Glossy liquid composition comprising a sequenced polymer

Translation of description of equivalent WO 2004028488 A2

brilliant liquid composition comprising a polymer block

The present invention relates to a liquid cosmetic makeup or skin care, including the scalp, both of the human face and body, lips or nails of human beings, like hair, eyelashes, the eyebrows or the nails, comprising a cosmetically acceptable medium containing a particular polymer sequence.

There are numerous cosmetic compositions for which the gloss properties of the deposited film, after application to keratinous substances (skin, lips or integuments) are very important. We may mention for example lipsticks, nail varnishes or certain hair products and some mascaras.

It is known to formulators of cosmetics that brightness property is favored when using oils characterized by a viscosity and a high refractive index and which possess, in addition, good dispersion properties of ^•pigments or fillers when they are present in the composition.

In this context, the formulator has several types of raw materials such as oily polymers such as polybutenes, sold under the reference Indopol H100, H300 and H1500 by Amoco, which have a very high viscosity but which exhibit the the disadvantage of being both very sticky and possess dispersion properties of pigments relatively low, limiting their use.

The present invention aims to propose a novel formulation route of a cosmetic product, in particular a makeup product, that allows good gloss properties.

In particular, the product of the invention allows obtaining continuous deposits on the skin or lips, good coverage, with very shiny, adapted to the desire of the consumer, not migrant, not transferring and good held, non-oily, do not dry the skin, hair or lips on which it is applied, either during application or over time. It has, in addition to good stability properties and thus allows a uniform and aesthetic application.

The invention relates to a bright liquid composition for caring for or making up the skin and / or lips and / or superficial body growths containing a polymer sequence that allows overcome the disadvantages of known brilliant compositions. Surprisingly, the inventors have found that the use of a sufficient amount of a particular polymer sequence provides a gloss composition and which, moreover, is of good performance.

The composition of the invention may in particular constitute a hair product or a body makeup product, the lips or superficial body growths of human beings having care properties and / or treatment. It is especially a lipstick or a lip gloss, eyeshadow, a tattoo product, a mascara, an eyeliner, a nail varnish, an artificial tanning product for the skin, a skin cream or possibly tinted protection, a coloring product or hair care.

More specifically, the invention relates to a liquid cosmetic composition containing a cosmetically acceptable organic liquid medium, and a polymeric film-forming linear ethylenic non-elastomeric block, said polymer being such that when present in sufficient amount in the composition, the mean gloss measured at 20 ° of a deposit of the said composition, once spread onto a support, is preferably greater than or equal to 30 100.

The invention also relates to a liquid cosmetic composition containing a cosmetically acceptable organic liquid medium and a film-forming linear ethylenic polymer free of styrene sequence pattern, said polymer being such that when present in sufficient amount in the composition, the gloss average measured at 20 ° of a deposit of the said composition, once spread onto a support, is preferably greater than or equal to 30 100.

"Liquid composition" means a composition which at 25 ° C and atmospheric pressure, in the form of the container in which it is paid.

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

Brilliance average composition

The term "mean gloss" means the gloss as may be measured using a glossmeter, in a conventional manner by the following method. 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. We allowed to dry the deposit 24 hours at a temperature of 30 ° C then proceed to measuring the 20 ° 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.

The mean gloss of the composition measured at 20 ° is preferably greater than or equal to 30, better still greater than or equal to 35, better still greater than or equal to 40, better still greater than or equal to 45, better still greater than or equal to 50 out of 100 , more preferably greater than or equal to 55, better still greater than or equal to 60, better still greater than or equal to 65, better still greater than or equal to 70 or better still greater than or equal to 75 out of 100. for certain compositions according to the invention such as nail varnishes, the gloss measured at 20 ° may be greater than or equal to 70, or even 80 out of 100.

Preferably, the mean gloss of the composition, once spread onto a support, measured at 60 ° is greater than or equal to 50, better still greater than or equal to 60, better still greater than or equal to 65, more preferably greater or equal to 70, better still greater than or equal to 75, better still greater than or equal to 80, better still greater than or equal to 85 or better still greater than or equal to 90 out of 100.

One proceeds to the measurement of the mean gloss at 60 ° as follows. The gloss may be measured using a glossmeter, in a conventional manner by the following method. 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. It is 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 brand glossmeter Byk Gardner reference microTri-GLOSS .

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.

According to one embodiment, the mean gloss of the composition measured at 20 ° is preferably greater than or equal to 35, preferably .40, 45 or 50 out of 100, and / or the mean gloss of the composition measured at 60 ° is preferably greater than or equal to 65, 70 or 75 out of 100. in this implementation mode, the composition comprises advantageously a liquid lipstick.

According to an embodiment, the mean gloss of the composition measured at 20 ° is preferably greater than or equal to 60, preferably 65, 70 or 75 out of 100, and / or the mean gloss of the composition measured at 60 ° is preferably greater than or equal to 80, 85 or 90 to 100. in this mode of implementation, the composition advantageously forms a nail varnish.

The invention also relates to a cosmetic composition comprising an organic liquid medium and at least one polymer block as described below.

The invention also relates to a skin makeup process and / or the lips and / or superficial body growths which consists in applying to the skin and / or lips and / or integuments the composition as defined above.

The composition according to the invention can be applied to the skin as well as the face of the scalp and body, mucous membranes such as the lips, the inside of the lower eyelids and skin appendages such as the nails, eyelashes, hair , eyebrows or hair.

The invention also relates to the use of a polymer block in an amount in a cosmetic composition for imparting gloss and / or held in a deposit of the said composition.

The invention also relates to the cosmetic use. e the composition defined above to improve the brightness of the makeup on the skin and / or lips and / or integuments.

The composition advantageously contains a lesser proportion of oils traditionally used to impart a gloss, which oils are generally sticky.

The composition according to the invention advantageously contains less than 30%, preferably less than 25%, less than 20%, and preferably less than 15% of at least one glossy oil.

The term "oil" means a compound not miscible with water in any proportion, liquid at room temperature (25 ° C) and atmospheric pressure (760 mmHg). By "glossy oil" means an oil having a molecular weight preferably ranges from 650 to 10,000 g / mol and preferably of 750-7500 g / mol.

molar mass of oil ranging from 650 to 10,000 g / mol may be chosen from:

- Lipophilic polymers such as:

- Polybutylenes such as Indopol H-100 (molecular weight or MW = 965 g / mol), Indopol H-300 (MW = 1340 g / mol), Indopol H-1500 (MW = 2160 g / mol) sold or manufactured by Amoco,

- Hydrogenated polyisobutylenes such as Panalane H-300 E sold or manufactured by Amoco (M = 1340 g / mol), Viseal 20000 sold or manufactured by the SYNTEAL company (MM = 6000 g / mol), the Rewopal GDP 1000 sold or manufactured by Witco (MM = 1000 g / mol)

- Polydecenes and hydrogenated polydecenes such as Puresyn 10 (MM = 723 g / mol), Puresyn 150 (MM = 9200 g / mol), sold or manufactured by the company Mobil Chemicals,

- Copolymers of vinylpyrrolidone such as: the vinylpyrrolidone / 1-hexadecene, Antaron V-216 sold or manufactured by ISP

(MW = 7300 g / mol),

- Esters such as:

- Esters of linear fatty acids having a total carbon number ranging from 35 to 70 as pentaerythrityl tetrapelargonate (MW = 697.05 g / mol),

-The esters. hydroxy strip which is such that triisostearate, polyglyceryl-2 (MW = 965.58 g / mol), -the aromatic esters such as tridecyl trimellitate (MW = 757.19 g / mol), -the fatty alcohol esters or branched fatty acids C₂₄-C₂₈ such as those described in EP-A-0955039, and in particular triisoarachidyl citrate (MW = 1033.76 g / mol), pentaerythrityl tetraisononanoate (MM = 697,05g / mol), glyceryl triisostearate (MW = 891.51 g / mol), tri 2-decyltetradecanoate glyceryl (MW = 1143.98 g / mol), pentaerythrityl tetraisostearate (MW = 1202.02 g / mol), polyglyceryl tetraisostearate -2 ( MW = 1232.04 g / mol) or tetra decyl -2 pentaerythrityl tetradecanoate (MW = 1538.66 g / mol),

- Silicone oils such as phenyl silicones such as BELSIL PDM 1000 from the company Wacker (MM = 9000 g / mol) - The vegetable oils such as sesame oil (820.6 g / mol),

- And mixtures thereof.

Polymer sequence:

The composition according to the present invention contains at least a polymer sequence. By "block polymer" means a polymer comprising at least two different blocks and preferably at least three sequences. distinct.

According to one embodiment, the block polymer of the composition according to the invention is an ethylene polymer. The term "ethylenic polymer" means a polymer obtained by polymerizing monomers comprising an ethylenic unsaturation.

According to one embodiment, the block polymer of the composition according to the invention is a linear polymer. In contrast, a non-linear structure polymer is, for example, a polymer of branched structure, star, graft, or otherwise.

According to one embodiment, the block polymer of the composition according to the invention is a film forming polymer. 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.

According to one embodiment, the block polymer of the composition according to the invention is a non-elastomeric polymer.

"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 R << 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.

This produces a film about 100 microns thick in -which are cut rectangular specimens (for example a punch) of a width of 15 mm and a length of 80 mm.

It requires that sample to a tensile stress using a machine sold 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 (if). .

The instantaneous recovery in% (R is given by the following formula:

Ri = (ε_maχ- εi) / 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 (R₂ ) Is given by the following formula:

R_h = (ε_max - ε_{2 hours}) / Ε_max) X 100

Purely as a guide, a polymer according to one embodiment of the invention has an instantaneous recovery R of 10% and a delayed recovery R_2r, 30%. According to another embodiment, the block polymer of the composition according to the invention does not comprise styrene unit. By polymer free of styrene units, means a polymer comprising less than 10%, preferably less than 5%, preferably less than 2%, more preferably less than 1% by weight i) of styrene of the formula -CH pattern ( C₆H₅) -CH₂- Or ii) of substituted styrene units, for instance 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.

According to one embodiment, the block polymer comprises at least one first block and at least one second sequence.

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.

According to one embodiment, the block polymer comprises at least one first block and at least one second block having glass transition temperatures (Tg).

In this implementation mode, the first and second blocks may be linked together via an intermediate segment having a glass transition temperature between the glass transition temperatures of the first and second sequences.

According to one embodiment, the polymer sequence comprises at least one first block and at least one second block linked together via an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second sequence. Preferably, the intermediate block is derived essentially from constituent monomers of the first sequence and second sequence. By "substantially" is meant to. least 85%, preferably at least 90%, more than 95% and even better still 100%. Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer.

According to one embodiment, the block polymer comprises at least one first block and at least one second sequence incompatible in the organic liquid medium of the composition of the invention.

"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 block is not miscible in the majority by weight liquid contained in the medium organic liquid 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 major organic liquid), it being understood that: i) the said polymers are present in the mixture in a content 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 liquids, in the hypothesis of two or more liquids present in identical mass proportions, the said polymer mixture is immiscible in at least one of them.

In the case where the organic liquid medium comprises only one organic liquid, the latter is obviously the majority liquid by weight.

By "organic liquid medium" means a medium containing at least one organic liquid, that is to say, at least one liquid organic compound at room temperature (25 ° C) and atmospheric pressure (10⁵ Pa). According to one embodiment, the majority liquid of the organic liquid medium is an oil (fat) volatile or nonvolatile. Preferably, the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and feel). The organic liquid is cosmetically acceptable medium, in that it is compatible with keratin materials, such as oils or organic solvents commonly used in cosmetic compositions.

According to one embodiment, the major liquid of the organic liquid medium is the polymerization solvent or one of the solvents of the block polymer as described below.

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 isododecane, and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol, or isododecane.

In general, the block polymer may be incorporated into the composition at a high dry contents, typically greater than 10%, greater than 20% and more preferably greater than 30% and more preferably greater than 45% by weight relative to the total weight of the composition while being easy to formulate.

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 inventive 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 containing from 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).

According to one embodiment, the block polymer has a polydispersity index I of greater than 2.

Advantageously, the block polymer used in the compositions 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, pa 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 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 70 000, it is for example from 10 000 to 60 000 and better still from 12 000 to 50 000.

Each sequence or block of the block polymer 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.

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 (πι / Tg), king i 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 block polymer comprises at least one first block and at least one second sequence such that the first block may be chosen from: a) a block with a Tg of greater than or equal to 40 ° C, b) a block with a Tg less than or equal to 20 ° C, - c) a block with a Tg of between 20 and 40 ° C, and the second sequence can be 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 terminals mentioned are excluded, and

"... To ..." and "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 copolymer a-.

The block with a Tg of greater than or equal to 40 ° C may be totally or partially derived from one or more monomers which are such that the homopolymer prepared from these monomers has a glass transition temperature exceeding 40 ° C.

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 a. single type of monomer (including Tg.de the corresponding homopolymer is greater than or equal to 40 ° C).

In the case where the first block 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 greater than or equal to 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 12Q ° C, and - of the 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 - 100-20 ° C, preferably below 15 ° C, especially ranging from - 80 ° C to 15 ° C and preferably below 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, also known as the main monomers:

- Methacrylates of formula CH₂ = C (CH₃) COOR. 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 -C₁₂,

- CH formula acrylates₂ = CH-COOR₂ wherein R₂ is cycloalkyl C₄ -C₁₂ such as isobornyl acrylate or a tert-butyl group,

- (Meth) acrylamides of formula:

<img id="imgf000014_0001" he="23" wi="56" file="imgf000014_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

wherein R₇ and R₈ identical or different, each represent a hydrogen atom or an alkyl group -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) isobornyl acrylate and mixtures thereof.

b) Block with 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 ° C may be a homopolymer or a copolymer.

The block with a Tg less than or equal to 20 ° C may be totally or partially derived from one or more monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature or equal to 20 ° C.

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 less than 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 of less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, preferably less than 15 ° C, especially ranging 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 of 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 C₁ -C₁₂Linear 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,

R is a substituted alkyl C₆ -C₁₂ linear or branched, in which is (are) optionally inter stalled (s) one or more heteroatoms selected from 0, N and S;

- Formula of vinyl esters R5-CO-O-CH = CH₂ wherein R₅ represents an alkyl group of C -C₁₂ straight or branched;

- Vinyl ethers of C -C ₂,

- N-alkyl C₄ -C₁₂ acrylamides, such as N-octylacryiamide,

- 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 comprises 1 to 10 carbon atoms, except the tert-butyl group, such as methyl acrylate, isobutyl acrylate, 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.

The block with a Tg of between 20 and 40 ° C may be totally or partially derived from one or more monomers which are such (s) that the homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C.

The block with a Tg of between 20 and 40 ° C may be totally or partly 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) than the homopolymer corresponding to a Tg less than or equal to 20 ° C.

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, Pisodécylacrylamide 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 that the Tg of the resulting 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 - monomer key whose corresponding homopolymer has a Tg of 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 to 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%.

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

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) comprise, in addition to the monomers indicated above, one or more other monomers known as additional monomers, 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 for example selected from: a) 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 I, 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, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylamide and dimethylaminopropylmethacrylamide, and salts thereof ,

- Methacrylates of formula CH₂ = C (CH₃) COOR₆ wherein R₆ represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as 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,

R is alkyl C₆ -C-ι₂ 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,

R₁₀ Representative alkyl | -C₁₂ 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 is alkyl (-C₁₂) O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 30 times, for example methoxy-POE, or R₁₀represents a polyoxyethylene group comprising from 5 to 30 ethylene oxide units

b) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloxypropyltrimethoxysilane trimethoxy silane, methacryloxypropyl tris (trimethylsiloxy) silane, - and mixtures thereof.

Particularly preferred additional monomers are acrylic acid, methacrylic acid, trifluoroethyl methacrylate and mixtures thereof. According to one embodiment, .chacune first and second block of the block polymer comprises at least one monomer selected from esters of (meth) acrylic acid and optionally at least one additional monomer such as (meth) acrylic acid, and mixtures thereof.

According to another embodiment, each first and second block of the block polymer is totally derived from at least one monomer selected from esters of (meth) acrylic acid and optionally at least one additional monomer such as the (meth) acrylic acid, and mixtures thereof.

According to a preferred embodiment, the block polymer is a non-silicone 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, from 7 to 15 % by weight of the total weight of the first and / or second blocks.

The block polymer may be obtained by radical solution polymerization according to the following preparation process: a portion 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 of 90%, the constituent monomers of the second block and the rest of the initiator are introduced, the mixture is allowed to react for a time T (ranging from 3 to 6 hours) after which the mixture is cooled to room temperature, the polymer was obtained in solution in the polymerization solvent.

First Embodiment According to a first embodiment, the block polymer comprises a first block having an equal or higher Tg to 40 ° C, as described above in a) and a second block with a Tg of 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%.

Thus, in a first variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example having a Tg ranging from 70 to 110 ° C, which is a methyl methacrylate / acrylic acid,

- A second sequence of less than or equal to Tg 20 ° C, for example ranging from 0 to 20 ° C, which is a methyl acrylate homopolymer, and - an intermediate block which is a methyl methacrylate / acrylic acid / acrylate methyl.

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 70 to 100 ° C, which is a copolymer of methyl methacrylate / acrylic acid / trifluoroethyl methacrylate,

- A second sequence Tg of less than or equal to 20 ° C, for example ranging from 0 to 20 ° C, which is a methyl acrylate homopolymer, and

- An intermediate block which is a random copolymer of methyl methacrylate / acrylic acid / methyl acrylate / trifluoroethyl methacrylate.

In 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 85 to 115 ° C, which is an isobornyl acrylate / isobutyl methacrylate,

- A second sequence of Tg^λ less than or equal to 20 ° C, for example ranging from -85 to - 55 ° C, which is a homopolymer of 2-ethylhexyl acrylate, and - an intermediate block which is an isobornyl acrylate random copolymer / methacrylate isobutyl acrylate / 2-ethyl hexyl.

In a fourth 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 an isobornyl acrylate / methyl 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 / methyl methacrylate / acrylate, 2-ethylhexyl.

According to a fifth variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl 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 a random copolymer of isobornyl acrylate / isobornyl methacrylate / acrylate, 2-ethylhexyl.

According to a sixth 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 / 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 a random copolymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate.

According to a seventh variant, the polymer according to the invention may comprise:

- A first Tg of greater than or equal to 40 ° C, for example ranging from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate, - 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 a random copolymer of isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate.

According to an eighth 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 following examples illustrate without limitation polymers corresponding to this first embodiment. The amounts are expressed in grams.

Example 1: Preparation of methyl polv.méthacrylate polymer / acrylic acid / methyl acrylate)

100 g of butyl acetate 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, 180 g of methyl methacrylate, 30 g of acrylic acid, 40 g of butyl acetate, 70 g of isopropanol and 1.8 g of 2.5- Bis ( 2- ethylhexanoylperoxy) -2.5-dimethyl hexane (Trigonox^® 141 Akzo Nobel).

The mixture is kept 1 hour at 90 ° C. then introduced into the above mixture, still at 90 ° C in 1 hour, 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and 1, 2 g of 2.5- Bis (2- ethylhexanoylperoxy) 2,5-dimethylhexane.

The mixture is kept 3 hours at 90 ° C, then diluted with 105 g of butyl acetate and 45 g of isopropanol and then the whole is cooled. This gives a 40% solution of polymer active material in the mixture of butyl acetate / isopropanol.

A polymer comprising a first sequence or the poly (methyl methacrylate / acrylic acid) having a Tg of 100 ° C a second sequence or methyl polyacrylate block having a Tg of 10 ° C and an intermediate block which is a random polymer methyl methacrylate / acrylic acid / polymethyl acrylate. This polymer has a weight-average mass of 52 000 and an average weight of 18000, a polydispersity index I of 2.89.

Example 2 Preparation of a polymer polv.acrylate 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-dimethyl hexane (Trigonbx^® 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.

A solution was obtained at 50% polymer active material in isododecane ..

We. A polymer comprising a first sequence or block poly (isobornyl acrylate / isobutyl methacrylate) having a Tg of 80 ° C, a second sequence of 2-ethylhexyl acrylate having a Tg of - 70 ° C and a sequence which intermediate is an acrylate random polymer isobornyl acrylate / isobutyl methacrylate / 2 ethyl hexyl acrylate.

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

Example 3 Preparation of a poly (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, 110 g of isododecane and 1, 8 g of 2.5- Bis (2- ethylhexanoylperoxy) - 2.5-dimethyl hexane (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-ethy! Hexanoylperoxy) 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 / isobornyl methacrylate) having a Tg of 110 ° C, a second polyacrylate sequence of 2-ethylhexyl acrylate having a Tg of - 70 ° C and a intermediate block which is an acrylate random polymer isobornyl acrylate / isobornyl methacrylate / acrylate, 2-ethylhexyl.

This polymer has a weight-average mass of 103 900 and an average weight of 21 300, ie a polydispersity index I of 4.89.

Example 4 Preparation of a polymer Poly (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 -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. and in 30 minutes, 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2.5- Bis (2-ethylhexanoylperoxy) -2.5- dimethylhexane.

The mixture is kept 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 sequence of isobutyl acrylate having a Tg of - 20 ° C and an intermediate block which is an acrylate random polymer isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate. Example 5: Preparation of methyl polvdnéthacrylate polymer / methyl acrylate / acrylic acid)

100 g of butyl acetate 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, 50.4 g of methyl methacrylate, 21 g of acrylic acid, 138.6 g of methyl acrylate, 40 g of butyl acetate, 70 g of isopropanol and

1, 8 g of 2.5-Bis (2-ethylhexanoylperoxy) 2,5-dimethylhexane (Trigonox^® 141 Akzo

Nobel). The mixture is kept 1 hour at 90 ° C.

then introduced into the above mixture, still at 90 ° C in 1 hour, 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2.5-

Bis (2-ethylhexanoylperoxy) -2.5-dimethyl hexane.

The mixture is kept 3 hours at 90 ° C, then diluted with 105 g of butyl acetate and 45 g of isopropanol and then the whole is cooled.

This gives a 40% solution of polymer active material in the mixture of butyl acetate / isopropanol.

The polymer obtained comprises a first block or the poly (methyl acrylate / methyl methacrylate / acrylic acid) having a Tg of 35 ° C a second block or the poly (methyl methacrylate) having a Tg of 100 ° C and a sequence intermediate which is a random polymer methyl methacrylate / acrylic acid / polymethyl acrylate.

Example 6 Preparation of a polymer Poly (isobornyl acrylate / isobornyl 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, 105 g of isobornyl acrylate, 105 g of isobomyl methacrylate, 110 g of isododecane and 1.8 g of 2.5- Bis (2- ethylhexanoylperoxy) - 2.5-dimethyl hexane (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 / isobornyl methacrylate) having a Tg of 110 ° C, a second sequence of isobutyl acrylate having a Tg of - 20 ° C and an intermediate block which acrylate random polymer is an isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate.

This polymer has a weight-average mass of 151 000 and an average weight of 41 200, ie a polydispersity index I of 3.66.

Example 7: Preparation of a poly (isobornyl methacrylate / 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 (isobornyl methacrylate / 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.

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

According to a second mode of 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 temperature 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 even better still from 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) than the homopolymer corresponding to 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.

Thus, according to first variant of this second embodiment, the block polymer may comprise:

- A first Tg sequence comprised between 20 and 40 ° C, for example having a Tg from 25 to 39 ° C, which is a copolymer comprising at least one methyl acrylate monomer, at least one monomer of methyl methacrylate and at least one acrylic acid monomer, - a second sequence of equal or higher Tg to 40 ° C, for example ranging from 85 to 125 ° C, which is a homopolymer composed of methyl methacrylate monomers and - An intermediate block comprising at least one methyl acrylate monomer, methyl methacrylate and

- An intermediate block comprising methyl methacrylate, at least one acrylic acid monomer and at least one methyl acrylate monomer.

According to a second variant of this second embodiment, the block polymer may comprise:

- 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 Tg of less than or equal to 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 third variant of this second embodiment, the block polymer may comprise:

- A first sequence Tg of between 20 and 40 ° C, for example with a Tg from 21 to 39 ° C, which is an isobornyl acrylate / methyl acrylate / acrylic acid,

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

- An intermediate block which is an isobornyl acrylate random copolymer / methyl acrylate / acrylic acid.

The composition of the invention advantageously contains from 0.1 to 60% by weight of active material (or solids) of block polymer, preferably from 0.5 to 50% by weight, and more preferably from 1 to 40% in weight.

The composition according to the invention may comprise a hydrophilic medium comprising water or a mixture of water and solvent (s) organic (s) hydrophilic (s) such as alcohols and especially linear or branched lower monoalcohols having 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols, or alternatively of ethers of C₂ aldehydes and C₂-C₄ hydrophilic. The water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably from 10% to 80% by weight.

The composition according to the invention comprises a cosmetically acceptable organic liquid medium (tolerance, toxicology and feel).

According to a particularly preferred embodiment, the organic liquid medium of the composition contains at least one organic solvent, which is the or one of the polymerization solvents of the block polymer as described above. Advantageously, said organic solvent is the majority liquid by weight in the organic liquid medium of the cosmetic composition.

According to one embodiment, the organic liquid medium comprises at least one fat that is liquid at room temperature (25 ° C in general). This liquid fat can be of animal, plant, mineral or synthetic.

Fats that are liquid at room temperature, often called oils, used in the invention include: hydrocarbon oils of animal origin such as perhydrbsqualène; hydrocarbon-based plant oils such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acid, or alternatively sunflower oil, corn oil, soybean oil, grapeseed oil, sesame oil, apricot, macadamia, castor oil, avocado oil, triglycerides of caprylic / capric acids, jojoba oil, shea butter; linear or branched hydrocarbons of mineral or synthetic origin such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; the synthetic esters and ethers, especially of fatty acids such as purcellin oil, isopropyl myristate, 2-ethyl-hexyl stearate, octyl-2-octyldodecyl erucate octyl-2-octyldodecyl erucate, isostearyl isostearate; hydroxy esters such as isostearyl lactate, octyl, octyldodecyl hydroxystearate, diisostearylmalate, triisocetyl citrate heptanoates, octanoates decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms as Poctyldodécanol, 2-butyloctanol, 2-hexyldécanoi, 2-undecylpentadecanol, oleyl alcohol; fluorinated oils which partially hydrocarbon and / or silicone; silicone oils such as polydimethylsiloxanes (PDMS), volatile or not, linear or cyclic, such as cyclomethicones, dimethicones, optionally comprising a phenyl, as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes siloxanes, diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyl dimethicones, polymethylphenylsiloxanes; mixtures thereof.

These oils may be present in a content ranging from 0.01 to 90%, and preferably from 0.1 to 85% by weight, relative to the total weight of the composition.

The organic liquid medium of the composition according to the invention may also comprise one or more organic solvents, cosmetically acceptable (acceptable tolerance, toxicology and feel). These solvents may generally be near nts in a content ranging from 0.1 to 90%, more preferably from 10 to 90% by weight, relative to the total weight of the composition and better still from 30 to 90%.

As solvents used in the composition of the invention include, besides the hydrophilic organic solvents mentioned above, ketones that are liquid at room temperature, such as methylethylketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; liquid propylene glycol ethers at room temperature, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, mono-n-butyl ether of dipropylene glycol; short-chain esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate 'isopentyl.e; ethers that are liquid at room temperature such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes that are liquid at room temperature, such as decane, heptane ,, dodecane, isododecane or cyclohexane; liquid aromatic cyclic compounds at room temperature such as toluene and xylene; aldehydes that are liquid at room temperature, such as benzaldehyde, acetaldehyde, and mixtures thereof.

The composition may comprise, besides the block polymer described above, an additional polymer such as a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, especially to keratin materials.

Among the film-forming polymers used in the composition of the present invention, synthetic polymers include, of radical type or of polycondensate type, natural polymers and mixtures thereof. Film-forming polymers can be cite in particular acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulose polymers such as nitrocellulose. The polymer may be associated with one or auxiliary film-forming agents. Such a film-forming agent can be chosen from all the compounds known to the art as being capable of fulfilling the desired function, and may be chosen from plasticizers and coalescing agents.

The composition according to the invention may comprise at least one wax. By wax in the sense of the present invention, means a lipophilic compound that is solid at room temperature (25 ° C), with reversible solid / liquid reversible, having a melting point up to 30 ° C up until to 120 ° C.

The melting point of the wax may be measured using a calorimeter, differential scanning (DSC), for example the calorimeter sold under the name DSC 30 by the company Mettler. The waxes can be hydrocarbon, fluorinated and / or silicone and may be of plant, mineral, animal and / or synthetic. In particular, the waxes have a melting point greater than 25 ° C and greater than 45 ° C. Gum wax usable in the composition of the invention include beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes or Fischer-Tropsch, silicone waxes such as alkyl or alkoxy dimethicones containing from 16 to 45 carbon atoms.

The nature and quantity of solid fats depend on the mechanical properties and textures. As a guide, the composition may contain from 0 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.

The composition according to the invention may further comprise one or more dyestuffs chosen from water-soluble dyes and pulverulent coloring materials such as pigments, pearlescent agents and glitter well known in the art. The dyestuffs may be present in the composition in a content ranging from 0.01% to 50% by weight, based on the weight of the composition, preferably from 0.01% to 30% by weight.

Pigments should be understood particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition. Pearlescent agents should be understood to mean iridescent particles of any form, especially produced by certain mollusks in their shell or synthesized.

The pigments can be white or colored, inorganic and / or organic. These include, among inorganic pigments, titanium dioxide, optionally surface-treated, the

^' zirconium oxide or cerium oxide, and zinc oxide, iron oxide (black, yellow or red) or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, and metal powders aluminum powder, copper powder.

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.

It may also be made of effect pigments, such as particles comprising an organic or inorganic substrate, natural or synthetic, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being uncoated or coated with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and mixtures thereof.

The pearlescent pigments can be chosen from white pearlescent pigments such as mica coated with titanium or with bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated especially with blue iron or chromium oxide, titanium mica coated with an organic pigment of the abovementioned type, and pearlescent pigments based on bismuth oxychloride. . One can also use interference pigments, in particular liquid crystal or multilayer.

Water-soluble dyes are for example beetroot juice, methylene blue.

The composition according to the invention may further comprise one or more fillers, especially in a content ranging from 0.01% to 50% by weight, based on the total weight of the composition, preferably from 0.01% to 30 % in weight. By fillers are meant particles of any shape, colorless or white, inorganic or synthetic, insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers serve especially to modify the rheology or texture of the composition. The fillers may be mineral or organic of any shape, platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Include talc, mica, silica, kaolin, polyamide powders (Nylon®) (Orgasol® from Atochem), poly-β- alanine and polyethylene, tetrafluoroethylene polymer powders (Teflon® ) lauroyllysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride / acrylonitrile, Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® of Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, microspheres hollow silica (silica Beads® from Maprecos), microcap'sules glass or ceramic, and metal soaps derived from organic carboxylic acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, example zinc stearate, magnesium or lithium, zinc laurate or magnesium myristate.

The composition according to the invention may especially be in the form of suspension, dispersion, solution, gel, emulsion, including oil-in-water (O / W) or water-in-oil (W / O ), or multiple (W / O / W or polyol / O / W or O / W / O), as a cream, paste, foam, dispersion of vesicles, especially of ionic or nonionic lipids, two-phase lotion or multiphase, spray, powder, a paste, especially a soft paste (in particular paste having a dynamic viscosity at 25 ° C of the order of 0.1 to 40 Pa.s at a shear rate of 200 s^"1After 10 minutes geometry measurement cone / plate). The composition may be anhydrous, for example it may be a flexible anhydrous paste.

The skilled person may select the appropriate dosage form and its method of preparation, on the basis of his general knowledge, taking into account both the nature of the constituents used, especially their solubility in the support, and secondly to the application envisaged for the composition.

The composition according to the invention may be a makeup composition such as products for the complexion (foundations), the blush or eye shadow, liquid lipsticks, concealer products, mascaras, Eye- eyeliners, eyebrow makeup products, nail products, such as nail polish, product body makeup, hair makeup products (hair lacquer or mascara).

The composition according to the invention may also be a care of body and facial skin, in particular a sunscreen or skin coloring (such as a self-tanning).

The present invention also relates to a cosmetic assembly comprising: - a container delimiting at least one compartment, said container being closed by a closing member; and - a composition as described above disposed within said compartment.

The container can be in any suitable form. It may especially be in the form of a bottle, a tube, a jar, a case, a box, a sachet or a carton.^•

The closing member may be in the form of a removable stopper, a lid, a cover, a tear-off strip or a capsule, especially of the type comprising a body fixed to the container and a cap articulated on the body. It may also be in the form of a member ensuring the selective closure of the container, especially a pump, a valve or a flap valve.

The container may be combined 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 in the form of a brush, as described for example in patent FR 2 722 380. The applicator may be in the form of a block of foam or of elastomer, a felt or a spatula. The applicator may be free (tuft or sponge) or securely fastened to a rod borne by the closing member, as described for example in US Patent 5 492 426. The applicator may be secured to the receptacle, as described for example FR 2761959.

The product may be contained directly in the container, or indirectly. For example, the product may be arranged on an impregnated support, especially in the form of a wipe or a pad, and arranged (individually or in plurality) in a box or in A sachet. Such a support incorporating the product is described for example in patent application WO 01/03538.

The closing member may be coupled to the container by screwing. Alternatively, the coupling between the closing member and the container is done other than by screwing, especially via a bayonet mechanism, by snap-fastening, gripping, welding, bonding or by magnetic attraction. "Snapping" in particular means any system involving the crossing of a bead or cord of material by elastic deformation of a portion, including the closing member, followed by return elastically unstressed position of the 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 may have rigid walls or deformable walls, especially in the form ^' a tube or a tubular bottle.

The container may comprise means for causing or facilitating the distribution dice the composition. For example, the container may have deformable walls so as to cause the output of the composition in response to an excess pressure inside the container, this positive pressure being caused by elastic (or non-elastic) squeezing of the container walls .

The container may consist of a carton with a base delimiting at least one housing containing the composition, and a lid, especially articulated on the base, and capable of covering at least partially said bottom. Such a case is described for example in application WO 03/018423 or in patent FR 2 791 042.

The container may be 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 composition may be at atmospheric pressure inside the container (at room temperature) or pressurized, especially by means of a propellent gas (aerosol). In the latter case, the container is equipped with a valve (of the type used for aerosols).

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

The following examples are not limited to illustrate the compositions according to the invention.

Example 8-12: Lipstick lèyres

Example 8 9 10 11 12

Polymer of Example 2 90.7

Polymer of Example 3 90.7

Polymer of Example 4 90.7

Polymer of Example 6 90.7

Polymer of Example 7 90.7

Polyisobutene 2,1 2,1 2,1 2,1 2,1

Hydrogen

Octyldodecanol 0.9 0.9 0.9 0.9 0.9

Phenyltrimethicone 2.1 2.1 2.1 2.1 2.1

(DC 556, 20 cSt, Dow Corning)

Vinylpyrrolidone / 1 -éicosène

(Antaron V-220, ISP) 1, 2 1, 2 1, 2 1, 2 1, 2 pigment 3 3 3 3 3

procedure

1. It makes the pigment millbase pigments in the oily phase by performing three passes of the mixture to the grinder sorting cylinders.

2. is weighed in a beaker the homogenate necessary for the composition and other ingredients.

3. Place the mixture Rayneri stirring for 45 min at room temperature.

4. It runs the formula in sealed water bottles in isododecane.

gloss meter 1. Using a mechanical applicator is carried out, for each composition, a film having a wet thickness of 50 microns and a film having a wet thickness of 150 .mu.m. Deposits are made on a Leneta brand contrast card of reference Form 1A Penopac.

2. It is allowed to dry 24 hours at a controlled temperature of 30 ° C.

3. They were performed gloss measurements micro-tri-gloss glossmeter Byk Gardner at a measurement angle of 20 ° and a measurement angle of 60 ° for each of the two deposits.

brightness in vitro results obtained are shown in the table below:

deposit 150 .mu.m

<img id="imgf000038_0001" he="45" wi="139" file="imgf000038_0001.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

Deposit 50 μ m

<img id="imgf000038_0002" he="45" wi="138" file="imgf000038_0002.tif" img-format="tif" img-content="table" orientation="portrait" inline="no" />

The mean gloss obtained is greater than 40 to 100 for a measuring angle of 20 ° and a thickness of 50 .mu.m or 150 .mu.m. The mean gloss obtained is greater than 65 to 100 for a measuring angle of 60 ° and a thickness of 50 .mu.m. The mean gloss obtained is greater than 70 on-100 for a measuring angle of 60 ° and a thickness of 150 .mu.m.

Example 13: Nail Polish

Polymer of Example 1 23.8 g AM

Butyl Acetate 24.99 g Isopropanol 10.71 g

Hexylene glycol 2.5 g

DC RED 7 g Lake 1

Hectorite modified chloride 1, 3 g of distearyl methyl benzyl ammonium (Bentone^® 27V from Elementis)

Example 14: Nail Polish

Polymer of Example 5 23.8 g AM Butyl acetate 24.99 g

Isopropanol 10.71 g-

Hexylene glycol 2.5 g

DC RED 7 g Lake 1

Hectorite modified chloride 1, 3 g of distearyl methyl benzyl ammonium (Bentone^® 27V from Elementis)

Ethyl acetate qs 100 g