsiloxysilicates, formula [(R 1) 3 SiO 2) X (SiO 4) y, wherein x and y are integers ranging from 50 to 80, and such that the group R 1 represents a radical as defined above, and preferably is an alkyl group having 1 to 8 carbon atoms or a hydroxyl group, preferably a methyl group, and (ii) phenylalkylsiloxysilicate resins, such as phenylpropyldimethylsiloxysilicate, and / or b) a type T resin, especially chosen from polysilsesquioxanes of formula ( RSiO312) X, wherein x is greater than 100 and the group R is an alkyl group having 1 to 10 carbon atoms, for example a methyl group, said polysilsesquioxanes being furthermore include Si-OH end groups, and / or c) a MQT type resin, in particular of the MQT-propyl type, which may comprise the units (i) (R13SiOli2) a, (ii) (R22SiO2 / 2) b, (iii) (R3SiO312) c and (iv) SiO4 / 2) d, with R1, R2 and R3 independently representing a hydrocarbon radical, in particular alkyl radical, having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or else still a hydroxyl group and preferably an alkyl radical having 1 to 8 carbon atoms or a phenyl group, a being between 0.05 and 0.5, b being between zero and 0.3, c being greater than zero; , d being between 0.05 and 0.6, a + b + c + d = 1 and a, b, c and d being mole fractions, provided that more than 40 mol% of the R3 groups of the resin siloxane are propyl groups. 10. Composition according to any one of the preceding claims, characterized in that said silicone resin is present in the composition in a total solids content of resin ranging from 1 to 40% by weight relative to the total weight of the composition, preferably from 2 to 30% by weight, and more preferably from 3 to 25% by weight. 11. Composition according to any one of the preceding claims, characterized in that said nonvolatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol is octyldodecyl neopentanoate. 12. Cosmetic composition according to any one of the preceding claims, characterized in that it comprises at least one wax, and / or a pasty fatty substance, and / or an additional nonvolatile oil, and / or a filler and / or a coloring matter. 13. Cosmetic makeup process and / or the care of keratinous materials comprising the application on said keratin materials, and in particular the lips or the skin, of a composition as defined in any one of the preceding claims. 14. A cosmetic process for making up and / or caring for keratin materials, comprising the application to said keratinous materials of at least one first composition comprising, in a physiologically acceptable medium, at least one silicone resin as defined in one of the following: Any of claims 9 to 10, and a second composition comprising, in a physiologically acceptable medium, at least: a) a block ethylenic polymer as defined in any one of claims 1 to 8, b) an oil nonvolatile hydrocarbon-based ester comprising at least 16 carbon atoms and having a molar mass of less than 650 g / mol, said second composition comprising from 0 to 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. 15. A makeup and / or care product for keratin materials comprising at least a first composition comprising, in a physiologically acceptable medium, at least one silicone resin as defined in any one of claims 9 to 10 and at least one second composition comprising, in a physiologically acceptable medium, at least: a) a block ethylenic polymer as defined in any one of claims 1 to 8, b) a non-volatile hydrocarbon ester oil comprising at least 16 carbon atoms and having a molecular weight of less than 650 g / mol, said second composition comprising from 0 to 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, said compositions being packaged separately in separate compartments or containers.