ES2362275T3 - GLOSSY LIQUID COMPOSITION CONTAINING A SEQUENCED POLYMER. - Google Patents

Abstract

Liquid cosmetic composition containing a cosmetically acceptable organic liquid medium and a non-elastomeric film-forming linear sequential ethylene polymer, whose sequenced polymer contains first and second sequences joined together by an intermediate segment, which is a statistical polymer that includes at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence, the first polymer sequence being selected from: - a) a sequence having a Tg greater than or equal to 40 ° C, - b) a sequence having a lower Tg or equal to 20 ° C and - c) a sequence having a Tg between 20 and 40 ° C, and the second sequence being selected in a category a), b) or c) different from the first sequence, and whose sequenced polymer it has a polydispersity index I greater than 2.8, said polymer being such that, when it is in sufficient quantity in the composition, the average brightness at 20 ° of a deposit of said composition, once extended on a support, is greater than or equal to 30 over 100.

Description

The present invention relates to a liquid cosmetic makeup or skin care composition, including the scalp, both of the face and of the human body, of the lips or of the slaves of human beings, such as the hair, the eyelashes, eyebrows or nails, which includes a cosmetically acceptable medium that contains a particular sequenced polymer.

There are numerous cosmetic compositions for which the gloss properties of the deposited film, after application on keratin materials (skin, lips, pimps), are very important. One can cite, for example, lipsticks, nail polishes or also certain hair products and certain mascaras.

Cosmetic product formulators know that this shine property is favored when oils characterized by a high viscosity and refractive index are used and that they also have good dispersion properties of pigments or fillers when the latter are present. In the composition.

From this point of view, the formulator has several types of raw materials, such as oily polymers such as polybutenes, sold especially under the Indopol H100, H300 and H1500 reference by the Amoco Company, which have a very high viscosity, but which have However, the disadvantage of being both very sticky and having dispersion properties of relatively weak pigments, which limits their use.

The present invention aims to propose a new way of formulating a cosmetic product, in particular a makeup product, which allows good gloss properties.

In particular, the product of the invention allows for continuous deposits on the skin or lips, of good coverage, which have a very bright appearance, adapted to the desire of the consumer, non-migratory, that are not transferred and of good persistence , not oily, that do not dry out the skin, hair or lips on which it is applied, both during its application and over time. It also has good stability properties and thus allows a homogeneous and aesthetic application.

A subject of the invention is a bright liquid composition for the care or makeup of the skin and / or lips and / or the legs that contains a sequenced polymer that allows to remedy the drawbacks of known bright compositions. Surprisingly, the inventors saw that the use of a sufficient amount of a particular sequenced polymer makes it possible to obtain a bright composition and that it also has good persistence.

The composition of the invention may, in particular, constitute a hair product or a make-up product of the body, lips or slanes of human beings having care and / or treatment properties. It is especially a lipstick or lip gloss, an eye shadow, a tattoo product, a mascara, an eyeliner, a nail polish, an artificial tanning product of the skin, a care cream

or possibly color protection or a hair coloring or care product.

More precisely, the object of the invention is a liquid cosmetic composition containing a medium cosmetically acceptable organic liquid and a non-elastomeric film-forming linear ethylenic sequencing polymer, whose sequenced polymer contains first and second sequences linked together by an intermediate segment, which it is a statistical polymer comprising at least one constituent monomer of the first sequence and at least a constituent monomer of the second sequence, the first polymer sequence being selected from:

-

 a) a sequence that has a Tg greater than or equal to 40 ° C,

-

 b) a sequence that has a Tg less than or equal to 20 ° C and

-

 c) a sequence having a Tg between 20 and 40 ° C, and

the second sequence being selected in a category a), b) or c) different from the first sequence; and whose sequenced polymer has a polydispersity index I greater than 2.8, said polymer being such that, when it is in sufficient quantity in the composition, the average gloss measured at 20 ° of a deposit of said composition, once extended on a support, is preferably greater than or equal to 30 over 100

A subject of the invention is also a liquid cosmetic composition containing an organic liquid medium cosmetically acceptable and a film-forming linear ethylenic sequenced polymer free of styrene unit, whose

sequenced polymer contains first and second sequences linked together by an intermediate segment, which is a statistical polymer comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence, the first polymer sequence being selected from:

-

 a) a sequence that has a Tg greater than or equal to 40 ° C,

-

 b) a sequence that has a Tg less than or equal to 20 ° C and

-

 c) a sequence having a Tg between 20 and 40 ° C, and

the second sequence being selected in a category a), b) or c) different from the first sequence; and whose sequenced polymer has a polydispersity index I greater than 2.8, said polymer being such that, when it is in sufficient quantity in the composition, the average gloss measured at 20 ° of a deposit of said composition, once extended on a support, is preferably greater than or equal to 30 over 100

U.S. Patent 6,153,206 describes a cosmetic composition that includes a polymer containing repetitive units having a Tg of -10 to 75 ° C and repetitive units having a Tg of 76 to 120 ° C. It also describes block polymers comprising polymethyl methacrylate blocks and polyisobutyl methacrylate blocks, and also triblock polymers comprising polymethyl methacrylate blocks, polyisobutyl methacrylate blocks and ethyl methacrylate blocks. Documents FR-A-2,809,306 and WO 03/046032 describe cosmetic compositions containing a sequenced ethylene polymer. In the examples, the only exemplified polymer has a polydispersity index respectively equal to 2.2 and 1.16.

By "liquid composition" is meant a composition that, at 25 ° C and atmospheric pressure, takes the form of the container in which it is poured.

Preferably, the composition according to the invention is a composition without rinsing.

Average brightness of the composition

By "medium brightness", the brightness is designated as can be measured with a brightness meter, in a conventional manner, by the following method.

On a contrast card of LENETA brand and reference FORM 1A PENOPAC, a layer between 50 m and 150 m thick of the composition is spread with an automatic extender. The layer covers at least the white background of the cardboard. The tank is allowed to dry 24 hours at a temperature of 30 ° C and then the brightness measurement is carried out at 20 ° on the white background with a BYK GARDNER brand and microTRIGLOSS reference brightness meter.

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

The average brightness of the composition measured at 20 ° is advantageously greater than or equal to 30, better 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, above 100, better still 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, above 100. For certain compositions according to invention, such as nail polishes, the brightness measured at 20 ° may be greater than or equal to 70, even 80, over 100.

Preferably, the average brightness of the composition, once extended on 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, better still greater than 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, over 100.

The average brightness at 60 ° is measured as follows. The brightness can be measured with a brightness meter, in a conventional manner, by the following method.

On a contrast card of LENETA brand and reference FORM 1A PENOPAC, a layer between 50 m and 150 m thick of the composition is spread with an automatic extender. The layer covers at least the white background of the cardboard. The tank is allowed to dry 24 hours at a temperature of 30 ° C and then the brightness measurement at 60 ° is then carried out on the white background with a BYK GARDNER brand and microTRIGLOSS reference brightness meter.

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

According to one embodiment, the average brightness of the composition measured at 20 ° is preferably greater than or equal to 35, preferably 40, 45 or 50, above 100, and / or the average brightness of the composition measured at 60 ° is preferably greater or equal to 65, 70 or 75 over 100. In this embodiment, the composition advantageously constitutes a liquid lipstick.

According to one embodiment, the average brightness of the composition measured at 20 ° is preferably greater than or equal to 60, preferably 65, 70 or 75, above 100, and / or the average brightness of the composition measured at 60 ° is preferably greater or equal to 80, 85 or 90 over 100. In this embodiment, the composition advantageously constitutes a nail polish.

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

The invention also relates to a method of makeup of the skin and / or lips and / or lips, consisting of applying the composition as defined above on the skin and / or lips and / or the lips .

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

The invention also relates to the use of a polymer sequenced in an amount sufficient in a cosmetic composition to impart gloss and / or persistence to a deposit of said composition.

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

The composition advantageously contains a smaller proportion of oils traditionally used to impart shine, whose oils are generally adherent.

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

By "oil" is meant a compound not miscible with water in any proportion, liquid at room temperature (25 ° C) and atmospheric pressure (760 mm Hg).

By "bright oil" is meant an oil whose molar mass is preferably 650 to 10,000 g / mol, and preferably 750 to 7,500 g / mol.

Oil that has a molar mass of 650 to 10,000 g / mol can be selected from:

- lipophilic polymers such as:

-

 polybutylenes, such as INDOPOL H-100 (molar mass or MM = 965 g / mol), INDOPOL H-300 (MM = 1,340 g / mol) and INDOPOL H-1500 (MM = 2,160 g / mol) , marketed or manufactured by AMOCO;

-

 hydrogenated polyisobutylenes, such as PANALANE H-300 E, marketed or manufactured by AMOCO (MM = 1,340 g / mol), VISEAL 20000, marketed or manufactured by SYNTEAL (MM = 6,000 g / mol) and REWOPAL PIB 1000, marketed or manufactured by WITCO (MM = 1,000 g / mol);

-

 polyidecenes and hydrogenated polydecenes, such as: PURESYN 10 (MM = 723 g / mol) and PURESYN 150 (MM = 9,200 g / mol), marketed or manufactured by MOBIL CHEMICALS;

-

 vinylpyrrolidone copolymers, such as: the vinylpyrrolidone / 1-hexadecene copolymer, ANTARON V-216, marketed or manufactured by the ISP company (MM = 7,300 g / mol);

-esters such as:

-

 esters of linear fatty acids having a total number of carbons from 35 to 70, such as pentaerythrityl tetrapelargonate (MM = 697.05 g / mol);

-

 hydroxylated esters, such as polyglycerol-2 triisoestearate (MM = 965.58 g / mol);

-

 aromatic esters, such as tridecyl trimellitate (MM = 757.19 g / mol);

-

 esters of fatty alcohol or branched C24-C28 fatty acids, such as those described in application EP-A-0.955.039, and especially triisoaraquidyl citrate (MM = 1.033.76 g / mol), pentaerythrityl tetraisononanoate (MM = 697.05 g / mol), glyceryl triisoestearate (MM = 891.51 g / mol), glyceryl 2-tridecyltetradecanoate (MM = 1,143.98 g / mol), pentaerythrityl tetraisoestearate (MM = 1,202, 02 g / mol), polyglyceryl-2 tetraisoestearate (MM = 1,232.04 g / mol) or also 2

5

fifteen

25

35

Four. Five

55

pentaerythrityl tetradecyltetradecanoate (MM = 1,538.66 g / mol);

-

 silicone oils, such as phenylated silicones, such as BELSIL PDM 1000 from WACKER (MM = 9,000 g / mol);

-

 Vegetable oils, such as sesame oil (820.6 g / mol);

-and their mixtures.

Sequenced polymer:

The composition according to the present invention contains at least one sequenced polymer. By "sequenced" polymer is meant a polymer comprising at least two different sequences, preferably at least three different sequences.

According to one embodiment, the sequenced polymer of the composition according to the invention is an ethylenic polymer. By "ethylenic" polymer is meant a polymer obtained by polymerization of monomers having an ethylenic unsaturation.

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

According to one embodiment, the sequenced polymer of the composition according to the invention is a film forming polymer. By "film-forming" polymer, is meant a polymer capable of forming, on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, especially on keratin materials.

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

By "non-elastomeric polymer", a polymer is understood which, when subjected to a tension intended to stretch it (for example by 30% in relation to its initial length), does not recover a length substantially identical to its initial length when it ceases the tension.

More specifically, by "non-elastomeric polymer" is meant a polymer that has an instantaneous recovery Ri <50% and a delayed recovery R2h <70% after having suffered an elongation of 30%. Preferably, Ri is <30% and R2h <50%.

More specifically, the non-elastomeric character of the polymer is determined according to the following protocol:

A polymer film is prepared by pouring a solution of the polymer into a Teflon matrix and then drying for 7 days in a controlled environment at 23  5 ° C and 50  10% relative humidity. A film of approximately 100 µm thick is then obtained in which rectangular test pieces (for example with the punch) of a width of 15 mm and a length of 80 mm are cut.

A tensile stress is imposed on this sample with an apparatus marketed under the Zwick reference, under the same temperature and humidity conditions as for drying.

The test pieces are stretched at a speed of 50 mm / min. and the distance between the jaws is 50 mm, which corresponds to the initial length (I0) of the test piece.

Instant recovery Ri is determined as follows:

-

 the test piece is stretched by 30% (max), that is, approximately 0.3 times its initial length (I0);

-

 the tension is relaxed by imposing a return speed equal to the traction speed, that is, 50 mm / min., and the residual elongation of the test piece is measured in percentage, after returning to zero voltage (i).

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

Ri = ((max - i) / max) x 100

5

To determine the delayed recovery, the residual elongation of the test piece is measured in percentage (2h) 2 hours after returning to zero voltage.

Delayed recovery in% (R2h) is given by the following formula:

R2h = ((max - 2h) / max) x 100

For purely indicative purposes, a polymer according to an embodiment of the invention has an instantaneous recovery of 10% Ri and a delayed recovery R2h of 30%.

According to another embodiment, the sequenced polymer of the composition according to the invention does not contain a styrene unit. By "free styrene unit polymer" is meant a polymer containing less than 10%, preferably less than 5%, preferably less than 2%, preferably even less than 1%, by weight i) of styrene unit of formula -CH (C6H5) -CH2- or ii) of substituted styrene unit, such as methylstyrene, chlorostyrene or chloromethylstyrene.

According to one embodiment, the sequenced polymer of the composition according to the invention is derived from aliphatic ethylenic monomers. By aliphatic monomer, is meant a monomer that has no aromatic group.

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

According to one embodiment, the sequenced polymer comprises at least a first sequence and at least a second sequence such as those defined above.

By "at least" one sequence, one or more sequences are understood.

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

Preferably, the intermediate sequence is essentially derived from monomers constituting the first sequence and the second sequence.

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

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

By "sequences incompatible with each other", it is understood that the mixture formed by the polymer corresponding to the first sequence and by the polymer corresponding to the second sequence is not miscible in the majority liquid by weight contained in the organic liquid medium of the composition, at room temperature (25 ° C) and atmospheric pressure (105 Pa), for a content in the polymer mixture greater than or equal to 5% by weight with respect to the total weight of the mixture (polymers and majority organic liquid), it being understood that :

i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90/10, and that ii) each of the polymers corresponding to the first and second sequences has a mean molecular mass ( by weight or number) equal to that of the sequenced polymer +/- 15%.

In case the organic liquid medium includes a mixture of organic liquids, in the hypothesis of two or more liquids present in identical mass proportions, said polymer mixture is not miscible in at least one of them.

If the organic liquid medium includes a single organic liquid, the latter obviously constitutes the majority liquid by weight.

By "organic liquid medium" is meant a medium that contains at least one organic liquid, that is, 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 a volatile or non-volatile oil (fatty body).

Preferably, the organic liquid is cosmetically acceptable (acceptable tolerance, toxicology and touch). The organic liquid medium is cosmetically acceptable, in the sense 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 solvent or one of the polymerization solvents of the sequenced polymer, such as those described below.

By polymerization solvent, is meant a solvent or a mixture of solvents. The polymerization solvent can be especially selected from ethyl acetate, butyl acetate, alcohols such as isopropanol or 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 sequenced polymer can be incorporated into the composition in a high dry matter content, typically greater than 10%, greater than 20% and preferably still greater than 30%, and preferably even greater than 45%, by weight with respect to to the total weight of the composition, yet easy to formulate.

Preferably, the sequenced polymer has no silicon atoms in its skeleton. By "skeleton", the main polymer chain is understood, as opposed to the pending side chains.

Preferably, the polymer according to the invention is not water soluble, that is, the polymer is not soluble in water.

or in a mixture of water and linear or branched lower monoalcohols of 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol, without pH modification, at an active matter content of at least 1% by weight, at room temperature (25 ° C).

Advantageously, the sequenced polymer used in the compositions according to the invention has a polydispersity index I of 2.8 to 6.

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

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

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

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

Each sequence or block of the sequenced polymer is derived from one type of monomer or several different types of monomers.

This means that each sequence can be constituted by a homopolymer or by a copolymer, this copolymer can be constituting the sequence in turn statistical or alternate.

The indicated glass transition temperatures of the first and second sequences may be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual, such as the Polymer Handbook, 3rd ed., 1989, John Wiley, according to the following relationship, called Fox's Law:

image 1

i being the mass fraction of monomer i in the sequence considered and Tgi being the glass transition temperature of homopolymer of monomer i.

Unless otherwise indicated, the Tg indicated for the first and second sequences in the present application are theoretical Tg.

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

It is intended to designate in the present invention by the expression:

"Between ... and ..." a range of values where the mentioned limits are excluded, and "from ... to ..." and "ranging from ... to ..." a range of values whose limits are included.

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a) Sequence that has a Tg greater than or equal to 40 ° C

The sequence having a Tg greater than or equal to 40 ° C has, for example, a Tg of 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example 50 ° C to 120 ° C, and better or equal to 60 ° C, for example from 60 ° C to 120 ° C.

10

The sequence having a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer.

The sequence having a Tg greater than or equal to 40 ° C can proceed in all or part of one or more monomers, which are such that the homopolymer prepared from these monomers has a temperature of

15 glass transition greater than or equal to 40 ° C.

If this sequence is a homopolymer, it is derived from monomers such that the homopolymers prepared from these monomers have glass transition temperatures greater than or equal to 40 ° C. This first sequence may be a homopolymer, consisting of a single type of monomer (where the Tg of the

20 corresponding homopolymer is greater than or equal to 40 ° C).

If the first sequence is a copolymer, it can proceed in whole or in part from one or more monomers, the nature and concentration of which are selected so that the Tg of the resulting copolymer is greater than or equal to 40 ° C. The copolymer may, for example, comprise:

25

- monomers such that homopolymers prepared from these monomers have higher Tg

or equal to 40 ° C, for example a Tg of 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example 50 ° C to 120 ° C, and better than or equal to 60 ° C, for example from 60 ° C to 120 ° C, and

- monomers such that homopolymers prepared from these monomers have lower Tg

30 to 40 ° C, selected from monomers that have a Tg between 20 and 40 ° C and / or monomers that have a Tg less than or equal to 20 ° C, for example a Tg of -100 to 20 ° C, preferably below 15 ° C, especially from -80 ° C to 15 ° C and better below 10 ° C, for example from -50 ° C to 0 ° C, such as those described below.

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

- methacrylates of formula CH2 = C (CH3) -COOR1,

wherein R1 represents an unsubstituted, linear or branched alkyl group of 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R1 represents a C4 to C12 cycloalkyl group;

-

 acrylates of formula CH2 = CH-COOR2, wherein R2 represents a C4 to C12 cycloalkyl group, such as isobornyl acrylate, or a tert-butyl group;

-

 the (meth) acrylamides of the formula:

Four. Five

image2

50 and R ’designates H or methyl. As an example of monomers, there can be mentioned N-butylacrylamide, N-tbutylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutyl acrylamide;

-and their mixtures.

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

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

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

The sequence having a Tg less than or equal to 20 ° C may be a homopolymer or a copolymer.

The sequence having a Tg less than or equal to 20 ° C can proceed in all or part of one or more monomers such that the homopolymer prepared from these monomers has a lower glass transition temperature

or equal to 20 ° C.

If this sequence is a homopolymer, it is derived from monomers such that the homopolymers prepared from these monomers have glass transition temperatures of less than or equal to 20 ° C. This second sequence may be a homopolymer, consisting of a single type of monomer (where the Tg of the corresponding homopolymer is less than or equal to 20 ° C).

In the event that the sequence having a Tg less than or equal to 20 ° C is a copolymer, it may proceed in whole or in part from one or more monomers, the nature and concentration of which are selected so that the Tg of the resulting copolymer is less than or equal to 20 ° C.

You can, for example, understand.

-

 one or more monomers whose corresponding homopolymer has a Tg less than or equal to 20 ° C, for example a Tg of -100 ° C to 20 ° C, preferably less than 15 ° C, especially from -80 ° C to 15 ° C and better below 10 ° C, for example from -50 ° C to 0 ° C, and

-

 one or more monomers whose corresponding homopolymer has a Tg greater than 20 ° C, such as monomers having a Tg greater than or equal to 40 ° C, for example a Tg of 40 to 150 ° C, preferably greater than or equal to 50 ° C, for example from 50 ° C to 120 ° C, and better than or equal to 60 ° C, for example from 60 ° C to 120 ° C, and / or monomers having a Tg between 20 and 40 ° C , such as those described above.

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

Monomers whose homopolymer has a Tg less than or equal to 20 ° C are preferably selected from the following monomers, or major monomers:

-

 acrylates of formula CH2 = CHCOOR3, R3 representing a C1 to C12 unsubstituted alkyl group, linear or branched, with the exception of the tert-butyl group, where one or more heteroatoms selected from O are eventually intercalated, N yS;

-

 methacrylates of formula CH2 = C (CH3) -COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group, where they are located possibly interleaved one or more heteroatoms selected from 0, N and S;

-

 vinyl esters of formula R5-CO-O-CH = CH2, where R5 represents a linear or branched C4 to C12 alkyl group;

-

 C4 to C12 vinyl and alkyl ethers;

-

 N-C4 to C12 alkyl acrylamides, such as N-octylacrylamide;

-and their mixtures.

Particularly preferred major monomers for the sequence having a Tg of less than or equal to 20 ° C are alkyl acrylates whose alkyl chain has 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as the acrylate of methyl, isobutyl acrylate, 2-ethylhexyl acrylate and mixtures thereof.

c) Sequence that has a Tg between 20 and 40 ° C

The sequence having a Tg between 20 and 40 ° C can be a homopolymer or a copolymer.

The sequence having a Tg between 20 and 40 ° C can be derived from all or part of one or more monomers such that the homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C.

The sequence having a Tg between 20 and 40 ° C can come from all or part of monomers such that the corresponding homopolymer has a Tg greater than or equal to 40 ° C and from monomers such that the corresponding homopolymer has a lower Tg or equal to 20 ° C.

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

Monomers whose homopolymer has a glass transition temperature between 20 and 40 ° C are preferably selected from n-butyl methacrylate, cyclodecyl acrylate, neopentyl acrylate, isodecyl acrylamide and mixtures thereof.

In the event that the sequence having a Tg between 20 and 40 ° C is a copolymer, it comes in whole or in part from one or more monomers (or main monomers) whose nature and concentration are selected such that the Tg of the resulting copolymer is between 20 and 40 ° C.

Advantageously, the sequence having a Tg between 20 and 40 ° C is a copolymer from all

or in part:

-

 of main monomers whose corresponding homopolymer has a Tg greater than or equal to 40 ° C, for example a Tg of 40 ° C to 150 ° C, preferably greater than or equal to 50 ° C, for example 50 to 120 ° C, and better greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C, such as those described above, and / or

-

 of main monomers whose corresponding homopolymer has a Tg of less than or equal to 20 ° C, for example a Tg of -100 to 20 ° C, preferably less than or equal to 15 ° C, especially of -80 ° C to 15 ° C and better less than or equal to 10 ° C., for example from -50 ° C to 0 ° C, such as those described above,

said monomers being selected such that the Tg of the copolymer forming the first sequence is between 20 and 40 ° C.

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

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

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

Advantageously, each of the first and second sequences comes entirely from at least one monomer selected from acrylic acid, esters of acrylic acid, (meth) acrylic acid, esters of (meth) acrylic acid and mixtures thereof.

Each of the sequences can, however, contain in a minor proportion at least one constituent monomer of the other sequence.

Thus, the first sequence may contain at least one constituent monomer of the second sequence and vice versa.

Each of the first and / or second sequences may include, apart from the monomers indicated above, one or more other monomers, called additional monomers, different from the main monomers mentioned above.

The nature and amount of this or these additional monomers are selected so that the sequence in which they are found has the desired glass transition temperature.

This additional monomer is, for example, selected from:

a) hydrophilic monomers, such as:

-

 monomers with ethylenic unsaturation (s) that have at least one carboxylic acid function or

sulfonic acid, such as: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinyl phosphoric acid and its salts;

-

 monomers with ethylenic unsaturation (s) that have at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,

dimethylaminopropyl methacrylamide and its salts;

-

 methacrylates of formula CH2 = C (CH3) -COOR6, where R6 represents a linear or branched alkyl group of 1 to 4 carbon atoms, such as a group methyl, ethyl, propyl or isobutyl, said alkyl group being substituted by one or more substituents selected from hydroxyl groups (such as 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I and F), such as trifluoroethyl methacrylate;

-

 methacrylates of formula CH2 = C (CH3) -COOR9, R9 representing a linear or branched C6 to C12 alkyl group, where they are eventually found intercalated one or more heteroatoms selected from 0, N and S, said alkyl group being substituted by one or more substituents selected from the hydroxyl groups and the atoms of halogens (Cl, Br, I and F);

-

 acrylates of formula CH2 = CHCOOR10, R10 representing a C1 to C12 alkyl group, linear or branched, substituted by one or more substituents selected from the hydroxyl groups and the halogen atoms (Cl, Br, I and F), such as the acrylate of 2-hydroxypropyl and 2-hydroxyethyl acrylate, or R10 represents a (C1-C12) -O-POE (polyoxyethylene) alkyl with repeating the oxyethylene unit 5 to 30 times, for example methoxy-POE, or R10 represents a polyoxyethylene group having 5 to 30 units of ethylene oxide;

b) ethylenically unsaturated monomers that include one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris (trimethylsiloxy) silane;

-and their mixtures.

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

According to one embodiment, each of the first and second sequences of the sequenced polymer comprises at least one monomer selected from the esters of (meth) acrylic acid and possibly at least one additional monomer such as (meth) acrylic acid, and its mixtures

According to another embodiment, each of the first and second sequences of the sequenced polymer comes entirely from at least one monomer selected from the esters of (meth) acrylic acid and possibly from at least one additional monomer such as acid (met ) acrylic, and mixtures thereof.

According to a preferred embodiment, the sequenced polymer is a non-siliconized polymer, that is, a polymer free of silicon atoms.

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

The sequenced polymer can be obtained by polymerization of radicals in solution according to the following preparation procedure:

- a part of the polymerization solvent is introduced into an adapted reactor and heated to the appropriate temperature for polymerization (typically between 60 and 120 ° C);

- once this temperature has been reached, the constituent monomers of the first sequence are introduced in the presence of a part of the polymerization initiator;

-

 after a time T corresponding to a maximum conversion ratio of 90%, the constituent monomers of the second sequence and the other part of the initiator are introduced;

-

 the mixture is allowed to react for a time T ’(which goes from 3 to 6 h), after which the mixture is brought back to room temperature;

-

 The polymer in solution is obtained in the polymerization solvent.

First embodiment

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

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

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

Preferably, the proportion of the sequence having a Tg greater than or equal to 40 ° C ranges from 20 to 90% by weight of the polymer, better from 30 to 80% and even better from 50 to 70%.

Preferably, the proportion of the sequence having a Tg of less than or equal to 20 ° C ranges from 5 to 75% by weight of the polymer, preferably from 15 to 50% and better from 25 to 45%.

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

-

 a first sequence of Tg greater than or equal to 40 ° C, for example with a Tg of 70 to 110 ° C, which is a copolymer of methyl methacrylate / acrylic acid;

-

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

-

 an intermediate sequence, which is a copolymer of methyl methacrylate / acrylic acid / methyl acrylate.

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

-

 a first sequence of Tg greater than or equal to 40 ° C, for example from 70 to 100 ° C, which is a copolymer of methyl methacrylate / acrylic acid / trifluoroethyl methacrylate;

-

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

-

 an intermediate sequence, which is a statistical copolymer of methyl methacrylate / acrylic acid / methyl acrylate / trifluoroethyl methacrylate.

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

-

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

-

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

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.

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

-

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

-

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

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / methyl methacrylate / 2-ethylhexyl acrylate.

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

-

 a first sequence of Tg greater than or equal to 40 ° C, for example from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate copolymer;

-

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

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / isobornyl methacrylate / 2-ethylhexyl acrylate.

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

-

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

-

 a second sequence of Tg less than or equal to 20 ° C, for example from -35 to -5 ° C, which is an isobutyl acrylate homopolymer, and

-

 an intermediate sequence, which is a statistical copolymer of isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate.

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

-

 a first sequence of Tg greater than or equal to 40 ° C, for example from 95 to 125 ° C, which is an isobornyl acrylate / isobornyl methacrylate copolymer;

-

 a second sequence of Tg less than or equal to 20 ° C, for example from -35 to -5 ° C, which is an isobutyl acrylate homopolymer, and

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate.

According to an eighth variant, the polymer according to the invention may comprise:

-

 a first sequence of Tg greater than or equal to 40 ° C, for example from 60 to 90 ° C, which is an isobornyl acrylate / isobutyl methacrylate copolymer;

-

 a second sequence of Tg less than or equal to 20 ° C, for example from -35 to -5 ° C, which is an isobutyl acrylate homopolymer, and

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate.

The following examples illustrate in a non-limiting manner polymers corresponding to this first embodiment.

The quantities are expressed in grams.

Example 1: Preparation of a poly (methyl methacrylate / acrylic acid / methyl acrylate) polymer

100 g of butyl acetate are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour. Then, at 90 ° C and within 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) are added ) 2.5-dimethylhexane (Trigonox® 141, from Akzo Nobel).

The mixture is maintained for 1 hour at 90 ° C.

Then 90 g of methyl acrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2.5-bis (2-ethylhexanoylperoxy) are introduced into the previous mixture, always at 90 ° C and in 1 hour. -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.

A 40% solution in polymer active material in the mixture of butyl acetate / isopropanol is obtained.

A polymer is obtained comprising a first sequence or block of poly (methyl methacrylate / acrylic acid) having a Tg of 100 ° C a second sequence or block of methyl polyacrylate having a Tg of 10 ° C and an intermediate sequence , which is a statistical polymer of methyl methacrylate / acrylic acid / methyl polyacrylate.

The polymer has a weight average mass of 52,000 and a number average mass of 18,000, that is, a polydispersity index I of 2.89.

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

100 g of isododecane are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour. Then, 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) are added ® 141, from Akzo Nobel).

The mixture is maintained for 1 h 30 at 90 ° C.

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

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

A 50% solution in polymer active material in the isododecane is obtained.

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

This polymer has a weight average mass of 77,000 and a numerical average mass of 19,000, that is, a polydispersity index I of 4.05.

Example 3: Preparation of a poly (isobornyl acrylate / isobornyl methacrylate / 2-ethylhexyl acrylate) polymer

100 g of isododecane are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour.

Then, 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-dimethylhexane ( Trigonox® 141, from Akzo Nobel).

The mixture is maintained for 1 h 30 at 90 ° C.

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

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

A 50% solution in polymer active material in the isododecane is obtained.

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

This polymer has a weight average mass of 103,900 and a number average mass of 21,300, that is, a polydispersity index 1 of 4.89.

Example 4: Preparation of a poly (isobornyl acrylate / isobutyl methacrylate / isobutyl acrylate) polymer

100 g of isododecane are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour. Then, 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) are added ® 141, from Akzo Nobel).

The mixture is maintained for 1 h 30 at 90 ° C.

Then 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane are introduced into the above mixture, always at 90 ° C and in 30 minutes.

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

A 50% solution in polymer active material in the isododecane is obtained.

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

Example 5: Preparation of a poly (methyl methacrylate / methyl acrylate / acrylic acid) polymer

100 g of butyl acetate are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour.

Then, 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 are added , 8 g of 2.5-bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane (Trigonox® 141, from Akzo Nobel).

The mixture is maintained for 1 hour at 90 ° C.

Then 90 g of methyl methacrylate, 70 g of butyl acetate, 20 g of isopropanol and 1.2 g of 2.5-bis (2-ethylhexanoylperoxy) are introduced into the previous mixture, always at 90 ° C and in 1 hour. -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.

A 40% solution in polymer active material in the mixture of butyl acetate / isopropanol is obtained.

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

Example 6: Preparation of a poly (isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate) polymer

100 g of isododecane are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour.

Then, at 90 ° C and within 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-dimethylhexane ( Trigonox® 141, from Akzo Nobel).

The mixture is maintained for 1 h 30 at 90 ° C.

Then 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane are introduced into the above mixture, always at 90 ° C and in 30 minutes.

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

A 50% solution in polymer active material in the isododecane is obtained.

A polymer is obtained comprising a first sequence or block of poly (isobornyl acrylate / isobornyl methacrylate) having a Tg of 110 ° C, a second sequence of isobutyl polyacrylate having a Tg of -20 ° C and a sequence intermediate, which is a statistical polymer of isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate.

This polymer has a weight average mass of 151,000 and a number average mass of 41,200, that is, a polydispersity index I of 3.66.

Example 7: Preparation of a poly (isobornyl methacrylate / isobutyl methacrylate / isobutyl acrylate) polymer

100 g of isododecane are introduced into a 1 liter reactor and then the temperature is increased to go from room temperature (25 ° C) to 90 ° C in 1 hour. Then, 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 dimethylhexane (Trigonox) are added ® 141, from Akzo Nobel).

The mixture is maintained for 1 h 30 at 90 ° C.

Then 90 g of isobutyl acrylate, 90 g of isododecane and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2.5-dimethylhexane are introduced into the above mixture, always at 90 ° C and in 30 minutes.

The mixture is kept 3 hours at 90 ° C and then the whole is cooled.

A 50% solution in polymer active material in the isododecane is obtained.

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

This polymer has a weight average mass of 100,700 and a numerical average mass of 20,800, that is, a polydispersity index I of 4.85.

Second embodiment

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

Preferably, the proportion of the first sequence having a Tg between 20 and 40 ° C ranges from 10 to 85% by weight of the polymer, better from 30 to 80% and even better from 50 to 70%.

When the second sequence is a sequence that has a Tg greater than or equal to 40 ° C, it is preferably present in a proportion of 10 to 85% by weight of the polymer, better than 20 to 70% and even better 30 to 70%.

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

Preferably, the first sequence having a Tg between 20 and 40 ° C is a copolymer from monomers such that the corresponding homopolymer has a Tg greater than or equal to 40 ° C and of monomers such that the corresponding homopolymer has a Tg less than or equal to 20 ° C.

Advantageously, the second sequence that has a Tg less than or equal to 20 ° C or that has a Tg greater than or equal to 40 ° C is a homopolymer.

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

-

 a first sequence of Tg comprised between 20 and 40 ° C, for example with a Tg of 25 to 39 ° C, which is a copolymer that includes at least one methyl acrylate monomer, at least one methyl methacrylate monomer and at less an acrylic acid monomer;

-

 a second sequence of Tg greater than or equal to 40 ° C, for example from 85 to 125 ° C, which is a homopolymer composed of methyl methacrylate monomers, and

-

 an intermediate sequence that includes at least one methyl acrylate, methyl methacrylate monomer and

-

 an intermediate sequence that includes 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 sequenced polymer may comprise:

-

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

-

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

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / isobutyl methacrylate / 2-ethylhexyl acrylate.

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

-

 a first sequence of Tg comprised between 20 and 40 ° C, for example with a Tg of 21 to 39 ° C, which is a copolymer of isobornyl acrylate / methyl acrylate / acrylic acid;

-

 a second sequence of Tg greater than or equal to 40 ° C, for example 85 to 115 ° C, which is an homopolymer of isobornyl acrylate, and

-

 an intermediate sequence, which is a statistical copolymer of isobornyl acrylate / methyl acrylate / acrylic acid.

The composition of the invention advantageously contains from 0.1 to 60% by weight in active matter (or dry matter) of sequenced polymer, preferably from 0.5 to 50% by weight and preferably even from 1 to a 40% by weight.

The composition according to the invention may include a hydrophilic medium carrying water or a mixture of water and hydrophilic organic solvent (s), such as alcohols and especially linear or branched lower monoalcohols of 2 to 5 atoms of carbon, such as ethanol, isopropanol or n-propanol, and polyols such as glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols, or also C2 ethers and hydrophilic C1-C4 aldehydes.

The water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content of 0.1% to 99% by weight with respect to the total weight of the composition, and preferably 10% to 80 % in weigh.

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

According to a particularly preferred embodiment, the organic liquid medium of the composition contains at least one organic solvent, which is the one or one of the polymerization solvents of the sequenced 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 includes at least one liquid fatty body at room temperature (25 ° C in general). This liquid fatty body can be of animal, vegetable, mineral or synthetic origin.

As liquid fatty bodies at room temperature, often called oils, usable in the invention, there may be mentioned: hydrocarbon oils of animal origin, such as perhydrosqualene; vegetable hydrocarbon oils, such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms, such as triglycerides of heptanoic or octanoic acids, or sunflower, corn, soybean, grape seed, sesame, apricot, macadamia, castor or avocado, triglycerides of caprylic / capric acids and jojoba oil or shea butter; linear or branched hydrocarbons, of mineral or synthetic origin, such as paraffin oils and their derivatives, petrolatum, polydecenes and hydrogenated polyisobutene, such as Parleam; esters and synthetic ethers, especially fatty acids, such as Purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate and isostearate isostearyl; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisoestearyl malate, triisocetyl citrate and heptanoates, octanoates and decanoates of fatty alcohols; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols of 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2undecylpentadecanol and oleic alcohol; partially hydrocarbon and / or silicone fluorinated oils; silicone oils, such as volatile or non-linear, linear or cyclic polymethylsiloxanes (PDMS), such as cyclomethicones and dimethicones, which eventually carry a phenyl group, such as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyl dimethylenes ; and their mixtures.

These oils may be present in a content of 0.01 to 90%, and better than 0.1 to 85%, by weight with respect to the total weight of the composition.

The organic liquid medium of the composition according to the invention may also include one or more cosmetically acceptable organic solvents (acceptable tolerance, toxicology and touch).

These solvents may generally be present in a content of 0.1 to 90%, preferably still 10 to 90%, by weight with respect to the total weight of the composition, and better than 30 to 90%.

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

The composition may include, apart from the sequenced polymer described above, an additional polymer, such as a film forming polymer. According to the present invention, "film-forming polymer" is understood as a polymer capable of forming a continuous and adherent film on a support, especially on keratin materials, alone or in the presence of an auxiliary film-forming agent.

Among the film-forming polymers usable in the composition of the present invention, there may be mentioned synthetic polymers, of the radical or polycondensate type, naturally occurring polymers and mixtures thereof. As the film-forming polymer, there may be mentioned, in particular, acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulosic polymers, such as nitrocellulose.

The polymer may be associated with one or more auxiliary film forming agents. Such a film-forming agent can be selected from all the compounds known to those skilled in the art as capable of fulfilling the function sought, and especially between the plasticizing agents and the coalescing agents.

The composition according to the invention may include at least one wax. Wax within the meaning of the present invention means a lipophilic compound, solid at room temperature (25 ° C), with reversible solid / liquid state change, which has a melting point greater than or equal to 30 ° C and which It can go up to 120 ° C.

The melting point of the wax can be measured with a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the designation DSC 30 by METLER.

The waxes can be hydrocarbon, fluorinated and / or silicone and be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting temperature of greater than 25 ° C and better than 45 ° C. As usable wax in the composition of the invention, there may be mentioned beeswax, Carnauba or Candelilla wax, paraffin, microcrystalline waxes, ceresin or ozocerite, synthetic waxes, such as polyethylene or Fischer Tropsch, and silicone waxes, such as alkyl- or alkoxy-dimethicones of 16 to 45 carbon atoms.

The nature and quantity of solid fatty bodies depend on the mechanical properties and the desired textures. By way of indication, the composition may contain from 0 to 50% by weight of waxes with respect to the total weight of the composition and better from 1 to 30% by weight.

The composition according to the invention may also include one or more dye materials selected from water-soluble dyes and powdery dyes, such as pigments, mother of pearl and sequins well known to those skilled in the art. The coloring materials may be present in the composition in a content of 0.01% to 50% by weight with respect to the weight of the composition, preferably 0.01% to 30% by weight.

By pigments, we must understand particles of any shape, white or colored, mineral or organic, insoluble in the physiological environment, intended to give color to the composition.

By mother of pearl, it is necessary to understand iridescent particles of any form, especially produced by some mollusks in their shell, or synthesized.

The pigments can be white or colored, mineral and / or organic. It is possible to mention, among the mineral pigments, titanium dioxide, possibly surface treated, zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, and metal powders, such as aluminum powder and copper powder. Among the organic pigments, carbon black, D&C type pigments and cochineal, barium, strontium, calcium or aluminum carmine lacquers can be mentioned.

It is also possible to cite the pigments with effect, such as particles carrying an organic or mineral substrate, natural or synthetic, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas said substrate being covered or not with metal substances, such as aluminum, gold, silver, platinum, copper or bronze, or metal oxides, such as titanium dioxide, iron oxide and chromium oxide , and their mixtures.

Pearlescent pigments can be selected from white pearlescent pigments, such as titanium coated mica or bismuth oxychloride, pearly colored pigments, such as titanium mica coated with iron oxides, titanium mica specially coated with ferric blue or chromium oxide and titanium mica coated with an organic pigment of the aforementioned type, as well as pearly pigments based on bismuth oxychloride. Interferential pigments, especially liquid crystals, can also be used

or multilayer.

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

The composition according to the invention may further include one or more fillers, especially in a content of 0.01% to 50% by weight with respect to the total weight of the composition, preferably 0.01% to 30% by weight. By charges, particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition must be understood regardless of the temperature at which the composition is manufactured. These charges are especially useful for modifying the rheology or texture of the composition.

The charges can be mineral or organic and in any way, platelet, spherical or oblong, whatever the crystallographic form (for example, laminar, cubic, hexagonal, orthorhombic, etc.). It is possible to mention talcum, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol®, from the Atochem house), poly--alanine and polyethylene, tetrafluoroethylene polymer powders ( Teflon®), lauroillisin, starch, boron nitride, hollow polymer microspheres, such as polyvinylidene / acrylonitrile chloride, such as Expancel® (Nobel Industrie) and acrylic acid copolymers (Polytrap®, from Dow Corning company) and silicone resin microbeads (Tospearls®, from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydrocarbonate, hydroxyapatite, hollow silica microspheres (Silica Beads®, from Maprecos), glass or ceramic microcapsules and metal soaps derived from carboxylic organic acids of 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, for example the est zinc, magnesium or lithium earate, zinc laurate and magnesium myristate.

The composition according to the invention can be presented especially in the form of a suspension, dispersion, solution, gel, emulsion, especially oil-in-water (Ac / Ag) or water-in-oil (Ag / Ac) emulsion ) or multiple (Ag / Ac / Ag or polyol / Ac / Ag or Ac / Ag / Ac), cream, paste, foam, vesicle dispersion, especially ionic lipids or not, biphasic or multiphasic lotion, of spray, of powder or of paste, especially of flexible paste (especially of paste with a dynamic viscosity at 25 ° C of the order of 0.1 to 40 Pa.s under a shear rate of 200 s-1, after 10 minutes of measurement in conical / flat geometry). The composition can be anhydrous; for example, it can be an anhydrous flexible paste

The person skilled in the art may select the appropriate galenic form, as well as its method of preparation, based on their general knowledge, taking into account, on the one hand, the nature of the constituents used, especially their solubility in the support, and by another the application contemplated for the composition.

The composition according to the invention can be a make-up composition, such as complexion products (make-up bases), blushes or eye shadows, liquid lipstick carmines, dark circles corrective products, mascaras, profilers eyes, eyebrow makeup products, nail products, such as nail polishes, body makeup products or hair makeup products (hairspray or hairspray).

The composition according to the invention can also be a body and face skin care product, especially a sunscreen or skin coloring product (such as a self tanner).

The present invention also has as its object a cosmetic set consisting of:

-

 a container that delimits at least one compartment, said container being closed by a closure element, and

-

 a composition as described above arranged inside said compartment.

The container can have any suitable shape. It can be especially shaped like a bottle, a tube, a canister, a case, a box, a bag or a briefcase.

The closure element may be in the form of a removable cap, a cover, an operculum, a tear strip or a capsule, especially of the type that carries a body fixed to the container and an articulated cap on the body. It can also be in the form of an element that ensures the selective closure of the container, especially a pump, a valve or a flip lid.

The container may be associated with an applicator, especially in the form of a brush that carries an arrangement of hairs maintained by a braided thread. Such braided brush is especially described in US Pat.

4,887,622. It can also be in the form of a comb that carries a plurality of application elements, especially obtained by molding. Such combs are described, for example, in FR 2,796,529. The applicator may be in the form of a brush, as described, for example, in FR 2,722,380. The applicator may be in the form of a foam or elastomer block, a marker or a spatula. The applicator can be free (borlite or sponge) or integral with a rod carried by the closure element, as described, for example, in US Pat. 5,492,426. The applicator may be integral with the container, as described, for example, in patent FR 2,761,959.

The product can be contained directly in the container or indirectly. By way of example, the product may be arranged on an impregnated support, especially in the form of a wipe or buffer, and disposed (as a unit or as a plurality) in a box or in a sachet. Such support incorporating the product is described, for example, in the application WO01 / 03538.

The closure element can be attached to the container by screwing. Alternatively, the coupling between the closure element and the container is carried out other than by screwing, especially by a mechanism

5

10

fifteen

twenty

25

30

35

40

bayonet, by ratchet, pressure, welding or gluing, or by magnetic attraction. By "ratchet", it is understood, in particular, any system that involves the passage of a weatherstrip or a cord of matter by elastic deformation of a portion, especially of the closure element, and then by return to the position of non-tension elastically of said portion after the passage of the weatherstrip or cord.

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

Alternatively, the container is made of non-thermoplastic material, especially glass or metal (or alloy). The container can be rigid walls or deformable walls, especially in the form of a tube

or from a tube jar.

The container may include means intended to cause or facilitate the distribution of the composition. By way of example, the container can be of deformable walls to cause the composition to exit in response to an overpressure inside the container, whose overpressure is caused by elastic (or non-elastic) crushing of the walls of the container.

The container may consist of a briefcase with a bottom that delimits at least one housing containing the composition and a lid, especially articulated on the bottom and suitable for covering at least part of said bottom. Such a briefcase is described, for example, in the application WO 03/018423 or in the patent FR 2,791,042.

The container may be equipped with a drainer arranged in proximity to the opening of the container. Such a drainer allows the applicator to drain and eventually the rod from which it can be integral. Such a drainer is described, for example, in FR 2,792,618.

The composition may be at atmospheric pressure inside the vessel (at room temperature) or pressurized, especially by means of a propellant gas

(aerosol). In the latter case, the container is equipped with a valve (of the type used for aerosols).

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

The following examples illustrate in a non-limiting manner the compositions according to the invention.

Examples 8 to 12: Lip Carmine

Example

 8 9 10 eleven 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

Hydrogenated Polyisobutene

2.1  2.1  2.1  2.1 2.1

Octyldodecanol

 0.9 0.9 0.9 0.9 0.9

Phenyltrimethicone (DC 556, 20 cSt, Dow Corning)

2.1  2.1  2.1  2.1 2.1

Copolymer of vinylpyrrolidone / 1-eicosen (Antaron V-220,

1.2  1.2  1.2  1.2 1.2

ISP)

Pigments

3 3 3 3 3

Operating mode

one.

 A pigmentary crushing of the pigments in the oil phase is performed by making three passes of the mixture through the three-cylinder crusher.

2.

 The crushing necessary for the composition and the other ingredients are weighed in a beaker.

3.

 The mixture is placed under Rayneri stirring for 45 min. at room temperature.

Four.

 The formula is poured into kettles tight to isododecane.

20 5

Brightness measurement

1. With the help of a mechanical applicator, a film is produced for each composition whose thickness

Wet is 50 ym and a film whose wet thickness is 150 m. Deposits are made on 10 a contrast card of LENETA brand and reference FORM 1A PENOPAC.

2.

 Allow to dry for 24 hours at a regulated temperature of 30 ° C.

3.

 The brightness measurements are made with the BYK GARDNER micro-tri-gloss brillometer at a measuring angle of 20º and a measuring angle of 60º for each of the two series of tanks.

15 The results obtained from in vitro brightness are shown in the following table:

150 m tank

Angle

Deposit Example Half (%) Typical deviation

20º angle

Deposit of 150 ósitom Example 8 54.2 2.0

Example 9

41.0 3.5

60º angle

Deposit of 150 ósitom Example 8 75.7 0.8

Example 9

73.6 1.6

20 Deposit of 50 ósitom

Angle

Deposit Example Half (%) Typical deviation

20º angle

50 m deposit Example 8 47.6 1.2

Example 9

42.6 5.2

60º angle

50 m deposit Example 8 69.3 0.7

Example 9

74.8 1.0

The average brightness obtained is greater than 40 over 100 for a measuring angle of 20 ° and a thickness of 50 m or 150 25 m.

The average brightness obtained is greater than 65 over 100 for a measuring angle of 60 ° and a thickness of 50 m. The average brightness obtained is greater than 70 over 100 for a measuring angle of 60 ° and a thickness of 150 m.

30 Example 13: Nail Polish

Polymer of example 1 23.8 g in MA Butyl acetate 24.99 g Isopropanol 10.71 g

35 Hexylene Glycol 2.5 g DC RED 7 Lake 1 g Hectorite modified with stearyl dimethylbenzyl ammonium chloride (Elementis Bentone® 27V) 1.3 g

Example 14: Nail Polish

Polymer of Example 5

 23.8 g in MA

Acetate of butilo

 24.99 g

5

Isopropanol  10.71 g

Hexylene glycol

 2.5 g

DC RED 7 Lake

 1 g

Hectorite modified with stearyl dimethylbenzyl ammonium chloride

(Elementis Bentone® 27V)

 1.3 g

10

Ethyl acetate  csp 100g

Claims (68)

1. Liquid cosmetic composition containing a cosmetically acceptable organic liquid medium and a polymer non-elastomeric film-forming sequential ethylenic, whose sequenced polymer contains first and second sequences linked together by an intermediate segment, which it is a statistical polymer that includes at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence, the first polymer sequence being selected from:

-

 a) a sequence that has a Tg greater than or equal to 40 ° C,

-

 b) a sequence that has a Tg less than or equal to 20 ° C and

-

 c) a sequence having a Tg between 20 and 40 ° C, and

the second sequence being selected in a category a), b) or c) different from the first sequence, and whose sequenced polymer has a polydispersity index I greater than 2.8, said polymer being such that, when it is in sufficient quantity in the composition, the average brightness at 20 ° of a Deposit of said composition, once extended on a support, is greater than or equal to 30 over 100. 2. Liquid cosmetic composition containing a cosmetically acceptable organic liquid medium and a polymer ethogenic sequential film-free linear styrene unit, whose sequenced polymer contains first and second sequences linked together by an intermediate segment, which it is a statistical polymer that includes at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence, the first polymer sequence being selected from:

-

 a) a sequence that has a Tg greater than or equal to 40 ° C,

-

 b) a sequence that has a Tg less than or equal to 20 ° C and

-

 c) a sequence having a Tg between 20 and 40 ° C, and

the second sequence being selected in a category a), b) or c) different from the first sequence, and whose sequenced polymer has a polydispersity index I greater than 2.8, the polymer being such that, when it is in sufficient quantity in the composition, the average brightness at 20 ° of a deposit of said composition, once extended on a support, is greater than or equal to 30 over 100.

3.

 Cosmetic composition according to claim 1 or 2, characterized in that the sequenced polymer is an ethylenic polymer from aliphatic ethylenic monomers having a carbon-carbon double bond and at least one ester group -COO- or amide -CON-.

Four.

 Cosmetic composition according to one of the preceding claims, characterized in that it is not the soluble polymer at an active matter content of at least 1% by weight in water or in a mixture of water and linear or branched lower monoalcohols of 2 to 5 atoms carbon, without pH modification, at room temperature (25 ° C).

5.

 Composition according to the preceding claim, characterized in that the first and second sequences are joined together by an intermediate segment having a glass transition temperature comprised between the glass transition temperatures of the first and second sequences.

6.

 Cosmetic composition according to any one of the preceding claims, characterized by containing the first and second incompatible sequenced polymer in said organic liquid medium.

7.

 Composition according to any one of the preceding claims, characterized in that the sequence having a Tg greater than or equal to 40 ° C proceeds in all or part of one or more monomers that are such that the homopolymer prepared from these monomers has a temperature glass transition greater than or equal to 40 ° C.

8.

 Composition according to the preceding claim, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between the following monomers:

-

 methacrylates of formula CH2 = C (CH3) -COOR1, where R1 represents an unsubstituted, linear or branched alkyl group of 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R1 represents a C4 to C12 cycloalkyl group;

-

 acrylates of formula CH2 = CH-COOR2, where R2 represents a C4 to C12 cycloalkyl group, such as isobornyl acrylate, or a tert group

butyl;

-

 the (meth) acrylamides of the formula:

image 1 5 where R7 and R8, identical or different, each represent a hydrogen atom or an alkyl group of 1 to 12 linear or branched carbon atoms, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, and R 'designates H or methyl; -and their mixtures. 10 9. Composition according to claim 7 or 9, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between methyl methacrylate, isobutyl (meth) acrylate, (meth) acrylate of isobornyl and mixtures thereof. Composition according to any one of claims 1 to 6, characterized in that the sequence having a Tg less than or equal to 20 ° C proceeds in all or part of one or more monomers that are such that the homopolymer prepared from These monomers have a glass transition temperature less than or equal to 20 ° C. 11. Composition according to the preceding claim, characterized by selecting the monomers whose The corresponding homopolymer has a glass transition temperature of less than or equal to 20 ° C between the following monomers: - acrylates of formula CH2 = CHCOOR3, R3 representing a C1 to C12 unsubstituted alkyl group, linear or branched, with the exception of the tert group 25 butyl, where one or more heteroatoms selected from O, N and S are eventually intercalated; - methacrylates of formula CH2 = C (CH3) -COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group, where they are located possibly interleaved one or more heteroatoms selected from 0, N and S; 30 - the vinyl esters of the formula R5-CO-O-CH = CH2, where R5 represents a linear or branched C4 to C12 alkyl group;

-

 C4 to C12 vinyl and alkyl ethers;

-

 N-C4 to C12 alkyl acrylamides, such as N-octylacrylamide;

-and their mixtures. 35 12. Composition according to claim 10 or 11, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20 ° C between the alkyl acrylates whose alkyl chain has 1 to 10 carbon atoms, a exception of the tert-butyl group. Composition according to any one of claims 1 to 6, characterized in that the sequence having a Tg comprised between 20 and 40 ° C proceeds in all or part of one or more monomers such as the homopolymer prepared from these Monomers have a glass transition temperature between 20 and 40 ° C. Composition according to the preceding claim, characterized in that the sequence having a Tg between 20 and 40 ° C proceeds in all or part of monomers such that the corresponding homopolymer has a Tg greater than or equal to 40 ° C and of monomers such that the corresponding homopolymer has a Tg less than or equal to 20 ° C. Composition according to claim 13 or 14, characterized in that the sequence having a Tg comprised between 20 and 40 ° C proceeds in all or part of monomers selected from methyl methacrylate, acrylate and isobornyl methacrylate, the butyl acrylate, 2-ethylhexyl acrylate and mixtures thereof. 16. Composition according to any one of claims 1 to 12, characterized by including a polymer 55 sequenced comprising at least a first sequence and at least a second sequence, the first sequence having a glass transition temperature (Tg) greater than or equal to 40 ° C and the second sequence having a glass transition temperature less than or equal to 20 ° C. 5 10 fifteen twenty 25 30 35 40 Four. Five fifty 55

17.

 Composition according to the preceding claim, characterized in that the first sequence proceeds in all or part of one or more monomers such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C.

18.

 Composition according to the preceding claim, characterized in that the first sequence is a copolymer from monomers such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C.

19.

 Composition according to claim 17 or 18, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between the following monomers:

-

 methacrylates of formula CH2 = C (CH3) -COOR1, where R1 represents an unsubstituted, linear or branched alkyl group of 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R1 represents a C4 to C12 cycloalkyl group;

-

 acrylates of formula CH2 = CH-COOR2, wherein R2 represents a C4 to C12 cycloalkyl group, such as isobornyl acrylate, or a tert-butyl group;

-

 the (meth) acrylamides of the formula:

-and their mixtures.

twenty.

 Composition according to one of claims 17 to 19, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between methyl methacrylate, isobutyl methacrylate, isobornyl (meth) acrylate and their mixtures

twenty-one.

 Composition according to one of claims 16 to 19, characterized in that the proportion of the first sequence ranges from 20 to 90% by weight of the polymer, better from 30 to 80% and even better from 50 to 70%.

22

 Composition according to one of claims 16 to 21, characterized in that the second sequence proceeds in whole or in part of one or more monomers such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C.

2. 3.

 Composition according to one of claims 16 to 22, characterized in that the second sequence is a homopolymer from monomers such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C.

24.

 Composition according to claim 22 or 23, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature of less than or equal to 20 ° C between the following monomers:

-

 acrylates of formula CH2 = CHCOOR3, R3 representing a C1 to C12 unsubstituted alkyl group, linear or branched, with the exception of the tert-butyl group, where one or more heteroatoms selected from O are eventually intercalated, N yS;

-

 methacrylates of formula CH2 = C (CH3) -COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group, where they are located possibly interleaved one or more heteroatoms selected from 0, N and S;

-

 vinyl esters of formula R5-CO-O-CH = CH2, where R5 represents a linear or branched C4 to C12 alkyl group;

-

 C4 to C12 vinyl and alkyl ethers;

-

 N-C4 to C12 alkyl acrylamides, such as N-octylacrylamide;

-and their mixtures.

25.

 Composition according to one of claims 22 to 24, characterized by selecting the monomers whose

image2 corresponding homopolymer has a glass transition temperature less than or equal to 20 ° C between the alkyl acrylates whose alkyl chain has 1 to 10 carbon atoms, with the exception of the tert-butyl group.

26.

 Composition according to one of claims 16 to 25, characterized in that the proportion of the second sequence having a Tg of less than or equal to 20 ° C is from 5 to 75% by weight of the polymer, better from 15 to 50% and even better from 25 to 45%.

27.

Composition according to one of claims 1 to 12, characterized in that it includes a sequenced polymer comprising at least a first sequence and at least a second sequence, the first sequence having a glass transition temperature (Tg) between 20 and 40 ° C and the second sequence having a glass transition temperature less than or equal to 20 ° C or a glass transition temperature greater than or equal to 40 ° C.

28.

 Composition according to the preceding claim, characterized in that the first sequence having a Tg between 20 and 40 ° C proceeds in all or part of one or more monomers such that the homopolymer prepared from these monomers has a glass transition temperature between 20 and 40 ° C.

10 fifteen Composition according to claim 27 or 28, characterized in that the first sequence having a Tg comprised between 20 and 40 ° C is a copolymer from monomers such that the corresponding homopolymer has a Tg greater than or equal to 40 ° C and of monomers such that the corresponding homopolymer has a Tg less than or equal to 20 ° C. Composition according to one of claims 27 to 29, characterized in that the first sequence having a Tg comprised between 20 and 40 ° C of monomers selected from methyl methacrylate, acrylate and isobornyl methacrylate, acrylate of butyl, 2-ethylhexyl acrylate and mixtures thereof. 31. Composition according to one of claims 27 to 30, characterized by the proportion of the first 30 sequence having a Tg comprised between 20 and 40 ° C from 10 to 85% by weight of the polymer, better from 30 to 80% and even better from 50 to 70%. 32. Composition according to any one of claims 27 to 31, characterized in that the second sequence has a Tg greater than or equal to 40 ° C and proceeds in all or part of one or more monomers such that the The homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. 33. Composition according to any one of claims 27 to 32, characterized in that the second sequence has a Tg greater than or equal to 40 ° C and is a homopolymer from monomers such that the Homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. 34. Composition according to one of claims 32 or 33, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between the following 45 monomers: - methacrylates of formula CH2 = C (CH3) -COOR1, where R1 represents an unsubstituted, linear or branched alkyl group of 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, or R1 represents a C4 to C12 cycloalkyl group; 50 - acrylates of formula CH2 = CH-COOR2, where R2 represents a C4 to C12 cycloalkyl group, such as isobornyl acrylate, or a tert-butyl group; - (meth) acrylamides of the formula: isooctyl or isononyl; or R7 represents H and R8 represents a 1,1-dimethyl-3-oxobutyl group, and R 'designates H or methyl; image3 -and their mixtures.

35

 Composition according to one of claims 32 to 35, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between methyl methacrylate, isobutyl methacrylate, isobornyl (meth) acrylate and their mixtures

36.

 Composition according to one of claims 32 to 35, characterized by the proportion of the second sequence having a Tg greater than or equal to 40 ° C of 10 to 85%, preferably 20 to 70% and better than 30 to 70% in polymer weight

37.

 Composition according to one of claims 27 to 31, characterized in that the second sequence has a Tg less than or equal to 20 ° C and proceeds in all or part of one or more monomers such that the homopolymer prepared from these monomers has a temperature glass transition less than or equal to 20 ° C.

38.

 Composition according to one of claims 27 to 31, characterized in that the second sequence has a Tg less than or equal to 20 ° C and is a homopolymer from monomers such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C

39.

 Composition according to claim 37 or 38, characterized in that the monomers are selected whose corresponding homopolymer has a glass transition temperature of less than or equal to 20 ° C between the following monomers:

-

 acrylates of formula CH2 = CHCOOR3, R3 representing a C1 to C12 unsubstituted alkyl group, linear or branched, with the exception of the tert-butyl group, where one or more heteroatoms selected from O are eventually intercalated, N yS;

-

 methacrylates of formula CH2 = C (CH3) -COOR4, R4 representing a linear or branched C6 to C12 unsubstituted alkyl group, where they are located possibly interleaved one or more heteroatoms selected from 0, N and S;

-

 vinyl esters of formula R5-CO-O-CH = CH2, where R5 represents a linear or branched C4 to C12 alkyl group;

-

 C4 to C12 vinyl and alkyl ethers;

-

 N-C4 to C12 alkyl acrylamides, such as N-octylacrylamide;

-and their mixtures.

40

 Composition according to one of claims 37 to 39, characterized by selecting the monomers whose homopolymers have glass transition temperatures of less than or equal to 20 ° C between the alkyl acrylates whose alkyl chain has 1 to 10 carbon atoms, with the exception of tert-butyl group.

41.

 Composition according to one of claims 37 to 40, characterized in that the proportion of the sequence having a glass transition temperature of 20 to 85% by weight of the polymer, better than 20 to 70% and still 20% better than 20 to 50%.

42

 Cosmetic composition according to any one of the preceding claims, characterized in that the first sequence and / or the second sequence includes at least one additional monomer.

43

 Composition according to the preceding claim, characterized by selecting the additional monomer among the hydrophilic monomers, the monomers with ethylenic unsaturation that include one or more silicon atoms and mixtures thereof.

44.

 Composition according to claim 42 or 43, characterized by selecting the additional monomer from:

a) hydrophilic monomers, such as:

-

 monomers with ethylenic unsaturation (s) that have at least one carboxylic acid function or

sulfonic acid, such as: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinyl phosphoric acid and its salts;

-

 monomers with ethylenic unsaturation (s) that have at least one tertiary amine function, such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and its salts;

-

 methacrylates of formula CH2 = C (CH3) -COOR6, where R6 represents a linear or branched alkyl group of 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents selected from the hydroxyl groups (such as 2-hydroxypropyl methacrylate and 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I and F), such as trifluoroethyl methacrylate;

-

 methacrylates of formula CH2 = C (CH3) -COOR9, R9 representing a linear or branched C6 to C12 alkyl group, where one or more heteroatoms selected from 0, N and S are intercalated, said alkyl group being substituted by one or more substituents selected from the hydroxyl groups and the halogen atoms (Cl, Br, I and F);

-

 acrylates of formula CH2 = CHCOOR10, R10 representing a C1 to C12 alkyl group, linear or branched, substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate, or R10 represents a (C1-C12) -O-POE (polyoxyethylene) alkyl with repeat of the oxyethylene unit 5 to 30 times, for example methoxy-POE, or R10 represents a polyoxyethylene group having 5 to 30 units of ethylene oxide; Y

b) ethylenically unsaturated monomers that include one or more silicon atoms, such as methacryloxypropyltrimethoxysilane and methacryloxypropyltris (trimethylsiloxy) silane; -and their mixtures.

Four. Five.

 Composition according to one of claims 42 or 43, characterized in that each of the first and second sequences includes at least one additional monomer selected from acrylic acid, (meth) acrylic acid, trifluoroethyl methacrylate and mixtures thereof.

46.

 Composition according to one of claims 42 or 43, characterized in that each of the first and second sequences includes at least one monomer selected from the esters of (meth) acrylic acid and possibly at least one additional monomer such as (meth) acrylic acid , and their mixtures.

47

 Composition according to one of claims 42 or 43, characterized in that each one of the first and second sequences comes in its entirety from at least one monomer selected from the esters of (meth) acrylic acid and possibly from at least one additional monomer such as the (meth) acrylic acid, and mixtures thereof.

48.

 Composition according to one of claims 42 to 47, characterized in that it represents the additional monomer (s) from 1 to 30% by weight of the total weight of the first and / or second sequences.

49.

 Composition according to any one of the preceding claims, characterized in that the difference between the glass transition temperatures (Tg) of the first and second sequences is greater than 10 ° C, better than 20 ° C, preferably greater than 30 ° C and better above 40 ° C.

fifty.

 Composition according to any one of the preceding claims, characterized by having a polydispersity index between 2.8 and 6.

51.

Composition according to one of the preceding claims, characterized in that the sequenced polymer has a weight average mass (Mw) of less than or equal to 300,000.

52

 Composition according to the preceding claim, characterized in that the weight average mass (Mw) ranges from 35,000 to 200,000, and better from 45,000 to 150,000.

53.

 Composition according to the preceding claim, characterized in that the number average mass (Mn) is less than or equal to 70,000.

54

 Composition according to one of claims 51 to 53, whose number average mass (Mn) ranges from 10,000 to 60,000, and better from 12,000 to 50,000.

55.

 Composition according to one of the preceding claims, characterized in that the average brightness of the composition is measured at 20 ° greater than or equal to 30, better 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 over 100, better still 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 over 100

56.

 Composition according to one of the preceding claims, characterized in that it is the average brightness of the composition, once extended on a support, measured at 60 °, greater than or equal to 50, better still greater than or equal to

60, better still greater than or equal to 65, better still greater than 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 over 100

57.

 Composition according to one of the preceding claims, characterized in that it is the average brightness of the composition measured at 20 ° greater than or equal to 35, preferably 40, 45 or 50 over 100, and / or the brightness of the composition measured at 60 ° higher or equal to 65, 70 or 75 over 100.

58.

 Composition according to one of the preceding claims, characterized in that the brightness of the composition is measured at 20 ° greater than or equal to 60, preferably 65, 70 or 75 over 100, and / or is the brightness of the composition measured at 60 ° higher or equal to 80, 85 or 90 over 100.

59.

 Composition according to one of the preceding claims, characterized in that it includes from 0.1 to 60% by weight in polymer active material, preferably from 5% to 50% by weight and preferably even from 10 to 40% in weight.

60

 Cosmetic composition according to any one of the preceding claims, characterized in that it also includes one or more dye materials selected from water-soluble dyes and powdery dyes, such as pigments, mother of pearl and sequins.

61.

 Cosmetic composition according to any one of the preceding claims, characterized in that it is in the form of a suspension, dispersion, solution, gel, emulsion, especially oil-in-water (Ac / Ag) emulsion or water-in- oil (Ag / Ac) or multiple (Ag / Ac / Ag or polyol / Ac / Ag or Ac / Ag / Ac), cream, foam, vesicle dispersion especially ionic or non-ionic lipids, biphasic or multiphasic lotion or pasta, especially flexible pasta or anhydrous pasta.

62

 Cosmetic composition according to any one of the preceding claims, characterized in that it is presented in an anhydrous form.

63.

 Cosmetic composition according to any one of the preceding claims, characterized in that it is a make-up or care composition of keratin materials.

64.

 Cosmetic composition according to one of the preceding claims, characterized in that it is a lip makeup product.

65

 Cosmetic composition according to one of the preceding claims, characterized in that it is an eye makeup product.

66.

 Cosmetic composition according to one of the preceding claims, characterized in that it is a nail makeup product.

67.

 Cosmetic set consisting of:

a) a container that delimits at least one compartment, said container being closed by a closure element, and b) a composition disposed within said compartment, the composition being in accordance with any one of the preceding claims.

68.

 Cosmetic assembly according to the preceding claim, characterized in that the container is formed, at least in part, in at least one thermoplastic material.

69.

 Cosmetic assembly according to claim 67, characterized in that the container is formed, at least in part, in at least one non-thermoplastic material, especially in glass or metal.

70.

 Assembly according to any one of claims 67 to 69, characterized in that the closure element is in the closed position of the container, screwed onto the container.

71.

 Assembly according to any one of claims 67 to 69, characterized in that the closure element is in the closed position of the container, coupled to the container other than by screwing, especially by ratchet, glueing or welding.

72.

 Assembly according to any one of claims 67 to 71, characterized in that the composition is sensitive to atmospheric pressure inside the compartment.

73

 Assembly according to any one of claims 67 to 71, characterized in that the composition is

pressurized inside the container.

74.

 Cosmetic method of makeup or care of keratin materials consisting of the application on keratin materials of a cosmetic composition according to one of claims 1 to 66.