EP1545450A2 - Composition for coating keratin fibres, comprising a high dry extract that contains a sequenced polymer - Google Patents

Abstract

Composition for coating keratinic fibers, comprising a film-forming linear ethylenic block copolymer and an organic liquid medium, forms a film with a staying power of at least 12 hours. An Independent claim is also included for a cosmetic kit comprising a composition as above in a compartment of a container with a closure.

Description

The subject of the present invention is a cosmetic composition for coating keratin fibers comprising a block polymer.

The invention also relates to a cosmetic process for making up or treating keratin fibers such as the eyelashes, the eyebrows, the hair.

The composition according to the invention can be a makeup composition, also called mascara, a makeup base for keratin fibers or base coat, a composition to be applied to makeup, also called a top coat, or even a treatment composition. keratin fibers. More specifically, the composition according to the invention is a mascara.

The term “mascara” is intended to mean a composition intended to be applied to the eyelashes: it may be a composition for making up the eyelashes, a make-up for eyelashes, a composition for applying to a mascara, known as still a top coat, or else a cosmetic treatment composition for eyelashes. The mascara is more particularly intended for the eyelashes of human beings, but also for false eyelashes.

Preferably, the composition according to the invention is a leave-in composition.

The compositions for making up the eyes and in particular the eyelashes, such as mascaras, can be in various forms: for example, in the form of oil-in-water or O / W or water-in-oil E two-phase emulsions. / H, aqueous or anhydrous dispersions. It is generally through the qualitative and quantitative choice of waxes and polymers that the application specificities sought for makeup compositions are adjusted, such as for example their fluidity, their covering power and / or their curling power. Thus, it is possible to produce various compositions which, applied in particular to the eyelashes, induce various effects of lengthening, curling and or thickening type (loading or volumizing effect).

It is known from the prior art that the more the solids content (provided in part by a fatty phase consisting for example of one or more waxes or one or more lipophilic polymers) in a composition will increase, the more the deposit of material on the eyelash will be important and therefore the more the result will be volumizing.

However, increasing the solids content in a composition such as an emulsion or dispersion results in an increase in the consistency of the product obtained and therefore an application on the eyelashes delicate and difficult because the product is thick, viscous, it is difficult to deposit, heterogeneously and in packs. The increase in the solid content is therefore often limited by the increase in consistency and does not exceed 45% of the total weight of the composition. This limitation on the solids content is often linked to the impossibility of increasing on the one hand the wax content in the fatty phase which does not exceed 25% for reasons of feasibility (the compositions comprising between 20 and 25% Weights of wax are often very thick, compact, difficult to apply and have unsatisfactory cosmetic properties) and on the other hand to incorporate liposoluble polymers in high content, which considerably increases the viscosity of the composition.

Another way to increase the solids content is to incorporate solid particles such as fillers or pigments but the increase in consistency also limits the maximum percentage of solids, moreover the use of solid particles in large quantities does not not favor the homogeneous and smooth deposit due not only to the consistency but also to the size of the particles introduced which gives a grainy and non-smooth appearance to the deposit.

This is generally the case with so-called volumizing mascaras which are difficult to apply and give a heterogeneous makeup.

It is therefore not difficult to obtain a makeup composition for keratin fibers, comprising a high solids content and therefore a satisfactory volumizing effect, having both an easy and homogeneous application.

On the other hand, the increase in the solid content and the non-homogeneity of the resulting deposit leads to poorer performance of the composition film: it is not sufficiently resistant to friction, in particular from the fingers, and / or in the water, during baths or showers for example, or even to tears or sweat. The mascara then tends to crumble over time: grains are deposited and leave marks around the eye.

The object of the present invention is therefore to propose another formulation route for a composition for coating keratin fibers leading to a loading effect on keratin fibers, and which resolves all or part of the problems associated with conventional formulation routes. In addition, the compositions according to the invention have a smooth and homogeneous application and to make-up of the keratin fibers having good hold. The inventors have discovered that such a composition can be obtained using a particular block polymer. Surprisingly, the incorporation of such a polymer at high or very high contents (up to 50% by weight) makes it possible to significantly increase the dry matter content of a composition for coating the fibers. keratin, while retaining a consistency which allows easy application to keratin fibers, and leads, after application to keratin fibers, to a make-up film with good hold over time: the film does not crumble.

More specifically, the subject of the invention is a composition for coating keratin fibers comprising, in a cosmetically acceptable organic liquid medium, a film-forming linear ethylene polymer, hereinafter called "block polymer", said composition having a dry matter content or dry extract greater than or equal to 45% by weight.

The subject of the invention is also a cosmetic process for making up or non-therapeutic care of keratin fibers, in particular the eyelashes, comprising the application to the keratin fibers of a composition as defined above.

The subject of the invention is also the use of a composition as defined above for obtaining make-up for keratin fibers, in particular for the eyelashes, loading, and or of good staying power.

The subject of the invention is also the use of a film-forming linear block ethylenic polymer in a composition for coating keratin fibers, in order to obtain a composition which is easily applied to keratin fibers and / or leading to a loading makeup, and or of good behavior on said keratin fibers.

The term “cosmetically acceptable” organic liquid medium is understood to mean an organic liquid medium compatible with the eyelashes or the skin.

Dry matter or dry extract content measurement protocol

The dry matter content, that is to say the non-volatile matter content, can be measured in different ways, for example, methods by oven drying, methods by drying by exposure to infrared radiation as well that the chemical methods by titration of water according to Karl Fischer

Preferably, the dry extract of the compositions according to the invention is measured on a Mettler Toledo HG 53 balance (Halogen Moisture Analyzer). A sample of mascara (2-3g) is placed on an aluminum cup and subjected to a temperature of 120 ° C for 60 minutes. The measurement of the dry extract corresponds to the monitoring of the mass of the sample as a function of time. The final solid content is therefore the percentage of the final mass (after 60 min) relative to the initial mass: ES = (final mass / initial mass) X 100.

The composition according to the invention has a dry matter content greater than or equal to 45%, preferably greater than 46%, better still greater than or equal to 47%, even better, greater than 48%, more preferably still, greater than or equal to 50%, up to 70%.

1) Sequence polymer

The polymer of the composition according to the invention is a film-forming linear block ethylenic polymer.

By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.

By "block" polymer is meant a polymer comprising at least 2 separate blocks, preferably at least 3 separate blocks.

The polymer is a polymer with a linear structure. In contrast, a polymer with a non-linear structure is, for example, a polymer with a branched, star, grafted, or other structure.

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 and adherent film on a support, in particular on keratin materials.

Advantageously, the block polymer of the composition according to the invention is free of styrene. By "styrene-free polymer" is meant a polymer containing less than 10% by weight, relative to the total weight of the polymer, preferably less than 5% by weight, better still less than 2% by weight, better still less than 1% by weight, or even not containing, styrenic monomer such as styrene, styrene derivatives such as methylstyrene, chlorostyrene or chloromethylstyrene. styrene or styrene derivatives such as, for example, methylstyrene, chlorostyrene or chloromethylstyrene. According to one embodiment, the block polymer of the composition according to the invention is derived from aliphatic ethylenic monomers. By aliphatic monomer is meant a monomer comprising no aromatic group.

According to one embodiment, the block polymer is an ethylenic polymer derived from aliphatic ethylenic monomers comprising a carbon carbon double bond and at least one ester group -COO- or amide -CON-. The ester group can be linked to one of the two carbons unsaturated by the carbon atom or the oxygen atom. The amide group can be linked to one of the two carbons unsaturated by the carbon atom or the nitrogen atom.

Preferably, the block polymer of the composition according to the invention comprises at least a first block and at least a second block having different glass transition temperatures (Tg), said first and second blocks being linked together by a block intermediate comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

By "at least" a sequence is meant one or more sequences.

It is specified that in the foregoing and what follows the terms "first" and "second" sequences in no way condition the order of said sequences (or blocks) in the structure of the polymer.

Advantageously, the first and second blocks and of the block polymer are incompatible with each other.

By "sequences incompatible with each other" is meant that the mixture formed of the polymer corresponding to the first sequence and the polymer corresponding to the second sequence is not m iscible in the majority organic liquid medium by weight of the organic liquid medium of the composition, at room temperature (25 ° C) and atmospheric pressure (10 ⁵ Pa), for a content of the polymer mixture greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and solvent), 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 an average molecular weight (by weight or by number) equal to that of the block polymer +/- 15%.

In the case where the organic liquid medium comprises a mixture of organic liquids, and in the hypothesis of two or more organic liquids present in identical mass proportions, said mixture of polymers is immiscible in at least one of them.

Of course, in the case where the organic liquid medium comprises a single organic liquid, the latter is the majority organic liquid.

Advantageously, the majority of the organic liquid in the composition is the organic solvent for the polymerization of the block polymer or the majority of the organic solvent for the organic solvent mixtures for the polymerization of the block polymer. The intermediate block is a block 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.

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

Preferably, the block polymer is not water-soluble, that is to say that the polymer is not soluble in water or in a mixture of water and of linear or branched lower monoalcohols having from 2 to 5 atoms of carbon such as ethanol, isopropanol or n-propanol, without modification of pH, at an active material content of at least 1% by weight, at room temperature (25 ° C).

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

By "non-elastomeric polymer" is meant a polymer which, when subjected to a stress intended to stretch it (for example 30% relative to its initial length), does not return to a length substantially identical to its length initial when the constraint ceases. More specifically, by "non-elastomeric polymer" is meant a polymer having an instantaneous recovery Rj <50% and a delayed _recovery R _2h <70% after having undergone an extension of 30%. Preferably, R _\ is <30%, and R _2h <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-coated matrix and then drying for 7 days in a controlled atmosphere at 23 ± 5 ° C and 50 ± 10% relative humidity. One then obtains a film of approximately 100 μm in thickness from which are cut rectangular test pieces (for example with a cookie cutter) with a width of 1 5 m m and a length of 80 mm.

This sample is subjected to a tensile stress using a device sold under the reference Zwick, under the same temperature and humidity conditions as for drying.

The test pieces are drawn at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (l ₀ ) of the test piece.

The instantaneous recovery Ri is determined as follows:

- the specimen is stretched by 30% (ε _max ), that is to say approximately 0.3 times its initial length (l ₀ )

- the stress is relaxed by imposing a return speed equal to the traction speed, ie 50 mm / min and the residual elongation of the test piece is measured in percentage, after return to zero stress (εi).

The instant recovery in% (Ri) is given by the following formula:

Ri ⁼ (Smax "Si) / ε _max ) X 100

To determine the delayed recovery, the residual elongation of the test piece is measured as a percentage (ε _2h ), 2 hours after returning to zero stress.

The delayed recovery in% (R _2h ) is given by the formula below:

R _2h = (ε _max - ε _2h ) / ε _ma χ) x 100 For purely indicative purposes, a polymer according to an embodiment of the invention has an instant recovery Rj of 10% and a delayed _recovery R _2h of 30%.

Advantageously, the block polymer of the composition 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 greater than or equal to 2.8 and in particular, ranging from 2.8 to 6.

The polydispersity index I of the block polymer is equal to the ratio of the average mass by weight Mw to the average mass by number Mn.

The average molar masses by weight (Mw) and by number (Mn) are determined by liquid chromatography by gel permeation (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector).

The weight average mass (Mw) of the block polymer is preferably less than or equal to 300,000, for example it ranges from 35,000 to 200,000, and better still from 45,000 to 150,000.

The number average mass (Mn) of the block polymer is preferably less than or equal to 70,000, it ranges for example from 10,000 to 60,000, and better still from 12,000 to 50,000.

Each block or block of the block polymer of the composition according to the invention is derived from one type of monomer or from several different types of monomer.

This means that each block can consist of a homopolymer or a copolymer; this copolymer constituting the sequence can be in turn statistical or alternating.

Advantageously, the intermediate block 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 block is essentially derived from monomers constituting the first block and the second block.

By "essentially" is meant at least 85%, preferably at least 90%, better at 95% and even better at 100%.

Advantageously, the intermediate sequence has a glass transition temperature Tg comprised between the glass transition temperatures of the first and second sequences. The glass transition temperatures indicated for the first and second sequences can be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3 ^rd ed, 1989, John Wiley, according to the following relation, known as Fox Law:

1 / Tg = Σ (nι / Tg,), im _t being the mass fraction of the monomer i in the sequence considered and Tgi being the glass transition temperature of the monomer of the monomer i.

Unless otherwise indicated, the Tg indicated 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 better still greater than 30 ° C.

In particular, the first sequence can be chosen from: a) a sequence having a Tg greater than or equal to 40 ° C, b) a sequence having a Tg less than or equal to 20 ° C, c) a sequence having a Tg between 20 and 40 ^C C, and the second sequence chosen from a category a), b) or c) different from the first sequence.

In the present invention is meant to denote by the expression: "between ... and ...", a range of values whose limits mentioned are excluded, and "from ... to ..." and "ranging from ... to ... ", a range of values whose limits are included.

a) Sequence before a Tg 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, ranging for example from 50 ° C to 120 ° C, and better still greater or equal to 60 ° C, ranging for example from 60 ° C to 120 ° C. The block having a Tg greater than or equal to 40 ° C can be a homopolymer or a copolymer.

In the case where this block 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 can be a homopolymer, constituted. by a single type of monomer (whose 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 wholly or in part from one or more monomers, the nature and concentration of which are chosen so that the Tg of the resulting copolymer is greater than or equal to 40 ° C. The copolymer can 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 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 below 40 ° C, chosen from monomers having a Tg of between 20 to 40 ° C and / or monomers having a lower Tg or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably less than 15 ° C, in particular ranging from - 80 ° C to 15 ° C and better still less than 10 ° C, for example ranging from -50 ° C to 0 ° C at, as described below,.

The monomers whose homopolymers have a glass transition temperature greater than or equal to 40 ° C. are preferably chosen from the following monomers, also called main monomers:

- methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₁ in which Ri represents an unsubstituted, linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl or R ^ represents a cycloalkyl group C ₄ to _{Cι 2ι}

- the acrylates of formula CH ₂ = CH-COOR ₂ in which R ₂ represents a C ₁₂ -C ₁₂ cycloalkyl group such as isobornyl acrylate or a tert-butyl group,

the (meth) acrylamides of formula:

where R ₇ and R _{8, which are} identical or different, each represent a hydrogen atom or a linear or branched C ₁ -C ₁₂ alkyl group, such as an n-butyl, t-butyl, isopropyl, isohexyl or isooctyl group , or isononyl; or R ₇ represents H and R ₈ represents a 1,1-dimethyl-3-oxobutyl group, and R 'denotes H or methyl. Examples of monomers that may be mentioned include N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide,

- and their mixtures.

Particularly preferred main monomers are methyl methacrylate, isobutyl (meth) acrylate, isobornyl (meth) acrylate and mixtures thereof.

b) Sequence before a Tg less than or equal to 20 ° C

The sequence having a Tg less than or equal to 20 ° C has for example a Tg ranging from - 100 to 20 ° C, preferably less than or equal to 15 ° C, in particular ranging from -80 ° C to 15 ° C and better still lower or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C.

The block having a Tg less than or equal to 20 ^C C can be a homopolymer or a copolymer.

In the case where this block is a homopolymer, it is derived from monomers, which are such that the homopolymers prepared from these monomers have temperatures glass transition tures less than or equal to 20 ° C. This second block can be a homopolymer, consisting of a single type of monomer (whose Tg of the corresponding homopolymer is less than or equal to 20 ° C).

In the case where the block having a Tg of less than or equal to 20 ° C. is a copolymer, it may be derived wholly or in part from one or more monomers, the nature and concentration of which are chosen so that the Tg of the resulting copolymer is less than or equal to 20 ° C. It may for example comprise - one or more monomers whose homopolymer corresponding to a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably less than 15 ° C, in particular ranging from - 80 ° C to 15 ° C and better still less than 10 ° C, for example ranging from -50 ° C to 0 ° C and

one or more monomers whose corresponding homopolymer has a Tg greater than 20 ° C, such as the monomers having a Tg greater than or equal to 40 ° C, for example a Tg ranging from 40 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 / or the monomers having a Tg of between 20 and 40 ° C, as described above.

Preferably, the block having a Tg less than or equal to 20 ° C is a homopolymer.

The monomers whose homopolymer has a Tg of less than or equal to 20 ° C. are preferably chosen from the following monomers, or main monomers:

- the acrylates of formula CH ₂ = CHCOOR ₃ ,

R ₃ representing an alkyl group unsubstituted at d to C ₁ , linear or branched, with the exception of the tert-butyl group, in which there are (are) optionally intercalated one or more heteroatoms chosen from O, N, S,

- methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₄ ,

R ₄ representing an unsubstituted alkyl group C ₆ to C-ι ₂ linear or branched, in which i is (are) optionally intercalated (s) one or more heteroatoms chosen from 0, N and S;

- vinyl esters of formula R ₅ -CO-O-CH = CH ₂ where R5 represents a linear or branched C ₄ to Cι ₂ alkyl group;

- vinyl alcohol ethers and C ₄ to C ₁₂ alcohol ethers,

- C ₄ to C ₁ N-alkyl acrylamides, such as N-octylacrylamide,

- and their mixtures.

The main monomers which are particularly preferred for the block having a Tg of less than or equal to 20 ° C. are alkyl acrylates, the alkyl chain of which comprises from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as l methyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.

c) Sequence before a Tg between 20 and 40 ° C

The block which has a Tg of between 20 and 40 ° C can be a homopolymer or a copolymer.

In the case where this block is a homopolymer, it comes from monomers (or main monomer), which are such that the homopolymers prepared from these monomers have glass transition temperatures between 20 and 40 ° C. This first block can be a homopolymer, consisting of a single type of monomer (the Tg of the corresponding homopolymer ranges from 20 ° C to 40 ° C).

The monomers whose homopolymer has a glass transition temperature of between 20 and 40 ° C. are preferably chosen from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate, isodecylacrylamide and their mixtures.

In the case where the block having a Tg of between 20 and 40 ° C is a copolymer, it comes in whole or in part from one or more monomers (or main monomer), the nature and concentration of which are chosen such that so that the Tg of the resulting co-polymer is between 20 and 40 ° C.

Advantageously, the block having a Tg of between 20 and 40 ° C is a copolymer derived in whole or in part: - from main monomers whose homopolymer corresponding to a Tg greater than or equal to 40 ° C, for example a Tg ranging from 40 ° C to 150 ° C, preferably higher or equal to 50 ° C, ranging for example from 50 to 120 ° C, and better still greater than or equal to 60 ° C, ranging for example from 60 ° C to 120 ° C, as described above, and / or

- main monomers whose corresponding homopolymer has a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably less than or equal to 15 ° C, in particular ranging from -80 ° C at 15 ° C and better still less than or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C, as described above, said monomers being chosen so that the Tg of the copolymer forming the first block is between 20 and 40 ° C.

Such principal monomers are, for example, chosen from methyl methacrylate, isobornyl acrylate and methacrylate, butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.

Preferably, the proportion of the second block having a Tg less than or equal to 20 ° C. ranges from 10 to 85% by weight of the polymer, better from 20 to 70% and even better still from 20 to 50%.

Each of the blocks may nevertheless contain a minority proportion of at least one constituent monomer of the other block. Thus the first block can contain at least one constituent monomer of the second block and vice versa.

Each of the first and / or second block, can (Fri) t, 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 the quantity of this or these additional monomers are chosen so that the sequence in which they are found has the desired glass transition temperature.

This additional monomer is for example chosen from: hydrophilic monomers such as:

ethylenically unsaturated monomers comprising at least one carboxylic or sulfonic acid function, for example: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof, - ethylenically unsaturated monomers comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and the salts of these, - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₆ in which R ₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl or ethyl group , propyl or isobutyl, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F ), such as trifluoroethyl methacrylate,

- methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₉ ,

R ₉ representing a C ₆ to C alkyl group | ₂ linear or branched, in which there are optionally intercalated one or more heteroatoms chosen from 0, N and S, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (CI, Br, I, F);

- the acrylates of formula CH ₂ = CHCOOR ₁₀ ,

Rio representing a linear or branched C ₁ -C ₁₂ alkyl group substituted by 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 R ₁₀ represents a C 1 to C ₁₂ alkyl -O-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R ₈ represents a polyoxyethylene group comprising from 5 to 30 ethylene oxide units

b) ethylenically unsaturated monomers comprising one or more silicon atoms such as methacryloxypropyl trimethoxy silane, methacryloxypropyl tris (trimethylsiloxy) silane,

- and their mixtures.

Particularly preferred additional monomers are acrylic acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof.

According to a preferred embodiment, the block polymer is a non-silicone polymer, that is to say a polymer free of silicon atom.

This or these additional monomers generally represent (s) an amount less than or equal to 30% by weight, for example from 1 to 30% by weight, preferably from 5 to 20% by weight. weight and, more preferably, from 7 to 15% by weight of the total weight of the first and / or second sequences.

Preferably, each of the first and second sequences comprises at least one monomer chosen from esters of (meth) acrylic acid, and optionally at least one monomer chosen from (meth) acrylic acid, and mixtures thereof.

Advantageously, each of the first and second blocks is derived entirely from at least one monomer chosen from acrylic acid, esters of (meth) acrylic acid, and optionally from at least one monomer chosen from (meth acid). ) acrylic, and mixtures thereof

The block polymer can be obtained by radical polymerization in solution according to the following preparation process: - part of the polymerization solvent is introduced into a suitable reactor and heated until reaching the temperature suitable for polymerization (typically between 60 and 120 ° C), once this temperature has been reached, the constituent monomers of the first block are introduced in the presence of part of the polymerization initiator, - after a time T corresponding to a maximum conversion rate of

90%, the constituent monomers of the second block and the other part of the initiator are introduced, the mixture is left to react for a time T '(ranging from 3 to 6 h) at the end of which the mixture is brought to room temperature , - the polymer is obtained in solution in the polymerization solvent.

By polymerization solvent is meant a solvent or a mixture of solvents. The polymerization solvent can be chosen in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol, ethanol, aliphatic alkanes such as isododecane and their mixtures. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

First embodiment

According to a first embodiment, the block polymer comprises a first block having a Tg greater than or equal to 40 ° C., as described above in a) and a second sequence having a Tg less than or equal to 20 ° C, as described above in b)

Preferably, the first block having a Tg greater than or equal to 40 ° C is a copolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, such than the monomers described above.

Advantageously, the second block having a Tg less than or equal to 20 ° C. is a homopolymer derived from monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20 ° C. , such as the monomers described above.

Preferably, the proportion of the block having a Tg greater than or equal to 40 ° C. ranges from 20 to 90% by weight of the polymer, better from 30 to 80% and even better still from 50 to 70%. Preferably, the proportion of the block having a Tg of less than or equal to 20 ° C. ranges from 5 to 75% by weight of the polymer, preferably from 15 to 50% and better still from 25 to 45%.

Advantageously, the block polymer can comprise:

a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl acrylate / isobutyl methacrylate copolymer,

a second sequence of Tg less than or equal to 20 ° C, for example ranging from -85 to - 55 ° C, which is a homopolymer of 2-ethylhexyl acrylate and

an intermediate block which is a random copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.

Second embodiment

According to a second embodiment, the block polymer comprises a first block having a glass transition temperature (Tg) of between 20 and 40 ° C, in accordance with the sequences described in c) and a second block having a glass transition temperature less than or equal to 20 ° C, as described above in b) or a glass transition temperature greater than or equal to 40 ° C, as described in a) above.

Preferably, the proportion of the first block having a Tg of between 20 and 40 ° C. ranges from 10 to 85% by weight of the polymer, better from 30 to 80%, and even better still from 50 to 70%. When the second block is a block having a Tg greater than or equal to 40 ° C., it is preferably present in a proportion ranging from 10 to 85% by weight of the polymer, better from 20 to 70% and even better still from 30 to 70 %.

When the second block is a block having a Tg less than or equal to 20 ° C., it is preferably present in a proportion ranging from 10 to 85% by weight of the polymer, better from 20 to 70% and even better still from 20 to 50 %.

Preferably, the first block having a Tg of between 20 and 40 ° C is a copolymer derived from monomers which are such that the homopolymer corresponding to a Tg greater than or equal to 40 ° C and from monomers which are such ( s) that the corresponding homopolymer has a Tg less than or equal to 20 ° C. Advantageously, the second sequence having a Tg less than or equal to 20 ° C or having a Tg greater than or equal to 40 ° C is a homopolymer.

According to a first variant, the block polymer comprises:

- A first sequence of Tg between 20 and 40 ° C, for example having a Tg of 21 to 39 ° C, which is a copolymer comprising isobornyl acrylate / isobutyl methacrylate / 2-ethyl hexylcrylate ,

a second sequence of Tg less than or equal to 20 ° C, for example ranging from -65 to - 35 ° C, which is a homopolymer of methyl methacrylate and

an intermediate block which is a random copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.

According to a second variant, the polymer according to the invention can comprise:

a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 85 to 115 ° C, which is an isobornyl methacrylate / isobutyl methacrylate copolymer,

- a second Tg of less ^u equal to 20 ° C, for example ranging from -35 to -5 ° C, which is a homopolymer of isobutyl acrylate and

an intermediate block which is a random copolymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate.

According to a third variant, the polymer according to the invention can comprise: a first sequence of Tg greater than or equal to 40 ° C, for example ranging from 60 to 90 ° C, which is an isobornyl acrylate / methacrylate copolymer isobutyl, a second sequence of Tg less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is a homopolymer of isobutyl acrylate and

an intermediate block which is a random copolymer of isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate.

The block polymer may be present in the composition according to the invention in a content ranging from dry materials (or active material) from 5 to 55% by weight relative to the total weight of the composition, preferably ranging from 6 to 45% and better ranging from 8 to 40% by weight.

2) Cosmetically acceptable organic liquid medium

By "organic liquid medium" is meant a medium containing at least one organic compound liquid at room temperature (25 ° C) and atmospheric pressure (10 ⁵ Pa) such as oils and organic solvents commonly used in cosmetic compositions.

According to a particularly preferred embodiment, the organic liquid medium of the composition contains at least one organic liquid which is the or one of the organic solvents for the polymerization of the sequenced p olymer as described previously. Advantageously, said organic polymerization solvent is the predominant organic liquid by weight in the organic liquid medium of the cosmetic composition.

The organic liquid medium of the composition may represent from 10 to 95% by weight relative to the total weight of the composition, preferably from 20 to 90%), and better still from 30 to 80% by weight.

Oils or organic solvents can in particular form a fatty phase, and in particular a continuous fatty phase. The composition can be an anhydrous composition.

The cosmetically acceptable organic liquid medium of the composition advantageously comprises at least one volatile organic solvent or oil defined below.

By "volatile organic oil or solvent" is meant within the meaning of the invention any non-aqueous medium capable of evaporating on contact with the keratin fiber in less than an hour, at room temperature and atmospheric pressure. The volatile organic solvent (s) and volatile oils of the invention are organic solvents and cosmetic oils. ques volatiles, liquid at room temperature, having a non-zero vapor pressure, at room temperature and atmospheric pressure, ranging from 0.13 Pa to 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 mm Hg). By "non-volatile oil" is meant a oil remaining on the keratin fiber at room temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 ⁻³ mm Hg (0.13 Pa).

These oils can be hydrocarbon oils, silicone oils, or mixtures thereof.

The term "hydrocarbon-based oil" means an oil mainly containing hydrogen and carbon atoms and optionally oxygen, nitrogen, sulfur, phosphorus atoms. The volatile hydrocarbon oils can be chosen from hydrocarbon oils having from 8 to 16 carbon atoms, and in particular branched C ₈ -C ₁₆ alkanes such as CQ-C- \ Q isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names of Isopars or Permyls, esters branched in CQ-C- \ Q iso-hexyl neopentanoate, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Either by the company SHELL, can also be used. Preferably, the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and their mixtures.

As volatile oils, volatile silicones can also be used, such as, for example, volatile linear or cyclic silicone oils, in particular those having a viscosity <6 centistokes (6 10 ^"6 m ² / s), and in particular having from 2 to 10 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 2 to 22 carbon atoms As volatile silicone oil which can be used in the invention, there may be mentioned in particular octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane and their mixtures.

The volatile oil can be present in the composition according to the invention in a content ranging from 0.5% to 95% by weight, preferably from 1 to 65% by weight and better still from 5 to 40% by weight, relative to the total weight of the composition. The nonvolatile silicone oils which can be used in the composition according to the invention can be the nonvolatile polydimethylsiloxanes (PDMS), the polydimethylsiloxanes comprising groups with an Ikyl or Icoxy, during and / or at the end of an ilonic chain, groups having each of 2 to 24 carbon atoms, phenylated silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates.

The fluorinated oils which can be used in the composition of the invention are in particular fluorosilicone oils, fluorinated polyethers, fluorinated silicones as described in the

10 EP-A-847752.

The non-volatile oils can be present in the composition according to the invention in a content ranging from 0 to 30% (in particular from 0.1 to 30%) by weight, preferably from 0% to 20% by weight (in particular 0, 1 to 20%), relative to the total weight of the composition, and better still from 0% to 10% by weight (in particular 0.1% to 10%).

15

In one embodiment of the invention, the organic liquid medium of the composition comprises at least one volatile organic oil which is the polymerization solvent for the block polymer and in which the block polymer is advantageously soluble. Preferably, this volatile organic oil is isododecane. Such a composition pre-

20 feel I have the advantage of being easily removed with a classic makeup remover for waterproof mascaras.

The composition according to the invention can comprise an aqueous medium, constituting an aqueous phase, which can form the continuous phase of the composition.

The aqueous phase can consist essentially of water; it can also include a mixture of water and water-miscible solvent (miscibility in water greater than 50% by weight at 25 ° C) such as lower monoalcohols having from 1 to 5 atoms

30. carbon such as ethanol, isopropanol, glycols having from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, C3 ketones C4, aldehydes C2-C4 _e t | _eur mixtures - The aqueous phase (water and optionally the water-miscible solvent) may be present, in a content ranging from 1% to 95% by weight, relative to the total weight of the composition,

Preferably ranging from 3% to 80% by weight, and preferably ranging from 5% to 60% by weight. Wax

The composition according to the invention can comprise a wax or a mixture of waxes. The wax considered in the context of the present invention is generally a lipophilic compound, solid at room temperature (25 ° C), with reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C up to 120 ° C.

By bringing the wax to the liquid state (fusion), it is possible to make it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, the wax is recrystallized in the oils in the mixture.

In particular, the waxes suitable for the invention can have a melting point greater than approximately 45 °, and in particular greater than 55 ° C. The melting point of the wax can be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company METLER.

The measurement protocol is as follows:

A 15 mg sample of product placed in a crucible is subjected to a first temperature rise ranging from 0 ° C to 120 ° C, at the heating rate of 10 ° C / minute, then is cooled from 120 ° C to 0 ° C at a cooling rate of 10 ° C / minute and finally subjected to a second temperature rise ranging from 0 ° C to 120 ° C at a heating rate of 5 ° C / minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the product sample is measured as a function of temperature. The melting point of the compound is the value of the temperature corresponding to the top of the peak of the curve representing the variation of the difference in power absorbed as a function of the temperature.

The waxes capable of being used in the compositions according to the invention are chosen from waxes, solid and rigid at room temperature, of animal, vegetable, mineral or synthetic origin and their mixtures.

The wax can also have a hardness ranging from 0.05 MPa to 30 MPa, and preferably ranging from 6 MPa to 15 MPa. The hardness is determined by measuring the compressive force measured at 20 ° C using the texturometer sold under the name TA-TX2i by the company RHEO, equipped with a stainless steel cylinder with a diameter of 2 mm. moving at the measuring speed of 0.1 mm / s, and penetrating into the wax at a penetration depth of 0.3 mm. The measurement protocol is as follows:

The wax is melted at a temperature equal to the melting point of the wax + 20 ° C. The melted wax is poured into a container 30 mm in diameter and 20 mm deep. The wax is recrystallized at room temperature (25 ° C) for 24 hours, then the wax is stored for at least 1 hour at 20 ° C before carrying out the hardness measurement. The hardness value is the maximum compression force measured divided by the surface area of the texturometer cylinder in contact with the wax.

It is possible in particular to use hydrocarbon waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Camauba wax, Candellila wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, ^" Japanese wax and sumac; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters. Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having fatty chains, linear or branched, in C8-C32. Among these, we could in particular c iterate the hydrogenated dej ojoba oil, the isomerized dej ojoba oil such as partially hydrogenated trans isomerized jojoba oil manufactured or marketed by Désert Whale under the trade name ISO-JOJOBA-50 ^® , hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and l hydrogenated lanolin oil e, di- (trimethylol-1, 1, 1 propane) tetrastearate sold under the name “HEST 2T-4S” by the company HETERENE, di- (trimethylol-1, 1, 1 propane) tetraphenenate sold under the name HEST 2T-4B by the company HETERENE. Mention may also be made of silicone waxes, fluorinated waxes.

It is also possible to use the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the name "PHYTOWAX Olive 18 L 57" or alternatively the waxes obtained by hydrogenation of castor oil esterified with alcohol cetyl sold under the name "PHYTOWAX ricin 16L64 and 22L73", by the company SOPHIM. Such waxes are described in application FR-A-2792190.

According to an advantageous embodiment, the composition according to the invention comprises at least one so-called "hard wax", which has a hardness greater than or equal to 6 MPa, in particular ranging from 6 MPa to 30 MPa, and preferably greater than or equal at 7 MPa, in particular al- from 7 MPa to 25 MPa and, better still greater than or equal to 8 MPa, in particular from 8 to 25 MPa, even better still greater than or equal to 9 MPa, for example from 9 to 20 MPa

The hardness of the hard wax is measured according to the same protocol described above.

As hard wax, it is possible to use Camauba wax, Candellila wax, polyethylene waxes, hydrogenated jojoba oil; sumac wax, ceresin, octacosanyl stearate, tetracontanyl stearate, Shellac wax, behenyl fumarate, di- (trimethylol-1,1,1 propane) tetrastearate sold under the name "HEST 2T- 4S "by the company HETERENE, di- (trimethyiol-1,1,1 propane) tetrabéhenate sold under the name HEST 2T-4B by the company HETERENE, ozokerites like that sold under the name" OZOKERITE WAX SP 1020 P ”by the company STRAHL & PITSCH the wax obtained by hydrogenation of olive oil esterified with stearyl alcohol sold under the name PHYTOWAX Olive 18 L 57 by the company SOPHIM.

The hard wax may be present in the composition according to the invention in a content ranging from 0.1% to 30% by weight, relative to the total weight of the composition, preferably ranging from 1% to 20% by weight, and more preferably ranging from 2% to 10% by weight.

The composition according to the invention may comprise a total content of waxes ranging from 1 to 50% by weight relative to the total weight of the composition, in particular it may contain from 5 to 30%, more particularly from 10 to 30%.

The wax (es) can be present in the form of an aqueous microdispersion of wax. The expression aqueous wax microdispersion is understood to mean an aqueous dispersion of wax particles, in which the size of said wax particles is less than or equal to approximately 1 μm.

Wax microdispersions are stable dispersions of colloidal wax particles, and are described in particular in "Microemulsions Theory and Practice", L.M. Prince Ed., Académie Press (1977) pages 21-32.

In particular, these wax microdispersions can be obtained by melting the wax in the presence of a surfactant, and optionally part of the water, then progressive addition of hot water with stirring. The intermediate formation of an emulsion of the water-in-oil type is observed, followed by a phase inversion with final obtaining of a oil-in-water type microemulsion. On cooling, a stable microdispersion of solid colloidal wax particles is obtained.

Wax microdispersion can also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high pressure homogenizer, turbines.

The particles of the wax microdispersion preferably have mean dimensions of less than 1 μm (in particular ranging from 0.02 μm to 0.99 μm), preferably less than 0.5 μm (in particular ranging from 0.06 μm to 0 , 5 μm). These particles consist essentially of a wax or a mixture of waxes. They may, however, in a minor proportion comprise oily and / or pasty fatty additives, a surfactant and / or a usual fat-soluble additive / active.

In some cases and according to the desire of consumers, it is desirable to produce cosmetic compositions having the advantages described above and having a shiny appearance. Therefore, another object of the present invention is a composition for coating keratin fibers without wax comprising a cosmetically acceptable liquid organic medium and a film-forming linear sequence ethylenic polymer, said polymer being such that when it is present in an amount sufficient in the composition, the latter is capable of forming a film having a resistance greater than or equal to 12 hours.

By "without wax" is meant a composition comprising less than 2% of waxes, preferably less than 1% and better still less than 0.5% of waxes.

Such a wax-free composition also has the advantage of allowing particularly smooth, homogeneous and non-granular deposition.

Another object of the present invention is the use of a composition for coating keratin fibers without wax comprising, in a cosmetically acceptable liquid organic medium, an ethylenic polymer film-forming linear sequence to obtain a film, deposited on said keratin materials, smooth and homogeneous and presenting a shiny appearance.

Such a wax-free composition can in particular be used as a top coat, that is to say as a composition to be applied to a layer of base mascara (base coat), to improve the hold of said mascara. The composition according to the invention may comprise at least one fatty compound which is pasty at room temperature. By "pasty fatty substance" within the meaning of the invention is meant fatty substances having a melting point ranging from 20 to 55 ° C, preferably 25 to 45 ° C, and / or a viscosity at 40 ° C ranging from 0.1 to 40 Pa.s (1 to 400 poises), preferably 0.5 to 25 Pa.s, measured with Contraves TV or Rhéomat 80, equipped with a mobile rotating at 60 Hz. Those skilled in the art can choose the mobile allowing to measure the viscosity, among the mobile MS-r3 and MS-r4, on the basis of his general knowledge, so as to be able to measure the pasty compound tested.

Preferably, these fatty substances are hydrocarbon compounds, optionally of the polymeric type; they can also be chosen from silicone compounds; they can also be in the form of a mixture of hydrocarbon and / or silicone compounds. In the case of a mixture of different pasty fatty substances, the pasty hydrocarbon compounds (preferably containing mainly carbon and hydrogen atoms and possibly ester groups) are preferably used, in the majority proportion.

Among the pasty compounds which can be used in the composition according to the invention, mention may be made of lanolins and lanolin derivatives such as acetylated lanolins or oxypropylene lanolins or isopropyl lanolate, having a viscosity of 18 to 21 Pa .s, preferably 19 to 20.5 Pa.s, and / or a melting point of 30 to 55 ° C and their mixtures. It is also possible to use fatty acid or alcohol esters, in particular those having 20 to 65 carbon atoms (melting point of the order of 20 to 35 ° C and / or viscosity at 40 ° C ranging from 0, 1 to 40 Pa.s) such as tri-isostearyl or cetyl citrate; arachidyl propionate; vinyl polylaurate; cholesterol esters such as triglycerides of vegetable origin such as hydrogenated vegetable oils, viscous polyesters such as poly (12-hydroxystearic acid) and their mixtures.

Mention may also be made of silicone pasty fatty substances such as polydimethylsiloxanes (PDMS) having pendant chains of the alkyl or alkoxy type having from 8 to 24 carbon atoms, and a melting point of 20-55 ° C., such as stearyl dimethicones in particular those sold by the company Dow Corning under the trade names of DC2503 and DC25514, and their mixtures.

The pasty fatty substance may be present in the composition according to the invention in a content ranging from 0.01 to 60% by weight, relative to the total weight of the composition, preferably ranging from 0.5 to 45% by weight. weight, and better ranging from 2% to 30% by weight, in the composition. The composition according to the invention may contain emulsifying surfactants present in particular in a proportion ranging from 2 to 30% by weight relative to the total weight of the composition, and better still from 5% to 15%. These surfactants can be chosen from anionic or nonionic surfactants. Reference may be made to the document “Encyclopedia of Chemical Technology, KIRK-OTHMER”, volume 22, p.333-432, 3rd edition, 1979, WILEY, for the definition of the properties and (emulsifying) functions of the surfactants, in particular p.347-377 of this reference, for anionic and nonionic surfactants.

The surfactants preferably used in the composition according to the invention are chosen:

- among the nonionic surfactants: fatty acids, fatty alcohols, polyethoxylated or polyglycerolated fatty alcohols such as stearyl or cetylstearyl polyethoxylated alcohols, fatty acid and sucrose esters, alkyl glucose esters, in particular fatty esters of CC ₆ alkyl glucose polyoxyethylenated, and mixtures thereof.

- among the anionic surfactants: C15-C30 fatty acids neutralized by amines, ammonia or alkaline salts, and their mixtures.

Surfactants are preferably used which make it possible to obtain an oil-in-water or wax-in-water emulsion.

The composition according to the invention can comprise, in addition to the block polymer described above according to the invention, an additional polymer such as a film-forming polymer.

The film-forming polymer may be present in the composition according to the invention in a dry matter content ranging from 0.1% to 60% by weight relative to the total weight of the composition, preferably from 0.5% to 40% by weight. weight, and better from 1% to 30% by weight.

In the present application, 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 and adherent film on a support, in particular on keratin materials such as the eyelashes.

Among the film-forming polymers which can be used in the composition of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and their mixtures. By radical film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, in particular ethylenic, each monomer being capable of homopolymerizing (unlike polycondensates).

The film-forming polymers of the radical type may in particular be vinyl polymers or copolymers, in particular acrylic polymers.

The vinyl film-forming polymers can result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acid monomers and or amides of these acid monomers.

As monomer carrying an acid group, α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid can be used. Preferably (meth) acrylic acid and crotonic acid are used, and more preferably (meth) acrylic acid.

The esters of acidic monomers are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C 3 -C 4 alkyl, preferably in CC ₂₀ , aryl (meth) acrylates, in particular C ₆ -C ₁₀ aryl, hydroxyalkyl (meth) acrylates, in particular C ₂ -C ₆ hydroxyalkyl.

Mention may be made, among alkyl (meth) acrylates, of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate. Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

Mention may be made, among aryl (meth) acrylates, of benzyl acrylate and phenyl acrylate. Particularly preferred esters of (meth) acrylic acid are alkyl (meth) acrylates.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, that is to say that some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms. As amides of the acid monomers, mention may, for example, be made of (meth) acrylamides, and in particular of N-alkyl (meth) acrylamides, in particular of C ₂ -C ₁₂ alkyl. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide.

The vinyl film-forming polymers can also result from the homopolymerization or from the copolymerization of monomers chosen from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above.

Examples of vinyl esters that may be mentioned include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. As styrene monomers, mention may be made of styrene and alpha-methyl styrene.

Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas.

The polyurethanes can be chosen from anionic, cationic, non-ionic or amphoteric polyurethanes, polyurethanes-acrylics, poly-urethanes-polyvinylpirrolidones, polyesters-polyurethanes, polyurethane-polyurethanes, polyurethanes , polyurea-polyurethanes, and their mixtures.

The polyesters can be obtained, in known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols. The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, acid 2 , 2- dimethylglutaric, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, acid 1, 3-cyclohexanedicarboxylic, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, digiycolic acid, thiodipropionic acid, acid 2, 5-naphthalenedicarboxylic, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers can be used alone or in combination of at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen. The diol can be chosen from aliphatic, alicyclic, aromatic diols. Use is preferably made of a diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol. As other polyols, glycerol, pentaerythritol, sorbitol, trimethylol propane can be used.

The polyester amides can be obtained in a similar manner to the polyesters, by polycondensation of diacids with diamines or amino alcohols. As diamine, there may be used ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine. As amino alcohol, monoethanolamine can be used.

The polyester may also comprise at least one monomer carrying at least one group -S0 ₃ M, with M representing a hydrogen atom, an ammonium ion NH ₄ ⁺ or a metal ion, such as for example an ion Na ⁺ , Li ⁺ , K +, Mg ²⁺ , Ca ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ . One can use in particular a bifunctional aromatic monomer comprising such a group -S0 ₃ M.

The aromatic nucleus of the bifunctional aromatic monomer further bearing a group -S0 ₃ M t el q ue described above could be chosen by e xample p armi I es benzene, naphthalene, anthracene, diphenyl, oxidiphenyl, sulfonyldiphenyl, methylenedediphenyl. As an example of a bifunctional aromatic monomer bearing in addition a group -SO ₃ M: sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, 4-sulfonaphthaene-2,7-dicarboxylic acid.

It is preferred to use isophthalate / sulfoisophthalate-based copolymers, and more particularly copolymers obtained by condensation of di-ethylene glycol, cyclohexane di-methanol, isophthalic acid, sulfoisophthalic acid.

The polymers of natural origin, optionally modified, can be chosen from shellac resin, sandara gum, dammars, elemis, copals, cellulose polymers, and mixtures thereof.

According to a first embodiment of the composition according to the invention, the film-forming polymer can be a water-soluble polymer and can be present in an aqueous phase of the composition; the polymer is therefore dissolved in the aqueous phase of the composition. As examples of water-soluble film-forming polymers, mention may be made of: - proteins such as proteins of plant origin such as proteins from wheat and soy; proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins; - cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, as well as quaternized derivatives of cellulose;

- acrylic polymers or copolymers, such as polyacrylates or polymethacrylates;

- vinyl polymers, such as polyvinylpyrrolidones, copolymers of methyl vinyl ether and malic anhydride, the copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; vinylpyrrolidone and capro | actam copolymers; polyvinyl alcohol; - polymers of natural origin, possibly modified, such as:

. gum arabic, guar gum, xanthan derivatives, kalaya gum;

. alginates and carrageenans;

. glycoaminoglycans, hyaluronic acid and its derivatives; . shellac resin, sandara gum, dammars, elemis, copals;

. deoxyribonucleic acid;

. muccopolysaccharides such as chondroitins sulfate, and mixtures thereof.

According to another alternative embodiment of the composition according to the invention, the film-forming polymer can be a polymer dissolved in a fatty oily phase comprising oils or organic solvents such as those described above (it is said that the film-forming polymer is a fat-soluble polymer). By "liquid fatty phase" is meant, within the meaning of the invention, a fatty phase liquid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg, or 105 Pa), composed of one or several fatty substances liquid at room temperature, such as the oils described above, generally compatible with one another.

Preferably, the liquid fatty phase comprises a volatile oil, optionally in admixture with a non-volatile oil, the oils being able to be chosen from the oils mentioned above.

By way of example of a liposoluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon radical, from 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkylvinyl ether (the alkyl group of which comprises from 2 to 18 carbon atoms), or an allyl or methallyl ester (having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl of the ester group).

These copolymers can be crosslinked using crosslinkers which can be either of the vinyl type, or of the allylic or methallyl type, such as tetraailyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecane - divinyl dioate.

As examples of these copolymers, mention may be made of the copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinyl ether, vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethylvinyl ether, vinyl propionate / cetyl vinyl ether, vinyl stearate / allyl acetate, 2-dimethyl, 2 vinyl octanoate / vinyl laurate, 2-dimethyl, 2 allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / stearate vinyl, allyl dimethyl propionate / vinyl stearate, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, dimethyl vinyl propionate / vinyl laurate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% of tetraailyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / crosslinked allyl stearate with 0.2% divinyl benzene.

As liposoluble film-forming polymers, mention may also be made of liposoluble copolymers, and in particular those resulting from copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having 10 to 20 carbon atoms.

Such liposoluble copolymers can be chosen from copolymers of vinyl polystearate, of vinyl polystearate crosslinked using divinylbenzene, of diallylether or of diallyl phthalate, of copolymers of poly (meth) acrylate of stearyl, of polylau - vinyl, poly (meth) acrylate spleen, these poly (meth) acrylates can be crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol. The water-soluble c opolymers I defined recently have been known and particularly written in application FR-A-2232303; they can have a weight-average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.

As liposoluble film-forming polymers which can be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C ₂ -C ₂₀ alkenes, such as polybutene, alkylcelluloses with a linear or branched alkyl radical, saturated or not saturated. Ci to C ₈ such as ethylcellulose and propylcellulose, vinylpyrolidone (VP) copolymers and in particular copolymers of vinylpyrrolidone and of C ₂ to C ₄₀ and better C ₃ to C ₂₀ alkene. By way of example of a VP copolymer which can be used in the invention, mention may be made of the copolymer of VP / vinyl acetate, VP / ethyl methacrylate, butylated polyvinylpyro lidone (PVP), VP / ethyl methacrylate / methacrylic acid , VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.

The film-forming polymer can also be present in the composition in the form of particles in dispersion in an aqueous phase or in a non-aqueous solvent phase, generally known under the name of latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art. As an aqueous dispersion of film-forming polymer, the acrylic dispersions sold under the names "Neocryl XK-90 ^® ", "Neocryl A-1070 ^® ", "Neocryl A-1090 ^® ", "Neocryl BT-62 ^® " can be used , "Neocryl A-1079 ^® " and "Neocryl A-523 ^® " by the company AVECIA-NEORESINS, "Dow Latex 432 ^® " by the company DOW CHEMICAL, "Daitosol 5000 AD ^® " or "Daitosol 5000 SJ" by the company DAITO KASEY KOGYO; "Syntran 5760" by the company Interpolymer or the aqueous dispersions of polyurethane sold under the names "Neorez R-981 ^® " and "Neorez R-974 ^® " by the company AVECIA-NEORESINS, the "Avalure UR-405 ^® "," Avalure UR- 410 ^® "," Avalure UR-425 ^® "," Avalure UR-450 ^® "," Sancure 875 ^® "," Sancure 861 ^® "," Sancure 878 ^® "and" Sancure 2060 ^® "by GOODRICH, "Impranil 85 ^® " by BAYER, "Aquamere H-1511 ^® " by HYDROMER; sulfopolyesters sold under the brand name "Eastman AQ ^® " by the company EASTMAN CHEMICAL PRODUCTS, vinyl dispersions such as "Mexomer PAM" and also acrylic dispersions in isododecane such as "Mexomer PAP" by company CHIMEX . According to one embodiment, the composition according to the invention advantageously comprises a film-forming linear ethylene block polymer as described above and particles of film-forming polymer dispersed in an aqueous phase.

The composition according to the invention may comprise a plasticizing agent promoting the formation of a film with the film-forming polymer. Such a plasticizing agent can be chosen from all the compounds known to a person skilled in the art as being capable of fulfilling the desired function.

additives

The composition according to the invention can also comprise a coloring matter such as pulverulent coloring matters, liposoluble dyes, water-soluble dyes. This coloring material can be present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition.

The pulverulent coloring matters can be chosen from pigments and pearlescent agents.

The pigments can be white or colored, mineral and / or organic, coated or not. Among the mineral pigments, mention may be made of titanium dioxide, optionally surface-treated, oxides of zirconium, zinc or cerium, as well as oxides of iron or chromium, manganese violet, ultramarine blue, hydrate of chromium and ferric blue. Among the organic pigments, mention may be made of carbon black, pigments of D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.

The nacres can be chosen from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as mica titanium with iron oxides, mica titanium with especially ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.

The liposoluble dyes are for example Sudan red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan brown, D&C Yellow 11, D&C Violet 2, D&C orange 5, quinoline yellow, annatto. The water-soluble dyes are, for example, beet juice, methylene blue, disodium salt of culvert, di- alizarin green sodium, quinoline yellow, trisodium amaranth salt, sodium salt of tartrazine, monosodium salt of rhodamine, disodium salt of fuchsin, xanthophyll.

The fillers can be chosen from those well known to those skilled in the art and commonly used in cosmetic compositions. The fillers can be mineral or organic, lamellar or spherical. There may be mentioned talc, mica, silica, kaolin, polyamide powders, for instance Nylon ^® (Orgasol from Atochem), poly-β- alanine and polyethylene, tetrafluoroethylene polymer powders such as Teflon ^® , lauroyl-lysine, starch, boron nitride, expanded polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as ExpansionL ^® (Nobel Industry), acrylic powders such as polytrap ^® (Dow Corning), polymethyl methacrylate particles and silicone resin microbeads (Tospearls ^® from Toshiba, for example), precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite , hollow silica microspheres (SILICA BEADS ^® from MAPRECOS), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms arbone, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate. The fillers can represent from 0.1 to 25%, and better still from 1 to 20% by weight of the total weight of the composition.

The composition of the invention may also comprise any additive usually used in cosmetics such as antioxidants, preservatives, perfumes, neutralizers, gelling agents, thickeners, vitamins, and their mixtures.

The gelling agents which can be used in the compositions according to the invention may be lipophilic or hydrophilic gelling agents, they may be organic or inorganic, polymeric or molecular.

As lipophilic gelling mineral include optionally modified clays such as hectorites modified with an ammonium chloride of a fatty acid C ₁ 0 -C _22, such as hectorite modified by chloride distearyl di-methyl ammonium such as, for example, that marketed under the name of "Bentone 38V ^® " by the company ELEMENTIS. Mention may also be made of fumed silica optionally treated hydrophobically at the surface, the particle size of which is less than 1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a reduction 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 can be:

- Trimethylsiloxyl groups, which are obtained in particular by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are named "Silica Silylate" according to the CTFA ^(6th edition, 1995). They are for example marketed under the references "Aerosil R812 ^® " by the company DEGUSSA, "CAB-O-SIL TS-530 ^® " by the company CABOT,

- Dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called “Silica dimethyl silylate” according to the CTFA (6 ^th edition, 1995). 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 the CABOT company. Hydrophobic fumed silica in particular has a particle size which can be nanometric to micrometric, for example ranging from approximately 5 to 200 nm.

The polymeric organic lipophilic gelling agents are, for example partially or totally crosslinked elastomeric organopolysiloxanes, of three-dimensional structure, such as those marketed under the names "KSG6 ^® ", "KSG16 ^® " and "KSG18 ^® " by the company SHIN-ETSU , from "Trefil E-505C ^® " and "Trefil E-506C ^® " by the company DOW-CORNING, from "Gransil SR-CYC ^® ", "SR DMF10 ^® ", "SR-DC556 ^® ", "SR 5CYC gel ^® "," SR DMF 10 gel ^® "and" SR DC 556 gel ^® "by the company GRANT INDUSTRIES," SF 1204 ^® "and" JK 113 ^® "by the company GENERAL ELECTRIC; ethyl cellulose such as that sold under the name of "Ethocel ^®" by Dow HEMICAL C; galactomannans comprising from a to s ix, and in particular two to four hydroxyl groups per saccharide, substituted with a saturated alkyl chain or not, such as guar gum alkylated with alkyl chains of C _6, and in particular in Ci to C ₃ and their mixtures. The block copolymers of "diblock" or "triblock" of the polystyrene / polyisoprene or polystyrene / polybutadiene type such as those marketed under the name "Luvitol HSB ^®" by the company BASF, of the polystyrene / copoly (ethylene-propylene) type such than those marketed under the name tion of "Kraton ^® " by the company SHELL CHEMICAL CO or of the polystyrene / copo! y (ethylene-butylene) type.

Among the lipophilic gelling agents which 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 marketed under the names of "Rheopearl TL ^® "or" Rheopearl KL ^® "by the company CHIBA FLOUR.

Of course, those skilled in the art will take care to choose any additional additives and / or their amount in such a way that the advantageous properties of the composition according to the invention are not or substantially not affected by the envisaged addition.

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

Preferably, the composition according to the invention is a mascara:

The composition according to the invention can be packaged in a cosmetic assembly comprising a container delimiting at least one compartment which comprises said composition, said container being closed by a closing element.

The container is preferably associated with an applicator, in particular in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US Pat. No. 4,887,622. It can also be in the form of a comb comprising a plurality of application elements, obtained in particular by molding. Such combs are described for example in patent FR 2 796 529. The applicator can be secured to the container, as described for example in patent FR 2 761 959. Advantageously, the applicator is secured to a rod which , itself, is integral with the closure element.

The closure element can be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is done other than by screwing, in particular via a bayonet mechanism, by snap-fastening, or by tightening. By "snap-on" is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the element closing, then by returning to the elastically unconstrained position of said portion after crossing the bead or cord.

The container can be at least partly made of thermoplastic material. As examples of thermoplastic materials, mention may be made of polypropylene or polyethylene.

Alternatively, the container is made of non-thermoplastic material, in particular glass or metal (or alloy).

The container is preferably equipped with a wringer disposed near the opening of the container. Such a wringer makes it possible to wipe the applicator and possibly, the rod of which it may be integral. Such a wringer is described for example in patent FR 2 792 618.

The content of the patents or patent applications cited above are incorporated by reference into the present application.

The invention is illustrated in more detail in the following examples. The quantities are given in grams.

Example 1: Preparation of a polymer of isobornyl polvacrylate / isobutyl methacrylate / 2-ethylhexyl acrylate)

100 g of isododecane are introduced into a 1 liter reactor, then the temperature is increased so as to go from room temperature (25 ° C) to 90 ° C in 1 hour. 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1.8 g of 2.5-bis (2-ethylhexanoylperoxy) are then added at 90 ° C. over 1 hour. 2.5- dimethylhexane (Trigonox ^® 141, Akzo Nobel). The mixture is maintained for 1 hour 30 minutes at 90 ° C.

Then introduced into the above mixture, still at 90 ° C. and in 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2.5-bis (2-ethylhexanoylperoxy) -2.5 -diméthylhexane.

The mixture is kept for 3 hours at 90 ° C., then the whole is cooled. A 50% solution of active polymer material in isododecane is obtained. A polymer is obtained comprising a first block or poly block (isobornyl acrylate / isobutyl methacrylate) having a Tg of 80 ° C, a second poly-2-ethylhexyl acrylate block having a Tg of - 70 ° C and an intermediate block which is a random polymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.

This polymer has an average mass by weight of 77,000 g / mol and a number average mass of 19,000, ie a polydispersity index I of 4.05.

Example 2: Preparation of a polymer of isobornyl polvacrylate / isobornyl methacrylate / 2-ethylhexyl acrylate)

100 g of isododecane are introduced into a 1 liter reactor, then the temperature is increased so as to go from room temperature (25 ° C) to 90 ° C in 1 hour. 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate, 110 g of isododecane and 1.8 g of 2.5-bis (2-ethylhexanoylperoxy) are then added at 90 ° C. over 1 hour. 2.5- dimethylhexane (Trigonox ^® 141, Akzo Nobel). The mixture is maintained for 1 hour 30 minutes at 90 ° C.

Then introduced into the above mixture, still at 90 ° C. and in 30 minutes, 90 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2.5-bis (2-ethylhexanoylperoxy) -2.5 -diméthylhexane.

The mixture is kept for 3 hours at 90 ° C., then the whole is cooled. A 50% solution of active polymer material in isododecane is obtained.

A polymer is obtained comprising a first block or poly block (isobornyl acrylate / isobornyl methacrylate) having a Tg of 110 ° C., a second poly-2-ethylhexyl acrylate block having a Tg of -70 ° C. and an intermediate block which is a random polymer of isobornyl acrylate / isobornyl methacrylate / 2-ethylhexyl acrylate.

This polymer has an average weight mass of 103,900 g / mol and a number average mass of 21,300, ie a polydispersity index I of 4.89. Example 3 Preparation of a Polymer of Isobornyl Polvimethacrylate / Isobutyl Methacrylate / Isobutyl Acrylate)

100 g of isododecane are introduced into a 1 liter reactor, then the temperature is increased so as to go from room temperature (25 ° C) to 90 ° C in 1 hour. 120 g of isobornyl methacrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1.8 g of 2.5-bis (2-ethylhexanoylperoxy) are added at 90 ° C. over 1 hour. -diméthylhexane (Trigonox ^® 141, Akzo Nobel). The mixture is maintained for 1 hour 30 minutes at 90 ° C.

Then introduced into the above mixture, still at 90 ° C and in 30 minutes, 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2.5-Bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane.

The mixture is kept for 3 hours at 90 ° C., then the whole is cooled. A 50% solution of active polymer material in isododecane is obtained.

A polymer is obtained comprising a first poly block or block (isobornyl methacryate / isobutyl methacrylate) having a Tg of 95 ° C, a second poly isobutyl block having a Tg of - 20 ° C and an intermediate block which is a random polymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate *.

This polymer has an average mass by weight of 100,700 g / mol and a number average mass by 20,800, ie a polydispersity index I of 4.85.

Example 4: Preparation of a Polymer of Isobornyl Polyfacrylate / Isobutyl Methacrylate / Isobutyl Acrylate)

100 g of isododecane are introduced into a 1 liter reactor, then the temperature is increased so as to go from room temperature (25 ° C) to 90 ° C in 1 hour. Then, at 90 ° C. and over 1 hour, 120 g of isobornyl acrylate, 90 g of isobutyl methacrylate, 110 g of isododecane and 1.8 g of 2.5-bis (2-ethylhexanoylperoxy) -2.5 are added. - dimethylhexane (Trigonox ^® 141 from Akzo Nobel). The mixture is maintained for 1 hour 30 minutes at 90 ° C. Then introduced into the above mixture, still at 90 ° C and in 30 minutes, 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2.5-Bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane.

The mixture is kept for 3 hours at 90 ° C., then the whole is cooled. A 50% solution of active polymer material in isododecane is obtained.

A polymer is obtained comprising a first poly block or block (isobornyl acrylate / isobutyl methacrylate) having a Tg of 75 ° C, a second poly isobutyl block having a Tg of - 20 ° C and a block intermediate which is a statistical polymer of isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate.

This polymer has an average mass by weight of 144,200 g / mol and a number average mass of 49,300, ie a polydispersity index I of 2.93.

The following polymer can be prepared

Example 5 Preparation of a Polv Polymer (Isobornyl Acrylate / Isobutyl Methacrylate / 2-Ethyl Hexyl Acrylate)

100 g of isododecane are introduced into a 1 liter reactor, then the temperature is increased so as to go from room temperature (25 ° C) to 90 ° C in 1 hour. Then, at 90 ° C. and over 1 hour, 54 g of isobornyl acrylate, 75.6 g of isobutyl methacrylate, 50.4 g of 2-ethylhexyl acrylate, 110 g of isododecane and 1.8 g of 2.5-Bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane (Trigonox ^® 141 from Akzo Nobel). The mixture is maintained for 1 hour 30 minutes at 90 ° C.

Then introduced into the above mixture, still at 90 ° C. and over 1 hour, 120 g of 2-ethylhexyl acrylate, 90 g of isododecane and 1.2 g of 2.5-Bis (2-ethylhexanoylperoxy) -2.5 -diméthylhexane.

The mixture is kept for 3 hours at 90 ° C., then diluted and then the whole is cooled. A 50% solution of active polymer material in isododecane is obtained.

A polymer is obtained comprising a first poly block or block (isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate) having a Tg of 25 ° C., a second poly-2 hexylacrylate block having a Tg of -50 ° C. and an intermediate sequence which is a random polymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate. Examples 6 to 10: Waterproof mascaras

The following were prepared (the mascara compositions 9 and 10 according to the invention 6 to 8 according to the prior art:

For each composition, the dry extract was measured according to the measurement method described previously in the description.

0 The resistance of the film formed by the composition according to the invention is evaluated by measuring the water resistance, as a function of time, of a film of composition spread on a glass plate and subjected to stirring in an aqueous medium. . The protocol is as follows: At ambient temperature (25 ° C.), a layer of composition 300 μm thick (before drying) is spread over an area of 9 cm × 9 cm on a glass plate of one - 5 sides of 10 cm X 10 cm, then allowed to dry for 24 hours at 30 ° C and 50% relative humidity. After drying, the plate is placed in a crystallizer with a diameter of 19 cm and a capacity of 2 liters filled with a liter of water placed on a magnetic heating stirrer sold under the name RCT basic by the company IKA labor technik. Then placed on the film a smooth cylindrical magnetic PTFE bar (length 6 cm; 0 diameter 1 cm). The stirring speed is adjusted to position 5. The temperature of the water is monitored using a thermometer at a temperature of 20 ° C or 40 ° C. At time t ₀ = 0, the agitation begins. The time t (expressed in minutes) is measured at the end of which the film begins to detach or peel off the plate or when a hole the size of the magnetic stirring bar is observed, that is to say when the hole has a diameter of 6 cm. The water resistance of the film corresponds to the time t measured.

The viscosity is measured with the Rhéomat RM 180 equipped with an MS-r3 or Ms-r4 mobile rotating at 240 min ^"1 for a current supply at 60 Hz or at 200 min ^{" 1} for a current supply at 50 Hz.

These mascaras composition according to the invention are easily applied to the eyelashes. The mascara forms a smooth and homogeneous make-up, and thickens the eyelashes. It has a very good hold.

Examples 11 and 12

A mascara was prepared comprising a block polymer according to the invention (example 12) and a mascara not forming part of the invention (example 11) having the following composition:

For each composition, the dry extract and the resistance were measured, according to the measurement method described previously in the description.

The in vitro charge is measured by gravimetry on test tubes of curved Caucasian hair (30 long hairs of 1 cm distributed over a distance of 1 cm). The test piece is made up by making 3 × 10 passes of mascara spaced 2 minutes apart with product taken up between each series of 10. The test piece is dried 10 min at room temperature and then weighed. This measurement is carried out on 6 test pieces

The load is in fact the quantity of material deposited on the test-tube = mass of made-up test-tube - mass of naked test-tube. The average load is the average of the measurements made on the 6 test pieces.

The following results have been obtained

It is found that the mascara of Example 12 according to the invention has an in vitro charge and a dry extract as well as a superior hold than the mascara not comprising a block polymer (Example 11), while having a lower viscosity. The mascara is easily applied to the eyelashes and, after application, has a lash-loading effect, while having good hold.

Examples 13 to 16

Mascaras were prepared comprising a block polymer according to the invention (examples 14 to 16) and a mascara not forming part of the invention (example 13) having the following composition:

For each compositiori, the dry extract was measured according to the measurement method described previously in the description.

The in vitro charge and the resistance were measured according to the method described in the previous examples.

The following results have been obtained

It can be seen that the mascaras of Examples 14 to 16 according to the invention have a higher resistance to mascara not comprising a block polymer (Example 13), as well as a higher in vitro charge.

Examples 17 to 19: Mascaras without wax

The following mascaras according to the invention were prepared

For each composition, the dry extract was measured according to the measurement method described previously in the description.

The mean gloss of these compositions was also measured according to the following protocol:

On a LENETA brand contrast card and FORM 1A PENOPAC reference card, a layer lying between 50 μm and 150 μm in thickness of the composition is spread out using an automatic spreader. At least the layer covers the white background of the card. The deposit is left to dry for 24 hours at a temperature of 30 ° C., then the brightness is measured at 60 ° on the white background using a glossmeter by BYK GARDNER brand and reference microTRI-GLOSS.

This measurement (between 0 and 100) is repeated at least three times, and the average brightness is the average of the at least three measurements taken.

The following results are obtained

These mascaras have good hold. The value of the gloss of the composition also increases with the level of block polymer. Example 20

1) The average gloss of the mascara of Example 13 according to the prior art is measured with the protocol described above.

2) A film of mascara composition from Example 13 is spread on a glass plate

(base coat) 300 micrometers thick.

Leave to dry for 2 hours at room temperature (25 ° C)

Then spread on the composition film of Example 13, a composition film of Example 18 (top coat) 300 micrometers thick.

The whole is left to dry for 24 hours at room temperature (25 ° C).

The average gloss and the resistance of the final film are then measured according to the protocols described above.

3) The results are presented in the following table:

The application of the mascara of Example 18 according to the invention as a top coat on the mascara of Example 13 according to the prior art makes it possible to obtain a film of composition having a gloss and a hold much superior to that of the film. of basic mascara alone.

Examples 21 to 24

The compositions of Examples 22 to 24 comprising a block polymer according to the invention and the composition of Example 21 (comparative) not comprising a block polymer were prepared.

For each composition, the dry extract was measured according to the measurement method described previously in the description, as well as.

The in vitro load was measured according to the method described in the previous examples.

The following results are obtained:

The mascaras according to the invention comprising the particular block polymer have a dry extract greater than or equal to 45% and a high in vitro load value while being easy to apply.

After application to the eyelashes, the composition film also has good resistance to crumbling and sebum, while being easily demaquillab.es with a conventional makeup remover.

Example 25

We prepare the following mascara Candellila wax 5 g

Copolymer of ethyl acrylate / methyl methacrylate 10 (MA) (80/20) in aqueous dispersion at 50% MA ("Daitosol 5000 AD ^® " from DAITO)

Sequence polymer of Example 4 10 (M A)

Stearic acid 5.8

Triethanolamine stearate 2.9

Black iron oxide 8

Hydroxyethylcellulose 0.9

Gum arabic 3,4

Water, preservatives Qsp 100

The dry extract and the strength were measured, according to the measurement method described previously in the description.

The results obtained are presented in the following table:

This mascara has good hold and thickening eyelash makeup.

Claims

1. Composition for coating keratin fibers comprising a cosmetically acceptable organic liquid medium and a film-forming linear block ethylenic polymer, said composition having a dry matter or dry extract content greater than or equal to 45% by weight. 2. Composition according to claim 1 characterized in that said block polymer is free of styrene. 3. Composition according to claim 1 or 2 characterized in that said block polymer is non-elastomeric. 4. Composition according to one of the preceding claims, characterized in that the block polymer comprises at least a first block and at least a second block having different glass transition temperatures (Tg), said first and second blocks being linked together by an intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. 5. Composition according to the preceding claim, characterized in that the first second block sequence of the block polymer are incompatible with each other. 6. Composition according to the preceding claim, characterized in that the first block of the block polymer is chosen from: a) a block having a Tg greater than or equal to 40 ° C, b) a block having a Tg less than or equal to 20 ° C, c) a sequence having a Tg of between 20 and 40 ° C, and the second sequence is chosen from a category a), b) or c) different from the first sequence. 7. Composition according to claims 5, characterized in that the block having a Tg greater than or equal to 40 ° C of the block polymer is derived wholly or in part from one or more monomers, which are such as the homopolymer prepared from these monomers at a glass transition temperature greater than or equal to 40 ° C. 8. Composition according to the preceding claim, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature greater than or equal to 40 ° C are chosen from the following monomers: - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₁ in which R represents an unsubstituted, linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl or R ₁ is cycloalkyl C ₄ Cι ₂ the acrylates of formula CH ₂ = CH-COOR ₂ in which R ₂ represents a C ₁₂ -C ₁₂ cycloalkyl group such as isobornyl acrylate or a tert-butyl group, - the (meth) acrylamides of formula: where R ₇ and R _{8, which are} identical or different, each represent a hydrogen atom or an alkyl group of 1 to 12 linear or branched carbon atoms, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl group, or isononyl; or R ₇ represents H and R ₈ represents a group 1, 1-dimethyl-3-oxobutyl, and R 'denotes H or methyl. - and their mixtures. 9. Composition according to claim 7 or 8, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature greater than or equal to 40 ° C are chosen from methyl methacrylate, isobutyl methacrylate, ( meth) isobornyl acrylate and mixtures thereof. 10. Composition according to Claim 5, characterized in that the block having a Tg less than or equal to 20 ° C of the block polymer is derived wholly or in part from one or more monomers, which are such that the homopolymer prepared from these monomers at a glass transition temperature less than or equal to 20 ° C. 11. Composition according to the preceding claim, characterized in that the monomers whose corresponding homopolymer has a glass transition temperature less than or equal to 20 ° C are chosen from the following monomers: - the acrylates of formula CH ₂ = CHCOOR ₃ , R ₃ representing an unsubstituted alkyl group of -C _12l linear or branched, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms selected from O, N, S; - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR, R ₄ representing an unsubstituted alkyl group C ₆ to Cι ₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms chosen from 0, N and S; - vinyl esters of formula R ₅ -CO-0-CH = CH ₂ where R ₅ represents a linear or branched C ₁₂ -C ₁₂ alkyl group; - vinyl alcohol ethers and C ₄ to C ₁₂ alcohol ethers; - C-C ₂ N-alkyl acrylamides, such as N-octylacrylamide, and mixtures thereof. 12. Composition according to claim 10 or 11, characterized in that the monomers whose homopolymers corresponding to a glass transition temperature less than or equal to 20 ° C are chosen from alkyl acrylates, the alkyl chain of which comprises 1 to 10 carbon atoms, with the exception of the tert-butyl group. 13. Composition. According to claim 5, characterized in that the block having a Tg of between 20 and 40 ° C of the block polymer is derived wholly or in part from one or more monomers, which are such that homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C. 14. Composition according to Claim 5, characterized in that the block having a Tg of between 20 and 40 ° C is derived wholly or in part from monomers which are such that the homopolymer corresponding to a Tg greater than or equal at 40 ° C and monomers which are such that the corresponding homopolymer has a Tg less than or equal to 20 ° C. 15. Composition according to claim 13 or 14, characterized in that the block having a Tg of between 20 and 40 ° C is derived wholly or in part from monomers chosen from methyl methacrylate, acrylate and methacrylate isobornyl, trifuoroethyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof. 16. Composition according to one of claims 1 to 6, characterized in that the block polymer comprises at least a first block and at least a second sequence- quence, the first sequence having a glass transition temperature (Tg) greater than or equal to 40 ° C and the second sequence having a glass transition temperature less than or equal to 20 ° C, said first and second sequences being interconnected by a intermediate block comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. 17. Composition according to the preceding claim, characterized in that the first block of the block polymer is derived wholly or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. 18. Composition according to claim 16, characterized in that the first block of the block polymer is a copolymer derived from monomers which are such that the homopolymer prepared from these monomers at a glass transition temperature greater than or equal to 40 ° C. 19. Composition according to Claim 17 or 18, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature greater than or equal to 40 ° C are chosen from the following monomers: - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₁ in which R ^ represents an unsubstituted, linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group or R ^ represents a cycloalkyl group C ₄ to C-ι ₂ , the acrylates of formula CH ₂ = CH-COOR ₂ in which R ₂ represents a C ₁₂ -C ₁₂ cycloalkyl group such as isobornyl acrylate or a tert-butyl group, - the (meth) acrylamides of formula: where R ₇ and R _{8, which are} identical or different, each represent a hydrogen atom or an alkyl group of 1 to 12 linear or branched carbon atoms, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl group, or isononyl; or R ₇ represents H and R ₈ represents a 1,1-dimethyl-3-oxobutyl group, and R ′ denotes H or methyl, - and their mixtures. 20. Composition according to one of claims 17 to 19, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature greater than or equal to 40 ° C are chosen from methyl methacrylate, isobutyl methacrylate , isobornyl (meth) acrylate and mixtures thereof. 21. Composition according to one of claims 4:20 pm, characterized in that the proportion of the first block having a Tg greater than or equal to 40 ° C of the block polymer ranges from 20 to 90% by weight of the polymer, better still from 30 to 80% and even better from 50 to 70%. 22. Composition according to one of claims 16 to 21, characterized in that the second block of the block polymer is derived wholly or in part from one or more monomers, which are such that the homopolymer prepared from these monomers have a glass transition temperature less than or equal to 20 ° C. 23. Composition according to one of claims 16 to 22, characterized in that the second block of the block polymer is a homopolymer derived from monomers which are such that the homopolymer prepared from these monomers has a transition temperature glassy less than or equal to 20 ° C. 24. Composition according to claim 22 or 23, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature lower than or equal to 20 ° C are chosen from the following monomers: - the acrylates of formula CH ₂ = CHCOOR ₃ , R ₃ representing an unsubstituted alkyl group Ci to C _12ι linear or branched, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms chosen from O, N, S; - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₄ , [^ representing an alkyl group unsubstituted C ₆ to C-ι ₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms chosen from 0, N and S; - vinyl esters of formula R ₅ -CO-O-CH = CH ₂ where R5 represents a linear or branched C ₁₂ -C ₁₂ alkyl group; - vinyl alcohol ethers and C ₄ to C ₁₂ alcohol ethers; - C-C ₁₂ N-alkyl acrylamides, such as N-octylacrylamide, and their mixtures. 25. Composition according to one of claims 22 to 24, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature less than or equal to 20 ° C are chosen from alkyl acrylates whose alkyl chain comprises from 1 to 10 carbon atoms, with the exception of the butyl group. 26. Composition according to one of claims 16 to 25 characterized in that the proportion of the second block having a Tg less than or equal to 20 ° C of the block polymer ranges from 5 to 75% by weight of the polymer, better still from 15 to 50% and even better from 25 to 45%. 27. Composition according to one of claims 1 to 6, characterized in that the block polymer comprises at least a first block and at least a second block, the first block having a glass transition temperature (Tg) of between 20 and 40 ° C and the second sequence having a glass transition temperature less than or equal to 20 ° C or a glass transition temperature greater than or equal to 40 ° C, said first and second sequences being linked together by an intermediate sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. 28. Polymer according to the preceding claim, characterized in that the first block having a Tg of between 20 and 40 ° C of the block polymer is derived wholly or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C. 29. Composition according to claim 27 or 28, characterized in that the first block having a Tg of between 20 and 40 ° C of the block polymer is a copolymer derived from monomers which are such that the homopolymer corresponding to a Tg greater than or equal to 40 ° C and of monomers which are such that the corresponding homopolymer has a Tg less than or equal to 20 ° C. 30. Composition according to one of claims 27 to 29, characterized in that the first block having a Tg of between 20 and 40 ° C of the block polymer is derived from monomers chosen from methyl methacrylate, acrylate and isobornyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof. 31. Composition according to one of claims 27 to 30, characterized in that the proportion of the first block having a Tg of between 20 and 40 ° C ranges from 10 to 85% by weight. of the polymer, better from 30 to 80% and even better from 50 to 70%. 32. Composition according to any one of claims 27 to 31, characterized in that the second block of the block polymer has a Tg greater than or equal to 40 ° C and is derived wholly or in part from one or more monomers, which are such as the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. 33. Composition according to any one of claims 27 to 32, characterized in that the second block of the block polymer has a Tg greater than or equal to 40 ° C and is a homopolymer derived from monomers, which are such as the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. 34. Composition according to claim 32 or 33, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature greater than or equal to 40 ° C are chosen from the following monomers: - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₁ in which R ^ represents an unsubstituted, linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl or propyl group or isobutyl or R ^ represents a C ₁₂ to cycloalkyl group, - the acrylates of formula CH ₂ = CH-COOR ₂ in which R ₂ represents a C ₁₂ -C cycloalkyl group such as isobornyl acrylate or a group tertio butyl, - the (meth) acrylamides of formula: where R ₇ and R _{8, which are} identical or different, each represent a hydrogen atom or an alkyl group of 1 to 12 linear or branched carbon atoms, such as an n-butyl group, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl; or R ₇ represents H and Rβ represents a 1,1-dimethyl-3-oxobutyl group, and R ′ denotes H or methyl, - and their mixtures. 35. Composition according to one of claims 32 to 34, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature greater than or equal to 40 ° C are chosen from methyl methacrylate, isobutyl methacrylate , isobornyl (meth) acrylate and mixtures thereof. 36. Composition according to one of claims 32 to 35, characterized in that the proportion of the second sequence having a Tg greater than or equal to 40 ° C ranges from 10 to 85%, preferably from 20 to 70% and better still from 30 to 70% by weight of the polymer. 37. Composition according to one of claims 27 to 31, characterized in that the second block of the block polymer has a Tg less than or equal to 20 ° C and is derived wholly or in part from one or more monomers, which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20 ° C. 38. Composition according to one of claims 27 to 31, characterized in that the second block of the block polymer has a Tg less than or equal to 20 ° C and is a homopolymer derived from monomers which are such as the homopolymer prepared from these monomers at a glass transition temperature less than or equal to 20 ° C. 39. Composition according to claim 37 or 38, characterized in that the monomers whose homopolymer corresponding to a glass transition temperature less than or equal to 20 ° C are chosen from the following monomers: - the acrylates of formula CH ₂ = CHCOOR ₃ , R ₃ representing an unsubstituted C1-C6 alkyl group | _2ι linear or branched, with the exception of the tert-butyl group, in which there is (are) optionally intercalated (s) one or more heteroatoms chosen from O, N, S; - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₄ , R ₄ representing a linear or branched C ₆ to C ₁₂ unsubstituted alkyl group, in which there are optionally intercalated one or more heteroatoms chosen from 0, N and S; - vinyl esters of formula R ₅ -CO-O-CH = CH ₂ where R ₅ represents a linear or branched C ₄ -C ₁₂ alkyl group; - vinyl alcohol ethers, and alcohol Cι to C _{4 2;} - C ₄ to C ₁₂ N-alkyl acrylamides, such as N-octylacrylamide, - and their mixtures. 40. Composition according to one of claims 37 to 39, characterized in that the monomers whose homopolymers have glass transition temperatures less than or equal to 20 ° C are chosen from alkyl acrylates whose alkyl chain comprises from 1 with 10 carbon atoms, except for the tert-butyl group. 41. Composition according to one of claims 37 to 40, characterized in that the proportion of the block having a glass transition temperature less than or equal to 20 ° C of the block polymer ranges from 20 to 90% by weight of the polymer, better from 30 to 80%) and even better from 50 to 70%. 42. Composition according to one of the preceding claims, characterized in that the first block and / or the second block of the block polymer comprises at least one additional monomer. 43. Composition according to claim 42, characterized in that the additional monomer is chosen from hydrophilic monomers, ethylenically unsaturated monomers comprising one or more silicon atoms and their mixtures. 44. Composition according to claim 42 or 43, characterized in that the additional monomer is chosen from: - ethylenically unsaturated monomers comprising at least one carboxylic or sulfonic acid function the methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₆ in which R ₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such that trifluoroethyl methacrylate, - methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₉ , R ₉ representing a linear or branched C ₆ to C ₁₂ alkyl group, in which there are optionally intercalated one or more heteroatoms chosen from 0, N and S, said alkyl group being substituted by one or more, substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I, F); - the acrylates of formula CH ₂ = CHCOOR ₁₀ , Rio representing a linear or branched C ₁₂ -C ₁₂ alkyl group substituted by 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 R ₈ represents a C1 to Cι alkyl ₂ -0-POE (polyoxyethylene) with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R ₁₀ represents a polyoxyethylene group comprising from 5 to 30 ethylene oxide units - ethylenically unsaturated monomers comprising at least one tertiary amine function, and their mixtures. 45. Composition according to one of claims 42 to 44, characterized in that the additional monomer (s) are chosen from acrylic acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof. 46. Composition according to one of claims 42 to 45, characterized in that the additional monomer (s) represents (s) from 1 to 30% by weight of the total weight of the first and / or second blocks of the block polymer. > 47. Composition according to one of the preceding claims, characterized in that each of the first and second block of the block polymer comprises at least one monomer chosen from esters of (meth) acrylic acid, and optionally at least one monomer chosen from l (meth) acrylic acid and mixtures thereof. 48. Composition according to one of the preceding claims, characterized in that each of the first and second block of the block polymer is derived entirely from at least one monomer chosen from acrylic acid, esters of (meth) acrylic acid , and optionally at least one monomer chosen from (meth) acrylic acid, and mixtures thereof. 49. Composition according to one of the preceding claims, characterized in that the difference between the glass transition temperatures (Tg) of the first and second blocks of the block polymer is greater than 10 ° C, better still, greater than 20 ° C, preferably greater than 30 ° C and better still greater than 40 ° C. 50. Composition according to one of the preceding claims, characterized in that the intermediate block of the block polymer has a glass transition temperature between the glass transition temperatures of the first and second sequences. 51. Composition according to one of the preceding claims, characterized in that the block polymer has a polydispersity index I greater than 2, better greater than or equal to 2.5, preferably greater than or equal to 2.8. 52. Composition according to one of the preceding claims, characterized in that the block polymer has a polydispersity index of between 2.8 and 6. 53. Composition according to one of the preceding claims, characterized in that the block polymer has a weight average mass (Mw) less than or equal to 300,000. 54. Composition according to one of the preceding claims, characterized in that the block polymer has a weight-average mass (Mw) ranging from 35,000 to 200,000, and better still from 45,000 to 150,000. 55. Composition according to one of the preceding claims, characterized in that the block polymer has a number average mass (Mn) less than or equal to 70,000. 56. Composition according to one of the preceding claims, characterized in that the block polymer has a weight average mass (Mn)) ranging from 10,000 to 60,000, and better still from 12,000 to 50,000. 57. Composition according to one of the preceding claims, characterized in that the block polymer is not soluble at an active material content of at least 1% by weight in water or in a mixture of water and linear or branched lower monoalcohols having from 2 to 5 carbon atoms, without modification of pH, at room temperature (25 ° C). 58. Composition according to one of the preceding claims, characterized in that the block polymer is present in a content ranging from dry matter (or active material) ranging from 5 to 55% by weight relative to the total weight of the composition, preferably ranging from 6 to 45% and better still ranging from 8 to 40% by weight. 59. Composition according to any one of the preceding claims, characterized in that it comprises a volatile oil. 60. Composition according to the preceding claim, characterized in that the volatile oil is chosen from hydrocarbon oils, silicone oils, or their mixtures. 61. Composition according to claim 59 or 60, characterized in that the volatile oil is present in a content ranging from 0.5% to 95% by weight, preferably from 1 to 65% by weight and better still from 5 to 40% by weight. 62. Composition according to any one of the preceding claims, characterized in that it comprises a non-volatile oil. 63. Composition according to the preceding claim, characterized in that the non-volatile oil is present in a content ranging from 0.1% to 30% by weight, preferably from 0.1% to 20% by weight, relative to the total weight of the composition, and better still from 0.1% to 10% by weight. 64. Composition according to any one of the preceding claims, characterized in that the organic liquid medium represents from 10 to 95% by weight relative to the total weight of the composition, preferably from 20 to 90%, and better still from 30 at 80% by weight. 65. Composition according to any one of the preceding claims, characterized in that it comprises an aqueous phase formed of water or of a mixture of water and of organic solvent miscible with water. 66. Composition according to the preceding claim, characterized in that the aqueous phase is present in a content ranging from 1% to 95% by weight, relative to the total weight of the composition, preferably ranging from 3% to 80% by weight. by weight, and preferably ranging from 5% to 60% by weight. 67. Composition according to any one of the preceding claims, characterized in that it comprises a wax. 68. Composition according to the preceding claim, characterized in that the total wax content of the composition ranges from 1 to 50% by weight relative to the total weight of the composition, in particular from 5 to 30%, more particularly from 10 at 30%. 69. Composition according to one of claims 1 to 66, characterized in that it is free of wax. 70. Composition according to any one of the preceding claims, characterized in that it comprises an additional film-forming polymer. 71. Composition according to any one of the preceding claims, characterized in that it comprises a film-forming polymer added in the form of an aqueous dispersion of particles of film-forming polymer. 72. Composition according to claim 70 or 71, characterized in that the film-forming polymer is present in a dry matter content ranging from 0.1% to 60% by weight relative to the total weight of the composition, preferably ranging from 0.5% to 40% by weight, and preferably ranging from 1% to 30% by weight. 73. Composition according to any one of the preceding claims, characterized in that it comprises a surfactant. 74. Composition according to any one of the preceding claims, characterized in that it comprises an additive chosen from coloring matters, antioxidants, fillers, pasty fatty substances, preservatives, perfumes, neutralizers, thickeners , vitamins, coalescing agents, plasticizers, and mixtures thereof. 75. Composition according to one of claims 1 to 74, characterized in that it is a mascara. 76. Composition according to one of the preceding claims, characterized in that it has a dry matter content greater than or equal to 40%, better, greater than 45%, preferably greater than 46%, better greater than or equal to 47%. even better, greater than 48%, more preferably, greater than or equal to 50%, up to 70%. 77. Cosmetic process for making up or non-therapeutic care of keratin fibers comprising the application to the keratin fibers of a composition according to any one of claims 1 to 76. 78. Use of a composition according to any one of the preceding claims, for obtaining a make-up of the keratin fibers, in particular of the eyelashes, charging, and or of good behavior. 79. Use of a styrene-free block polymer in a composition for coating keratin fibers, in order to obtain a composition which is easily applied to keratin fibers and / or leading to a filling makeup, and / or of good hold on said said keratin fibers. 80. Cosmetic assembly comprising: i) i) a container delimiting at least one compartment, said container being closed by a closing element; and ii) ii) a composition for coating keratin fibers placed inside said compartment, the composition being according to any one of claims 1 to 75. 81. Cosmetic assembly according to claim 80, characterized in that the container is formed, at least in part, of at least one thermoplastic material. 82. Cosmetic assembly according to claim 80 characterized in that the container is formed, at least in part, of at least one non-thermoplastic material, in particular glass or metal. 83. An assembly according to any one of claims 80 to 82 characterized in that, in the closed position of the container, the closing element is screwed onto the container. 84. An assembly according to any one of claims 80 to 82 characterized in that, in the closed position of the container, the closing element is coupled to the container other than by screwing, in particular by snap-fastening. 85. An assembly according to any one of claims 80 to 84 characterized in that it comprises an applicator in the form of a twisted brush comprising a plurality of bristles trapped in a twisted core. 86. Assembly according to any one of claims 80 to 84 characterized in that the applicator is different from a twisted brush.