Composition for coating keratin fibres, comprising a high dry extract that contains a sequenced polymer

Translation of description of equivalent WO 2004028493 A2

The present invention relates to a cosmetic composition for keratin fiber coating comprising a polymer block.

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

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

For mascara, means a composition intended to be applied to the eyelashes: it may be a composition dem es ake of eyelashes u ns es makeup of eyelashes u composition applied over a mascara, called top coat, or a composition for cosmetic treatment of the eyelashes. The mascara is more particularly intended for human beings eyelashes, but also for false eyelashes.

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

The eye makeup compositions and especially the eyelashes, such as mascaras, may take different forms: for example, in the form of emulsions two-phase oil-in-water or O / W or water-in-oil E / H, aqueous or anhydrous dispersions. This is usually through the qualitative and quantitative choice of the waxes and polymers that are adjusted for the application specificities for makeup compositions, such as their fluidity, their covering power and / or their curling power. Thus, it is possible to produce various compositions which, when applied in particular to the eyelashes, induce various effects such lengthening, and curling or thickening (charging or volumizing effect).

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

Nevertheless, the increase dela years solids u composition, such q u'une emulsion or dispersion increases the consistency of the resulting product and So an application on the difficult and delicate eyelashes because the product is thick, viscous, it hardly deposited heterogeneously and packet. Increasing the solids content is 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 inability to raise one hand the wax content in the fat component does not exceed 25% for feasibility reasons (the compositions comprising 20 to 25% in wax weight is often very thick and compact, difficult to apply and have unsatisfactory cosmetic properties) and secondly to incorporate soluble polymer in a high content, which significantly increases the viscosity of the composition.

Another way to increase the solids content is to incorporate solid particles as fillers or pigments, but the increase in consistency also limits the maximum percent solids, more use of solid particles in large quantity promotes not homogeneous and smooth deposition not only because of the consistency but also the size of the particles introduced to give a grainy, not smooth filing.

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

It is therefore difficult to obtain a composition for making up keratin fibers, comprising a high solids content and therefore a satisfactory volumizing effect, presented both easy and homogeneous application.

On the other hand, increasing the solids content and the non-homogeneity of drags-trust causes poorer staying power of the film of composition: it is not sufficiently resistant to friction, in particular the fingers, and / or water when bathing or showering, for example, or even to tears or sweat. The mascara has a tendency to crumble over time: grains are deposited and leave marks around the eye.

The present invention therefore aims to propose another formulation route for a composition for coating keratin fibers leading to a loading effect of keratin fibers, and which solves all or part of the problems associated with conventional formulation routes. In addition, the compositions according to the invention have smooth and homogeneous application and to a keratin fiber makeup having good hold. The inventors have discovered that such a composition could be obtained by using a particular polymer sequence. Surprisingly, incorporation of such a polymer at high levels or very high (up to 50% by weight) can significantly increase the solids content of a composition of re- garment fibers keratin, while maintaining a consistency that allows easy application to the keratin fibers and leads, after application to keratin fibers, a good holding makeup film in time: the film does not crumble.

More specifically, the invention relates to a composition for coating keratinous fibers comprising, in a cosmetically acceptable organic liquid medium, a polymer film-forming ethylenic linear block, hereinafter referred to as the text "block polymer", said composition having a dry matter content or solids content greater than or equal to 45% by weight.

The invention also relates to a cosmetic process or for the nontherapeutic care of keratinous fibers, especially the eyelashes, comprising the application to the keratin fibers of a composition as defined above.

The invention also relates to the use of a composition as defined above to obtain a make-up of keratin fibers, especially the eyelashes, charging, and or good staying power.

The invention also relates to the use of an ethylene polymer forming linear sequence in a composition for coating keratin fibers, to obtain a composition which is easily applied lès keratin fibers and / or leading to a charging makeup, and or resilience to the keratin fibers.

The term organic liquid medium "cosmetically acceptable" organic liquid medium compatible with the skin or lashes.

Protocol for Measuring the solids content or dry extract

The dry matter content, i.e. the non-volatile content, can be measured in different ways, there may be mentioned for example, methods by oven drying, methods by drying by exposure to infrared radiation and as chemical treatments by water titration according to Karl Fischer

Preferably, the solids content of the compositions according to the invention is measured on a Mettler Toledo HG 53 (Halogen Moisture Analyzer). A mascara sample (2-3 g) is placed on an aluminum dish and undergoes a temperature of 120 ° C for 60 minutes. Measuring the dry extract is to monitor the mass of the sample versus time .The final solids content is the percentage of the final weight (after 60 min) compared to the initial mass: ES = (final weight / initial weight) X 100.

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

1) Polymer sequence

The polymer of the composition according to the invention is an ethylene polymer film-forming linear sequence.

The term "ethylenic polymer" means a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.

By "block polymer" means a polymer comprising at least two different blocks and preferably at least three distinct sequences.

The polymer is a polymer of linear structure. In contrast, a polymer non-linear structure is, for example, a polymer of branched structure, star, graft, or au be.

By polymer "film" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, especially to keratin materials.

Advantageously, the block polymer of the composition according to the invention is free of styrene. "Polymer free of styrene" is meant a polymer containing less than 10% by weight, based on the total weight of polymer, preferably less than 5% by weight, preferably less than 2% by weight, preferably less than 1% by weight, or not containing, styrenic monomer such as styrene, styrene derivatives such as me- thylstyrène, chlorostyrene or chloromethylstyrene. styrene or styrene derivatives such as methylstyrene, chlorostyrene or chloromethylstyrene. According to one embodiment, the block polymer of the composition according to the invention is derived from aliphatic ethylenic monomers. Aliphatic monomer means a monomer comprising no aromatic groups.

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 may be linked to one of the two unsaturated carbons via the carbon atom or the oxygen atom. The amide group may be linked to one of the two unsaturated carbons via the carbon atom or the nitrogen atom.

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

By "at least one block" means one or more sequences.

It was noted that in the above and following the terms "first" and "second" blocks do not in any way condition the order of the said sequences (or blocks) in the polymer structure.

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

"Mutually incompatible blocks with each other" means that the mixture formed from the polymer corresponding to the first block and the polymer corresponding to the second sequence, is not m iscible in the majority organic liquid medium by weight of organic liquid medium of the composition at room temperature (25 ° C) and atmospheric pressure (10⁵ Pa), for a content of the upper polymer blend or equal to 5% by weight, relative to the total weight of the mixture (polymers and solvent), it being understood that: i) the said polymers are present in the mixture in an amount such that the respective weight ratio ranges from 10/90 to 90/10, and ii) each of the polymers corresponding to the first and second blocks has an average molecular weight (weight or number) equal to that of the block polymer +/- 15%.

In the case where the organic liquid medium comprises a mixture of organic liquid, and in the event of two or more organic liquids present in identical mass proportions, the said polymer mixture 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 organic liquid of the composition is the organic solvent for polymerization of the block polymer or the majority of the organic solvent me- organic solvent diapers of polymerization of the block polymer. The intermediate sequence is a sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer used to "compatibilize" these sequences.

Preferably, the block polymer comprises no silicon atoms in its skeleton. The term "skeleton" means the main chain of the polymer, as opposed to the pendent side chains.

Preferably, the block polymer is not water soluble, i.e. the polymer is not soluble in water or in a mixture of water and of linear or branched lower monoalcohols having 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without pH modification, 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.

"Non-elastomeric polymer" means a polymer which, when subjected to a stress intended to stretch it (for example by 30% relative to its initial length), does not return to a length substantially identical to its length initial when the stress. More specifically, "non-elastomeric polymer" denotes a polymer with an instantaneous recovery Ri <50% and a delayed recovery R_{2 hours} <70% after having undergone an elongation of 30%. Preferably R_\ is <30%, and R_{2 hours} <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 in a Teflon-coated mold and then drying for 7 days in a controlled environment at 23 ± 5 ° C and 50 ± 10% relative humidity. then obtained a film about 100 microns thick in which are cut rectangular specimens (for example to the punch) a I argeur 1 5 mm and a length of 80 mm.

It requires that sample to a tensile stress using a machine is marketed under the reference Zwick, under the same conditions of temperature and humidity for drying.

The specimens are pulled at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (l₀) Of the test piece.

It determines the instantaneous recovery R as follows:

- Is drawn the test piece by 30% (ε_max), That is to say about 0.3 times its initial length (l₀)

- The stress is released by applying a return speed equal to the tensile speed, ie 50 mm / min and measuring the percentage of the residual elongation of the specimen, after returning to zero constraint (εi).

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

Ri ⁼ (Smax "Si) / ε_max) X 100

To determine the delayed recovery, the residual elongation is measured in percent specimen (ε_{2 hours}), 2 hours after returning to zero stress.

The% delayed recovery (R_{2 hours}) Is given by the following formula:

R_{2 hours}= (Ε_max - ε_{2 hours}) / Ε_myχ) x 100 Purely as a guide, a polymer according to one embodiment of the invention has an instantaneous recovery R i of 10% and a delayed recovery R_{2 hours} 30%.

Advantageously, the block polymer of the composition according to the invention has a polydispersity index I of greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still greater than or equal to 2.8 and in particular, ranging from 2.8 to 6.

The polydispersity index I of the polymer sequence is equal to the ratio of the average mass Mw to the number-average mass Mn.

the average molecular weights are determined by weight (Mw) and number (Mn) 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, it is for example 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 70000, it will for example 10000-60000 and better still from 12 000 to 50 000.

Each sequence 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 may consist of a homopolymer or a copolymer; this copolymer constituting the block may be his turn random 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 derived essentially from constituent monomers of the first sequence and second sequence.

By "substantially" means 85% at least, preferably at least 90%, more than 95% and even better still 100%.

Advantageously, the intermediate block has a glass transition temperature Tg between the glass transition temperatures of the first and second sequences. The glass transition temperatures indicated for the first and second blocks may be theoretical Tg values ​​determined from the theoretical Tg values ​​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 relationship, known as Fox's law:

1 / Tg = Σ (nι / Tg), im_t being the mass fraction of the monomer i in the block under consideration and Tgi being the glass transition temperature of the homopolymer of the monomer i.

Unless otherwise indicated, the Tg values ​​indicated for the first and second blocks in the present patent application are theoretical Tg.

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

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

Is meant in the present invention, the expression "between ... and ...", a range of values ​​which the limits mentioned are excluded, and "from ... to ..." and "going from ... to ... ", a range of values ​​whose terminals are included.

a) Block with a Tg of greater than or equal to 40 ° C The block with a Tg of 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, for example ranging from 50 ° C to 120 ° C and better still greater or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C. The block with a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer.

In the case where this block is a homopolymer, it is derived from monomers which are such (s) that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. This first block may be a homopolymer consisting of. by a single type of monomer (for which the Tg of the corresponding homopolymer is greater than or equal to 40 ° C).

In the case where the first block is a copolymer, it may be from an entirely or partly from one or more monomers, the nature and concentration are selected sies so that the Tg of the resulting copolymer is greater than or equal at 40 ° C. The copolymer may for example include:

- Monomers which are such (s) that the homopolymers prepared from these monomers have or above Tg 40 ° C, for example a Tg ranging from 40 to 150 ° C, preferably greater than or equal to 50 ° C , for example ranging from 50 ° C to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C, and

- Monomers which are such (s) that the homopolymers prepared from these monomers have lower Tg at 40 ° C, chosen from monomers with a Tg of between 20 to 40 ° C and / or monomers with a Tg of less than or equal to 20 ° C, for example a Tg ranging from -100 to 20 ° C, preferably below 15 ° C, especially ranging from - 80 ° C to 15 ° C and better less than 10 ° C, for example ranging from -50 ° C to 0 ° C, as described further.

The monomers whose homopolymers have a glass transition temperature exceeding 40 ° C are preferably chosen from the following monomers, Missed Call strip which is also the main monomers:

- Methacrylates of formula CH₂ = C (CH₃) COOR₁ wherein R represents an unsubstituted alkyl group, linear or branched, containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl group or R represents a cycloalkyl group C₄ to Cι_2ι

- CH formula acrylates₂ = CH-COOR₂ wherein R₂ represents a cycloalkyl group of C -C₁₂ such as isobornyl acrylate or a tert-butyl group,

(meth) acrylamides of formula:

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wherein R₇ and R₈ identical or different, each represent a hydrogen atom or an alkyl group C ^ -C₁₂ linear or branched, such as n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl; or R₇ is H and R₈ 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 mixtures thereof.

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

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

The block with a Tg less than or equal to 20 ° C for example a Tg ranging from - 100-20 ° C, preferably less than or equal to 15 ° C, especially ranging from -80 ° C to 15 ° C and preferably less or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C.

The block with a Tg less than or equal to 20^CC may be a homopolymer or a copolymer.

In the case where this block is a homopolymer, it is derived from monomers which are such (s) that the homopolymers prepared from these monomers have temperature lower glass transition structures or equal to 20 ° C. This second block may be a homopolymer consisting of one type of monomer (for which the Tg of the corresponding homopolymer is less than or equal to 20 ° C).

In the case where the block with a lower or Tg at 20 ° C is a copolymer, it may be totally or partially derived from one or more monomers, the nature and concentration are chosen such 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 corresponding homopolymer has a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably below 15 ° C, in particular from - 80 ° C to 15 ° C and preferably below 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 monomers with a Tg of 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, for example ranging from 50 ° C to 120 ° C and better still greater than or equal to 60 ° C, for example ranging from 60 ° C to 120 ° C and / or monomers with a Tg of between 20 and 40 ° C, as described above.

Preferably, the block with 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 monomer:

- CH formula acrylates₂ = CHCOOR₃,

R₃ representing a substituted alkyl of C₁ 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 CH₂ = C (CH₃) COOR₄,

R₄ representing a substituted alkyl C₆ -C-ι₂ linear or branched, wherein i is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S;

- A formula of vinyl esters₅-CO-O-CH = CH₂ wherein R5 represents an alkyl group C₄ to Cι₂ straight or branched;

- Vinyl alcohol ethers, and alcohol C₄ -C₁₂,

- N-alkyl C₄ -C₁ acrylamides, such as N-octylacrylamide,

- And mixtures thereof.

Particularly preferred main monomers for the block with a Tg less than or equal to 20 ° C are alkyl acrylates whose alkyl chain contains from 1 to 10 carbon atoms, except the tert-butyl group, such as methyl acrylate, isobutyl acrylate, 2-ethylhexyl and mixtures thereof.

c) Block with a Tg of between 20 and 40 ° C.

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

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

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

In the case where the block with a Tg of between 20 and 40 ° C is a copolymer, it is totally or partially derived from one or more monomers (or main monomer) whose nature and concentration are chosen such so that the resulting Tg of the copolymer is between 20 and 40 ° C.

Advantageously, the block with a Tg of between 20 and 40 ° C is a copolymer outcome in whole or in part: - main monomers whose corresponding homopolymer has a Tg of greater than or equal to 40 ° C, for example a Tg ranging from 40 ° C to 150 ° C, preferably greater than or equal to 50 ° C, for example ranging from 50 to 120 ° C and better still greater than or equal to 60 ° C, for example ranging 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, especially ranging from -80 ° C at 15 ° C and preferably less than or equal to 10 ° C, for example ranging from -50 ° C to 0 ° C, as described above, the said monomers being chosen such that the Tg of the copolymer forming the first block is between 20 and 40 ° C.

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

Preferably, the proportion of the second block with a Tg less than or equal to 20 ° C is from 10 to 85% by weight of the polymer, more preferably from 20 to 70% and more preferably 20 to 50%.

Each of the blocks may contain in small proportion at least one constituent monomer of the other sequence. Thus, the first block may contain at least one constituent monomer of the second block, and vice versa.

Each of the first and / or second blocks (Fri) t, include, in addition to the monomers indicated above, one or more other monomers known as monomers ad- ditional, different from the main monomers mentioned above.

The nature and amount of this or these additional monomer are chosen so that the sequence in which they are present has the desired glass transition temperature.

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

- Unsaturated monomers (s) ethylenic (s) comprising at least one carboxylic or sulfonic acid function, for instance: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof, - Unsaturated monomers (s) ethylenic (s) comprising at least one tertiary amine function, for instance 2-vinylpyridine, 4-vinylpyridine, methacrylate minoéthyle dimethylamine, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and salts mide thereof, - methacrylates of formula CH₂ = C (CH₃) COOR₆ wherein R₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups (such as methacrylate 2-hydroxypropyl methacrylate 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as trifluoroethyl methacrylate,

- Methacrylates of formula CH₂ = C (CH₃) COOR₉,

R₉ Representative alkyl C₆ to C- |₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S, said alkyl group being substituted by one or more substituents chosen from hydroxyl groups and halogen atoms ( Cl, Br, I, F);

- CH formula acrylates₂ = CHCOOR₁₀,

Rio is alkyl C to C ^₁₂ linear or branched substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as acrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl, or R₁₀ represents an alkyl C, to C₁₂-O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 30 times, for example methoxy-POE, or R₈ 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 (trimethyl thylsiloxy) silane,

- And mixtures thereof.

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-silico-born polymer, i.e. a polymer free of silicon atoms.

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

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

The block polymer is obtainable by radical solution polymerization according to the following preparation process: - part of the polymerization solvent is introduced into a suitable reactor and heated until the adequate temperature for the polymerization (typically between 60 and 120 ° C), once this temperature is reached, the constituent monomers of the first block are introduced in the presence of a portion 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 rest of the initiator are introduced, are allowed to react for a time T '(ranging from 3 to 6 hours) after 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 solvent mixture. The polymerization solvent may be chosen especially from ethyl acetate, butyl acetate, alcohols such as isopropanol and ethanol, aliphatic alkanes such as dodecane iso- and mixtures thereof. 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 with a Tg greater than or equal to 40 ° C, as described above in a) and second block with a Tg less than or equal to 20 ° C, as described above in b)

Preferably, the first block with a Tg of 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 exceeding 40 ° C, such as the monomers described above.

Advantageously, the second block with a Tg of less than or equal to 20 ° C is a homopolymer derived from monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature not exceeding 20 ° C. such as the monomers described above.

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

Advantageously, the block polymer may comprise:

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

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

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

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, according to the blocks described in c) and a second block having a glass transition tempera- ture less than or equal to 20 ° C, as described above in b) or a glass transition temperature exceeding 40 ° C, as described in a) above.

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

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

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

In a first variant, the block polymer comprises:

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

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

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

In a second variant, the polymer according to the invention may comprise:

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

- A second lower Tg sequence ^' 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 may comprise: - a first Tg of greater than or equal to 40 ° C, for example ranging from 60 to 90 ° C, which is an isobornyl acrylate / methacrylate isobutyl, - A second sequence Tg of less than or equal to 20 ° C, for example ranging from -35 to -5 ° C, which is an isobutyl acrylate homopolymer and

- An intermediate block which is an isobornyl acrylate random copolymer / isobutyl methacrylate / isobutyl acrylate.

The block polymer may be present in the composition according to the invention in an amount ranging of solids (or active material) 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.

2) Middle cosmetically acceptable organic liquid

By "organic liquid medium" means a medium containing at least one liquid organic compound at room temperature (25 ° C) and atmospheric pressure (10⁵ Pa), such as oil 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 a solvent or organic (s) dep olymerisation dup olymère sequence s such that d p reviously written. Advantageously, said organic polymerization solvent is the major organic liquid by weight in the organic liquid medium of the cosmetic composition.

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

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

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

By "volatile oil or organic solvent" is meant in the sense of the invention any non-aqueous medium capable of evaporating on contact with the keratin fiber in less than one hour at room temperature and atmospheric pressure. The volatile organic solvents and the volatile oils of the invention are organic solvents and cosmetic oils c volatile liquid at room temperature, having a nonzero vapor pressure, at room temperature and atmospheric pressure, ranging from 0.13 Pa to 40 000 Pa (10^"3 to 300 mmHg), in particular ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mmHg), more particularly from 1, 3 Pa to 1300 Pa (0.01 to 10 mm Hg). By "non-volatile oil" means an oil that remains on the keratin fiber at room temperature and atmospheric pressure for at least several hours and that especially has a vapor pressure of less than 10^"3 mmHg (0,13Pa).

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

The term "hydrocarbon oil" means an oil mainly containing hydrogen and carbon atoms and possibly oxygen, nitrogen, sulfur, phosphorus. Volatile hydrocarbon oils may be chosen from hydrocarbon oils having 8 to 16 carbon atoms, and especially branched alkanes C₈-C₁₆ isoalkanes CQ-C \ Q of petroleum origin (also known as isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane) isodecane, isohexadecane, for example the oils sold under the trade names iso pars or Permethyl, branched esters CQ-C \ Q neopentanoate iso-hexyl, and mixtures thereof. Other volatile hydrocarbon oils such as petroleum distillates, especially those sold under the name Shell either by the company Shell, may also be used. Preferably the volatile solvent is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof.

Volatile oils can also be used are volatile silicones such as the oils of linear or cyclic volatile silicones, especially those with a viscosity &lt;6 centistokes (6 October^"6 m²/ S) and especially containing from 2 to 10 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having 2 to 22 carbon atoms. As volatile silicone oil in the invention include in particular octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodeca methyl cyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyl tetrasiloxane, the dodeca-methyl pentasiloxane and mixtures thereof.

The volatile oil may be present in the composition according to the invention in an amount al lant from 0.5% to 95% by weight, preferably 1 to 65% by weight and better still from 5 to 40% by weight, relative to the total weight of the composition. The non-volatile silicone oils used in the composition according to the invention can be polydimethylsiloxane (PDMS), polydimethylsiloxanes comprising o f g roupements has Ikyle wa Icoxy, p uring and / or out enb December iliconée s Chain Initiative, which groups each 2 to 24 carbon atoms, phenyl silicones 5 phenyltrimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphénylsi- siloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2- phenylethyltrimethylsiloxysilicates.

Fluorinated oils used in the composition of the invention are especially fluorosilicone oils, fluoro polyethers and fluorosilicones as described in

10 EP-A-847752.

The non-volatile oils may be present in the composition according to the invention in a content ranging from 0 to 30% (especially 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 of the polymer block and wherein the block polymer is preferably soluble. Preferably, the volatile organic oil is isododecane. Such a composition pre-

20 I feel advantage of being easily démaquillable with classic makeup remover waterproof mascaras.

The composition according to the invention may comprise an aqueous medium, constituting an aqueous phase 25, which may form the continuous phase of the composition.

The aqueous phase may consist essentially of water; it may also comprise a mixture of water and water miscible solvent (miscibility in water of greater than 50% by weight at 25 ° C), for instance lower monoalcohols containing from 1 to 5 carbon

30. atoms such as ethanol, isopropanol, glycols containing from 2 to 8 carbon atoms such as propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, ketones C3 C4, C2-C4 aldehydes _et |_eur mélanges- 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,

35 preferably from 3% to 80% by weight and preferentially ranging from 5% to 60% by weight. Wax

The composition according to the invention may comprise a wax or a mixture of waxes. The wax under consideration in the context of the present invention is generally a lipophilic compound that is solid at room temperature (25 ° C), with a reversible solid / liquid reversible, having a melting point above or equal to 30 ° C up to 120 ° C.

By bringing the wax to the liquid state (melting), it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but on returning the temperature of the mixture at room temperature, recrystallization of the wax in the oils of the mixture.

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

The measurement protocol is the following:

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

The waxes that may be used in the compositions according to the invention are selected among sies waxes that are solid and rigid at room temperature, of animal, plant, mineral or synthetic oils and mixtures thereof.

The wax may 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 compression force, measured at 20 ° C using the texture analyzer sold under the name TA TX2i by Rheo, equipped with a stainless steel cylinder with a diameter of 2 mm moving at the speed of measurement of 0.1 mm / s, and penetrating into the wax to a penetration depth of 0.3 mm. The measurement protocol is the following:

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

hydrocarbon waxes such as beeswax, lanolin wax may especially be used, and Chinese insect waxes; rice wax, carnauba wax, candelilla wax, ouricurry wax, alfalfa wax, wax, cork fiber, sugar cane wax,^" Japan wax and sumach wax; montan wax, microcrystalline waxes, paraffins and ozokerite; polyethylene waxes, waxes obtained by the Fischer-Tropsch synthesis and waxy copolymers, and esters thereof. It is also made of waxes obtained by catalytic hydrogenation of animal or plant oils containing fatty chains, linear or branched C8-C32. C Among them one, ONP had otamment c n iter oil dej ojoba h ydrogénée, oil dej ojoba isomerized as partially hydrogenated trans isomerized jojoba oil manufactured or sold by the company Desert Whale under the commercial reference ISO - Jojoba-50^®, Hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated copra oil and hydrogenated lanolin oil, tetrastearate di- (trimethylol-1, 1, 1 propane) sold under the name "Hest 2T-4S "by Heterene the tele- trabéhénate di- (trimethylol-1, 1, 1 propane) sold under the name Hest 2T-4B by Heterene. It may also be made of silicone waxes and fluoro waxes.

One can also use the esterified wax obtained by hydrogenation of olive oil with stearyl alcohol sold under the name "PHYTOWAX Olive 18 L 57" or even the waxes obtained by hydrogenation of castor oil esterified with alcohol cetyl sold under the name "ricin 16L64 and 22L73 PHYTOWAX" by 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 said wax "hard wax", which has a hardness greater than or equal to 6 MPa, especially ranging from 6 MPa to 30 MPa, and preferably greater than or equal 7 MPa, in particular al lant of 7 MPa to 25 MPa and more preferably greater than or equal to 8 MPa, in particular from 8 to 25 MPa, more preferably 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 can be used carnauba wax, candelilla, polyethylene waxes, hydrogenated jojoba oil; sumach wax, ceresin, octacosanyl stearate, tetracontanyl stearate, shellac wax, behenyl fumarate, tetrastearate di- (1,1,1-trimethylolpropane) sold under the name "Hest 2T-4S "by Heterene, tetrabehenate di- (1,1,1-triméthyiol) sold under the name Hest 2T-4B by Heterene the ozokerites as that sold under the name" ozokerite WAX ​​SP 1020 P "by the company Strahl &amp; Pitsch wax ester obtained by hydrogenation of olive oil 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, based on the total weight of the composition, preferably ranging from 1% o to 20% by weight, and more preferentially ranging from 2% to 10% by weight.

The composition according to the invention may comprise a total wax content 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 or waxes (Fri) t be present (s) in the form of an aqueous microdispersion of wax. Means aqueous microdispersion of wax, an aqueous dispersion of wax particles, wherein the size of said wax particles is less than or equal to about 1 micron.

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

In particular, these wax microdispersions may be obtained by melting the wax presence of a surfactant, and optionally a portion of the water, followed by gradual addition of hot water with stirring. The intermediate formation is observed of an emulsion of water-in-oil type, followed by a phase inversion with final production of a microemulsion of the oil-in-water type. On cooling, u is obtained only steady microdispersion of solid colloidal particles of wax.

The wax microdispersions may also be obtained by stirring the mixture of wax, surfactant and water using stirring means such as ultrasound, high-pressure homogenizer homo-, turbines.

Particles of wax microdispersion preferably have mean sizes of less than 1 .mu.m (especially ranging from 0.02 .mu.m to 0.99 .mu.m), preferably less than 0.5 .mu.m (especially ranging from 0.06 microns to 0 5 .mu.m). These particles consist essentially of a wax or mixture of waxes. However, they may comprise a small proportion of oily fatty additives and / or pasty, a surfactant and / or additive / active usual fat-soluble.

In certain cases and according to the desire of consumers, it is desirable to provide cosmetic compositions having the advantages described above and with a glossy finish. Therefore, another object of the present invention is a composition for coating keratin fibers without wax comprising a cosmetically acceptable organic liquid medium and a film-forming linear ethylenic polymer block, said polymer being such that when present in an amount sufficient in the composition, the latter is capable of forming a film having a higher or equal held at 12 hours.

By "wax-free" means a composition comprising less than 2% of waxes, preferably less than 1% and preferably less than 0.5% of waxes.

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

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

Such a composition without wax may especially be used as a top coat that is commme composition for application to a base coat of mascara (base coat), to improve the holding of the said mascara. The composition according to the invention may comprise at least one pasty fatty compound at room temperature. "Pasty fatty substance" within the meaning of the invention, means fatty substances with 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 using a Contraves TV or Rheomat 80 viscometer, equipped with a spindle rotating at 60 Hz. the skilled artisan can select the spindle for measuring the viscosity from the MS-r3 and MS-r4 mobile, on the basis of his general knowledge, so as to realize the extent of the pasty compound tested.

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

Among the pasty compounds that may be used in the composition according to the invention include the lanolin and lanolin derivatives, for instance acetylated lanolin or oxypropylenated or isopropyl lanolate, having a viscosity of 18-21 Pa .s, preferably 19 to 20.5 Pa.s, and / or a melting point of 30 to 55 ° C and mixtures thereof. Can also be used esters of fatty acids or fatty alcohols, especially those having 20 to 65 carbon atoms (the order of melting point 20 to 35 ° C and / or viscosity at 40 ° C from 0, 1 to 40 Pa · s) such as citrate triisostearyl or cetyl; the arachidyl propionate; polyvinyl laurate; cholesterol esters such as triglycerides of plant origin such as hydrogenated plant oils, viscous polyesters such as poly (12-hydroxy) and mixtures thereof.

It can also be made of silicone pasty fatty substances such as polydimethylsiloxane (PDMS) having pendant chains of the alkyl or alkoxy type having 8 to 24 carbon atoms, and a melting point of 20-55 ° C, such as stearyl dimethicone especially those sold by Dow Corning under the trade names DC2503 and DC25514, and mixtures thereof.

The pasty fatty substance may be present in the composition according to the invention a con- tent ranging from 0.01 to 60% by weight, relative to the total weight of the composition, preferably from 0.5 to 45% by weight and better still 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 may be chosen from anionic or nonionic surfactants. We can refer 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 functions (emulsifier) ​​of surfactants, in particular p.347-377 of this reference, for the 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 alcohol ethoxylated glycol, fatty acid esters of sucrose, alkyl glucose esters, especially DC fatty esters₆ polyoxyethylenated alkyl glucose, and mixtures thereof.

- From anionic surfactants: fatty acids C15-C30 neutralized with amines, aqueous ammonia or alkaline salts, and mixtures thereof.

Preferably used surfactants allow to obtain an oil-in-water or wax-in-water emulsion.

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

Forming polymer may be present in the composition according to the invention in a solids 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 and better still from 1% to 30% by weight.

In this application, the term "film-forming polymer" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, especially to keratin materials such as eyelashes.

Among the film-forming polymers used in the composition of the present invention include synthetic polymers of radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. Radical film-forming polymer means a polymer obtained by polymerization of monomers including ethylenically unsaturated, each monomer being capable of homopolymerizing (unlike polycondensates).

The radical type film-forming polymers can be polymers or copolymers, vinyl, 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 acidic monomers and or amides of these acidic monomers.

An acid group bearing monomer, there can be used unsaturated carboxylic acids α, β-ethylenic such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. preferably acid is used (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid.

The acid monomer esters are advantageously chosen from esters of (meth) acrylic acid (also known as (meth) acrylates), especially (meth) acrylates, in particular C C3O alkyl, preferably DC₂₀, (Meth) acrylates, aryl, in particular aryl C₆-C₁₀, (Meth) acrylates, hydroxyalkyl Kyle, in particular hydroxy-C₂-C₆ .

From (meth) acrylates include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate 2-ethyl hexyl methacrylate, lauryl cyclohexyl methacrylate. From (meth) acrylates include hydroxyethyl acrylate, the late acrylate, 2-hydroxypropyl methacrylate, hydroxyethyl methacrylate 2-hydroxypropyl.

Among the (meth) aryl acrylates include acrylate, benzyl acrylate and phenyl. Esters of (meth) acrylic acid are particularly preferred are (meth) acrylates.

According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, that is to say that a portion or all of hydrogen atoms of the alkyl group are substituted by fluorine atoms. As amides of acid monomers, there may be mentioned are (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular alkyl C₂.-C₁₂. Among the alkyl N- (meth) acrylamides include N-ethyl acrylamide, Nt-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide.

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

Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and vinyl t-butyl benzoate. Styrene monomers include styrene and alpha-methyl styrene.

Among the film-forming polycondensates include polyurethanes, polyesters, polyesters, polyamides, epoxy ester resins and polyureas.

The polyurethanes may be chosen from anionic polyurethanes, cationic, nonionic and amphoteric surfactants, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, t he p olyester polyurethanes, I es p olyéther polyurethanes, I es p oly- urea , polyurea-polyurethanes, and mixtures thereof.

The polyesters may be obtained in known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols. The dicarboxylic acid may be aliphatic, alicyclic or aromatic. There may be mentioned as examples of such acids: oxalic acid, malonic acid, diméthylmalo- nic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2 , 2-dimethyl glutaric, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1 acid, 3-cyclohexanedicarboxylic, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, digiycoli- acid, thiodipropionic acid, 2, 5-naphthalenedicarboxylic, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or in combination of at least two dicarboxylic acid monomers. Among these monomers, preferably one chosen are phthalic acid, isophthalic acid, terephthalic acid. The diol may be chosen from aliphatic diols, alicyclic, aromatic. a diol is preferably used selected from: ethylene glycol, diethylene glycol, triethylene glycol, 1, 3-propanediol, cyclohexanedimethanol and 4-butanediol. As other polyols, glycerol can be used, pentaerythritol, sorbitol and trimethylolpropane.

The polyesteramides may be obtained in a similar manner to the polyesters, by polycondensation of diacids with diamines or amino alcohols. Diamines can be used ethylenediamine, hexamethylenediamine and meta- or para-phenylenediamine. An amino alcohol can be used monoethanolamine.

The polyester may also comprise at least one monomer carrying at least one group -S0₃M, with M representing a hydrogen atom, an ammonium ion NH₄⁺ or a metal ion such as an Na ion⁺, Li⁺, K +, Mg²⁺, Ca²⁺, Cu²⁺, Fe²⁺, Fe³⁺. in particular one can use a bifunctional aromatic monomer comprising such a group -S0₃Mr.

The aromatic nucleus of the difunctional aromatic monomer also bearing a group -S0₃M t el q ue c i described above was p ê be hoisi c E p xample mong I es n oyaux benzene, naphthalene, anthracene, biphenyl, oxybiphenyl, sulfonylbiphenyl méthylènedi- phenyl. One can cite as an example of bifunctional aromatic monomer also bearing a group -S0₃M: sulphoisophthalic acid, sulphoterephthalic acid, sulphophthalic acid, 4-sulfonaphtaIène-2,7-dicarboxylic acid.

It is preferred to use copolymers based on isophthalate / sulphoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexanedimethanol, isophthalic acid and sulfoisophthalic acid.

Polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac 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 may be a water-soluble polymer and may be present in an aqueous phase of the composition; the polymer is donations solubilized in the aqueous phase of the composition. Examples of water-soluble film-forming polymers there may be mentioned: - the proteins such as proteins of plant origin such as wheat proteins and soybean proteins; the proteins of animal origin such as keratins, for example keratin hydrolysates and sulfonic keratins; - Cellulose polymers such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethylcellulose and carboxymethylcellulose, and quaternized derivatives of cellulose;

- Acrylic polymers or copolymers such as polyacrylates or polymethacrylates;

- Vinyl polymers, for instance polyvinylpyrrolidones, copolymers of methyl vinyl ether and of malic anhydride, vinyl acetate copolymer and of crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and of capro | actame; polyvinyl alcohol; - The polymers of natural origin, optionally modified, such as:

. gums arabic, guar gum, xanthan derivatives, gum ka- raya;

. alginates and carrageenans;

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

. the deoxyribonucleic acid;

. mucopolysaccharides such as chondroitin sulfate, and mixtures thereof.

According to another variant of the composition according to the invention, the film-forming polymer may be a polymer dissolved years of u p hase the fat iquide comprising oils or organic solvents such as those described above (we say that the film-forming polymer is a fat-soluble polymer). "Liquid fatty phase" is understood in the sense of the invention, a liquid fat phase at room temperature (25 ° C) and atmospheric pressure (760 mmHg, ie 105 Pa), composed of one or several fatty bodies liquid at ambient temperature, such as the oils described above, are generally mutually compatible.

Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil, the oils can be chosen from the oils above tees previously.

Examples of fat-soluble polymers include copolymers of vinyl ester (the vinyl group being directly linked to the ester oxygen atom and the vinyl ester having a saturated hydrocarbon radical, linear or branched from 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and of at least one other monomer which may be a vinyl ester (other than the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group contains from 2 to 18 carbon atoms) or an allyl or methallyl ester (containing a saturated hydrocarbon radical, linear or branched, of 1 to 19 carbon atoms, linked to the ester carbonyl).

, These copolymers may be crosslinked using crosslinking agents which can be either of the vinyl type or of the allyl or methallyl type, such as tetraailyloxyethane, divinylbenzene, divinyl octanedioate, divinyl and octadecane - dioate divinyl.

Examples of such copolymers include copolymers: vi- nyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecyl, vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, stearate vi- nyl / 1-octadecene, vinyl acetate / 1-dodecene, vinyl stearate / ethyl vinyl ether, pro- vinyl propionate / cetyl vinyl ether, vinyl stearate / allyl acetate, dimethyl-2, 2 octa- vinyl hexanoate / vinyl laurate, dimethyl-2, 2 pentanoate allyl / vinyl laurate, vinyl dimethyl propionate / stearate vinyl, allyl dimethyl propionate / vinyl stearate, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinylbenzene, vinyl dimethylpropionate / vinyl laurate, crosslinked with 0.2% divinylbenzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetraailyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinylbenzene, vi- nyl acetate / 1-octadecene, crosslinked with 0.2 % divinylbenzene and allyl propionate / allyl stearate, crosslinked with 0.2% divinylbenzene.

As liposoluble film-forming polymers, 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 may also be mentioned, alkylene radicals having from 10 to 20 carbon atoms.

Such liposoluble copolymers may be chosen among copolymers of vinyl polystéa- spleen, polyvinyl stearate crosslinked with divinylbenzene, with diallyl ether or with diallyl phthalate, polystearyl (meth) acrylate, of polylau - vinyl spleen, poly (meth) acrylate, these poly (meth) acrylates to be crosslinked with ethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate. The c opolymères I iposolubles de ned reviously p s c onnus have andn otamment d written in FR-A-2232303; they may have an average molecular weight ranging from 2,000 to 500,000, preferably 4,000 to 200,000.

As liposoluble film-forming polymers used in the invention, can also be made of polyalkylenes and in particular copolymers of alkenes C₂-C₂₀As the po- lybutène, alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated C, to C₈ such as ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and an alkene C₂ -C₄₀ and better still C₃ -C₂₀. As an example of VP copolymer used in the invention include the copolymers of VP / vinyl acetate, VP / ethyl methacrylate, the polyvinylpyro pyrrolidone (PVP) butylated, VP / ethyl methacrylate / methacrylic acid VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene and VP / acrylic acid / lauryl methacrylate.

The film-forming polymer may also be present in the composition in the form of particles dispersed in an aqueous phase or in a non-aqueous solvent phase, generally known as a latex or pseudolatex. these dispersions preparation techniques are well known in the art. Aqueous dispersions of film-forming polymer can be used acrylic lic dispersions sold under the names "Neocryl XK-90^® "" Neocryl A-1070^® "" Neocryl A-1090^® "" Neocryl BT-62^® "" Neocryl A-1079^® "And" A- 523 Neocryl^® "By the company Avecia-Neoresins," Dow Latex 432^® "By the company Dow Chemical," Daitosol 5000 AD^® "Or" Daitosol SJ 5000 "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 Avecia-Neoresins," 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^® "HYDROMER by the company; the sulfopolyes- ters sold under the brand name "Eastman AQ^® "By the company Eastman Chemical Products, vinyl dispersions, for instance" Mexomer PAM "and also acrylic dispersions in isododecane, for instance" Mexomer PAP "by the company Chimex. According to one embodiment, the composition according to the invention advantageously comprises an ethylene polymer film-forming linear block as described above and the film-forming polymer particles dispersed in an aqueous phase.

The composition according to the invention may comprise a plasticizer that promotes the formation of a film-forming polymer. Such a plasticizer may be chosen from all the compounds known to the art as being capable of fulfilling the desired function.

additives

The composition according to the invention may also comprise a dyestuff such as pulverulent dyestuffs, liposoluble dyes, drosolubles hydro- dyes. This dyestuff may be present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition.

The pulverulent dyestuffs may be chosen from pigments and nacres.

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

The nacres may be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, colored pearlescent pigments such as titanium mid ca with iron oxides, titanium mica with ferric blue or chromium oxide, titanium mica with an organic pigment of the abovementioned type, and pearlescent pigments based on bismuth oxychloride.

The fat-soluble dyes are for example Sudan red, D &amp; C Red 17, D &amp; C Green 6, β-carotene, soybean oil, Sudan Brown, D &amp; C Yellow 11, D &amp; C Violet 2, D &amp; C Orange 5, quinoline yellow, annatto. Water-soluble dyes are for example beetroot juice, methylene blue, the disodium salt of ponceau, the salt di- sodium of alizarin green, quinoline yellow, the trisodium salt of amaranth, the disodium salt of tartrazine, the monosodium salt of rhodamine, the 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 may be mineral or organic, lamellar or spherical. There may be mentioned talc, mica, silica, kaolin, pud polyamide such as nylon res^® (Orgasol from Atochem), poly-β- alanine and polyethylene, tetrafluoroethylene polymer powders such as Teflon^®, Lauroyl-lysine, starch, boron nitride, expanded hollow spheres polymerization c such as those of polyvinylidene chloride / acrylonitrile, Ex panceL^® (Nobel Industrie), 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 hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads^® of Maprecos), glass microcapsules or ceramic, metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example zinc stearate, magnesium or lithium, zinc laurate or magnesium myristate. The fillers may 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, fragrances, neutralizing agents, gelling agents, thickeners, vitamins, and mixtures thereof.

The gelling agents used in the compositions of the invention may be lipophilic or hydrophilic gelling agent, they may be organic or inorganic, polymeric or molecular.

Mineral lipophilic gelling agents include optionally modified clays, such as hectorites modified with a fatty acid ammonium chloride C₁0 -C₂₂, Such as hectorite modified by chloride distearyl dimethyl ammonium chloride such as, for example, that marketed under the name of "Bentone 38V^® "By Elementis society. It is also made of fumed silica optionally subjected to a hydrophobic surface treatment, the particle size is less than 1 .mu.m. It is possible to chemically modify the surface of the silica by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. One can substitute silanol groups with hydrophobic groups to obtain a hydrophobic silica. The hydrophobic groups may be:

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

- Dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained especially by treating fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are known as "silica dimethyl silylate" according to the CTFA (6^èmβ edition, 1995). They are for example marketed under the references "Aerosil R972^® "And" Aerosil R974^® "By Degussa," CAB-O-SIL TS-610^® "And" CAB-O-SIL TS-720^® "By the company Cabot. The hydrophobic fumed silica particularly has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm.

The polymeric organic lipophilic gelling agents are, for example elastomeric organopolysiloxa- nes partially or totally crosslinked, three-dimensional structure, such as those sold under the names "KSG6^® "" KSG16^® "And" KSG18^® "By Shin-Etsu, the" Trefil E-505C^® "And" Trefil E-506C^® "By the DOW-CORNING society," Gransil SR-CYC^® "" SR DMF10^® "," SR-DC556^® "" SR 5CYC gel^® "" SR DMF 10 gel^® "And" SR DC 556 gel^® "By the company GRANT INDUSTRIES, of" 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 C₆, And in particular to C₃ and mixtures thereof. Copolymers like sequences "diblock" or "triblock" of the polystyrene / polyisoprene or polystyrene / polybutadiene, such as those marketed under the name "Luvitol HSB^® "By BASF, of the polystyrene / copoly (ethylene-propylene) such as those marketed under the denomination tion of "Kraton^® "By Shell Chemical Co., or of the type polystyrene / copo! Y (ethylene-butylene).

Among the gelling agents that may be used in the compositions according to the invention can also be made of esters of dextrin fatty acid, such as your palmita- dextrin, such as those sold under the names "Rheopearl TL^® "Or" Rheopearl KL^® "By the company Chiba Flour.

Of course the skilled care to select the optional additional additives and / or their amounts so that the advantageous properties of the composition according to the invention are not, or not substantially impaired by the addition envisaged.

The composition according to the invention can be manufactured by the known processes generally used in cosmetics.

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

The composition according to the invention may be packaged in a cosmetic assembly comprising a container delimiting at least one compartment that comprises the composition, the container being closed by a closure element.

The container is preferably associated with an applicator, especially in the form of a brush comprising an arrangement of bristles maintained by a twisted wire. Such a twisted brush is described especially in patent US 4 887 622. It may also be in the form of a comb comprising a plurality of application members, obtained especially by molding. Such combs are described for example in patent FR 2 796 529. The applicator may be secured to the receptacle, as described for example patent FR 2 761 959. Advantageously, the applicator is integral with a rod , itself, is secured to the closure element.

The closing member may be coupled to the container by screwing. Alternatively, the coupling between the closing element and the container is done other than by screwing, especially via a bayonet mechanism, by click-fastening or by clamping. By "snap-mounting" in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion including the element closure, followed by return to the elastically unstressed position of said portion after the crossing of the bead or cord.

The container may be at least partly made of thermoplastic material. Examples of thermoplastic materials include polypropylene or polyethylene.

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

The container is preferably equipped with a drainer arranged in the vicinity of the container opening. Such a drainer makes it possible to wipe the applicator and possibly the rod to which it may be secured. Such a drainer is described for example in FR 2792618.

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

The invention is further illustrated in the following examples. The amounts are given in grams.

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

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and 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) - 2.5- dimethylhexane (Trigonox^® 141 Akzo Nobel). The mixture was held for 1 h 30 to 90 ° C.

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

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

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

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

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and in 1 hour, 105 g of isobornyl acrylate, 105 g of isobornyl methacrylate and 110 g of isododecane and 1, 8 g of 2.5- Bis (2-ethylhexanoylperoxy) - 2.5- dimethylhexane (Trigonox^® 141 Akzo Nobel). The mixture was held for 1 h 30 to 90 ° C.

Is then introduced into the above mixture, still at 90 ° C in 30 minutes, 90 g of acrylate 2-ethylhexyl, 90 g of isododecane and 1, 2 g of 2.5- Bis (2- ethylhexanoylperoxy) -2.5 -diméthylhexane.

The mixture is kept 3 hours at 90 ° C and then the whole is cooled. This gave a solution containing 50% polymer active material in isododecane.

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

This polymer has a weight-average mass of 103 900 g / mol and an average weight of 21 300, ie a polydispersity index I of 4.89. Example 3 Preparation of a polymer polvimethacrylate isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate)

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and 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) - 2.5 -diméthylhexane (Trigonox^® 141 Akzo Nobel). The mixture was held for 1 h 30 to 90 ° C.

then introduced into the above mixture, still at 90 ° C 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 3 hours at 90 ° C and then the whole is cooled. This gave a solution containing 50% polymer active material in isododecane.

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

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

Example 4 Preparation of a polymer polyfacrylate isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate)

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and 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) -2.5 - dimethylhexane (Trigonox^® 141 Akzo Nobel). The mixture was held for 1 h 30 to 90 ° C. then introduced into the above mixture, still at 90 ° C 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 3 hours at 90 ° C and then the whole is cooled. This gave a solution containing 50% polymer active material in isododecane.

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

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

The following polymer can be prepared

Example 5: Preparation of a polymer Poly (isobornyl acrylate / isobutyl methacrylate / acrylate 2-ethylhexyl)

100 g of isododecane are introduced into a 1 liter reactor and the temperature is increased so as to pass from room temperature (25 ° C) to 90 ° C over 1 hour. are then added at 90 ° C and 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 Akzo Nobel). The mixture was held for 1 h 30 to 90 ° C.

then introduced into the above mixture, still at 90 ° C in 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 3 hours at 90 ° C, then diluted and then the whole is cooled. This gave a solution containing 50% polymer active material in isododecane.

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

Was prepared (es mascara compositions 9 and 10 according to the invention 6-8 according to the following prior art:

<img id="imgf000043_0001" he="104" wi="168" file="imgf000043_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

For each composition were measured dry extract according to the measuring method described previously in the description.

0 The holding of the film formed by the composition according to the invention is evaluated by measuring the water resistance, a function of time, of a composition film spread on a glass plate and subjected to an aqueous medium by stirring . The protocol is as follows: At room temperature (25 ° C) was spread a layer of composition of 300 .mu.m thickness (before drying) with an area of ​​9 cm x 9 cm on a glass plate on a - 5 side of 10 cm X 10 cm, then dried 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 one liter of water placed on a heating magnetic stirrer sold under the name RCT basic by the company IKA labor technik. then placed on the film a smooth cylindrical bar magnet PTFE (length 6 cm 0 1 cm diameter). stirring rate is adjusted to 5. The water temperature is controlled using a thermometer at temperature of 20 ° C or 40 ° C. At time t₀ = 0, it starts shaking. the time t is measured (in minutes) after which the film begins to detach or come off the plate or when there is a hole the size of the magnetic stirring bar, that is to say, when the hole has a diameter of 6 cm. the water resistance of the film is measured at time t.

The viscosity measurement is made using a Rheomat RM 180 with a MS-r3 or r4 Ms- rotating at 240 min^"1 for a power supply at 60 Hz or at 200 min^"1 for a power supply at 50 Hz.

<img id="imgf000044_0001" he="43" wi="138" file="imgf000044_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

These mascara composition according to the invention are easily applied to the eyelashes. Mascara form a smooth, uniform makeup and thickens lashes. It has very good performance.

Examples 11 and 12

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

<img id="imgf000044_0002" he="72" wi="138" file="imgf000044_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

<img id="imgf000045_0001" he="111" wi="139" file="imgf000045_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

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

In vitro load is measured gravimetrically on Caucasian hair curves of specimens (30 cm long hair 1 spread over a distance of 1cm). The test tube is masked by performing 3x10 mascara passages spaced at 2 minutes with product recovery between each set of 10. The specimen is dried 10 min at room temperature and weighed. This measurement is carried out on 6 specimens

The charge is in fact the amount of material deposited on the test specimen = mass makeup - bare specimen mass. The average charge is the average of measurements made on 6 specimens.

The following results were obtained

<img id="imgf000045_0002" he="37" wi="131" file="imgf000045_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" /> It is noted that the mascara of Example 12 of the invention has a load in vitro and dry extract and a holding above the mascara containing no polymer sequence (Example 11), while having a lower viscosity. The mascara applied easily to the eyelashes and presents, after application, a loading effect eyelashes, while having a good performance.

Examples 13-16

mascaras was prepared comprising a block polymer according to the invention (Examples 14 to 16) and a mascara that is not part of the invention (Example 13) having the following composition:

<img id="imgf000046_0001" he="158" wi="160" file="imgf000046_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

<img id="imgf000047_0001" he="64" wi="160" file="imgf000047_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

Each compositiori was measured according to the dry measurement method described above in the description.

In vitro load and holding were measured according to the method described in the preceding examples.

The following results were obtained

<img id="imgf000047_0002" he="36" wi="160" file="imgf000047_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

It is found that mascaras of Examples 14 to 16 according to the invention exhibit superior resistance to mascara containing no polymer sequence (Example 13), and a load in vitro higher.

Examples 17-19: Mascaras without wax

the following mascaras were prepared according to the invention

<img id="imgf000047_0003" he="34" wi="131" file="imgf000047_0003.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

<img id="imgf000048_0001" he="85" wi="131" file="imgf000048_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="yes" />

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

Was also measured, the mean gloss of these compositions according to the following protocol:

On a Leneta brand contrast card of reference Form 1A Penopac, is spread a layer between 50 .mu.m and 150 .mu.m thick of the composition using an automatic spreader. The layer covers at least the white background of the card. Allowed to dry the deposit for 24 hours at a temperature of 30 ° C, then proceed to measuring the 60 ° gloss on the white background with a mark of Byk Gardner gloss microTri-GLOSS reference.

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

We obtain the following results

<img id="imgf000048_0002" he="36" wi="116" file="imgf000048_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

These mascaras have a good performance. There is also the value of the gloss of the composition increases with the rate of polymer block. example 20

1) the average brightness of the mascara of Example 13 according to the prior art was measured with the protocol described above.

2) was spread on a glass plate a mascara composition film of Example 13

(Base coat) 300 micrometers thick.

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

Then plated on the film composition of Example 13, a composition film of Example 18 (top coat) is 300 microns thick.

Is allowed to dry all 24 hours at room temperature (25 ° C).

It then measures the average brightness and the holding of the final film as de- scribed above protocols.

3) The results are shown in the following table:

<img id="imgf000049_0002" he="29" wi="143" file="imgf000049_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

The application of mascara of Example 18 of the invention in top coat of the mascara of Example 13 of the prior art provides a composition film having a gloss and good-behavior to those of the film basic mascara alone.

Examples 21-24

The compositions of Examples 22-24 comprising a block polymer according to the invention and the composition of Example 21 (Comparative) containing no polymer sequence were prepared.

<img id="imgf000049_0001" he="15" wi="162" file="imgf000049_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="yes" /><img id="imgf000050_0001" he="83" wi="162" file="imgf000050_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

Each composition was measured by the dry measurement method described above in the description, as well.

In vitro load was measured according to the method described in the preceding examples.

We obtain the following results:

<img id="imgf000050_0002" he="33" wi="155" file="imgf000050_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

Mascaras according to the invention comprising the polymer particular sequence have a solids content greater than or equal to 45% and in vitro load value high while being easy to apply.

After application to the eyelashes, the composition of the film also has good resistance to weathering and sebum, while being easily demaquillab.es with classic makeup remover.

example 25

the following mascara was prepared Candelilla wax 5 g

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

Block polymer of Example 4 10 (MA)

stearic acid 5.8

Triethanolamine stearate 2.9

Black iron oxide 8

0.9 hydroxyethyl

Gum arabic 3.4

Water, preservatives qs 100

Sec was measured and holding extract, according to measurement method described above in the description.

The results obtained are shown in the following table:

<img id="imgf000051_0001" he="30" wi="111" file="imgf000051_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

This mascara has a good performance and a thickening up the eyelashes.