ES2355374T3 - COMPOSITION THAT INCLUDES A SEQUENCED POLYMER AND A FILMOGEN AGENT. - Google Patents

Abstract

Cosmetic composition containing an organic liquid medium, at least one non-elastomeric film-forming linear ethylenic sequencing polymer and at least one other soluble or dispersible film-forming agent in said organic liquid medium, whose sequenced polymer contains first and second sequences joined together by a statistical intermediate segment which 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 that has a Tg of less than or equal to 20 ° C and - c) a sequence that has 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 having said polymer sequenced a polydispersity index I greater than 2.8.

Description

Composition comprising a polymer sequencing and a film forming agent.

The present invention relates to a cosmetic makeup or skin care composition, including the scalp, both of the face and body human, from the lips or the faneras of human beings, such as the hair, eyelashes, eyebrows or nails, which includes a cosmetically acceptable medium containing a sequenced polymer film forming associated with another film forming agent.

The composition may be a free powder or compacted, a makeup base, a blusher or a shade of eyes, a concealer product, a lipstick, a lip balm, lip gloss, lipstick or eyes, a mascara, an eyeliner, a nail polish or also a product of body makeup or skin coloring.

The known compositions have a bad persistence over time, and in particular a bad persistence of color This bad persistence is characterized by a color modification (turn, whiteness) usually at consequence of an interaction with sebum and / or sweat segregated by the skin in the case of a makeup base and a makeup, or an interaction with saliva in the case of the bars of lips. This forces the user to re-make up very frequently, which can be a waste of time.

An improvement of the persistence, in particular the persistence of the bars of lips, associating a volatile oil with a film-forming polymer, such as silicone resins. However, the properties of Persistence obtained are still lower than expected by the consumers.

A cosmetic product is still needed that lead to a deposit on keratin materials, in Particularly a makeup, of good persistence.

The composition of the invention can in particular constitute a body makeup product, of the lips or the faces of humans in particular with properties of care and / or non-therapeutic treatment. It constitutes especially a lipstick or lip gloss, a blusher or an eye shadow, a tattoo product, a mascara, a eye liner, a nail polish, a tan product artificial skin or a coloring or care product hair.

Surprisingly, the inventors discovered which, associating a particular sequenced polymer with an agent known film forming, cosmetic compositions are obtained which give place to deposits on persistence keratin materials superior to classical compositions containing film-forming agents.

More specifically, the invention aims at a cosmetic composition containing an organic liquid medium, by at least one film-forming linear sequential ethylene polymer and at least another film forming agent,

said first sequenced polymer containing and second sequences linked together by an intermediate segment statistic that includes at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence,

the first sequence of the polymer between:

- a) a sequence that has a higher Tg or equal to 40 ° C,

- b) a sequence that has a lower Tg or equal to 20ºC and

- c) a sequence that has a Tg comprised between 20 and 40 ° C, and

the second sequence being selected in a category a), b) or c) different from the first sequence,

and said sequenced polymer having an index of polydispersity I greater than 2.8.

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In particular, the invention aims at a cosmetic composition containing an organic liquid medium, at less a film-forming linear sequential ethylenic polymer as it is described above and at least one other soluble film forming agent in the organic liquid medium.

The invention has as another object a cosmetic composition containing an organic liquid medium, at less a film-forming linear sequential ethylenic polymer as it is described above and at least one other film forming agent water soluble.

The invention has as yet another object a cosmetic composition containing an organic liquid medium, at less a film-forming linear sequential ethylenic polymer as it is described above and at least one aqueous dispersion of film-forming polymer particles.

The invention has as yet another object a cosmetic composition containing an organic liquid medium, at less a film-forming linear sequential ethylenic polymer as it is described above and at least one non-aqueous dispersion of film-forming polymer particles.

U.S. Patent 6,153,206 describes a cosmetic composition that includes a polymer containing units repetitive that have a Tg of -10 to 75ºC and repetitive units which have a Tg of 76 to 120 ° C. It also describes polymers of blocks comprising polymethyl methacrylate blocks and polyisobutyl methacrylate blocks, and also polymers triblocks comprising polymethyl methacrylate blocks, polyisobutyl methacrylate blocks and methacrylate blocks of ethyl.

The linear sequenced ethylenic polymer Filmogen is advantageously non-elastomeric. Ethylene polymer Linear film sequencing is advantageously exempt from unit of styrene

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

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

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

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

In particular, in the case of a composition of lining of the eyelashes or mascara, such composition allows the obtaining, after application on the eyelashes, a film of makeup that has a good resistance, particularly when water, during baths or showers for example, to friction, especially from the fingers, and / or also to tears, to sweat or to tallow

The invention finally aims at the use of a film forming agent in a composition containing a sequenced polymer as described above to get a good texture composition, easy to apply and that gives place on the lips and / or the legs to a good deposit persistence.

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Sequenced polymer

The composition according to the present invention It contains at least one sequenced polymer. By polymer "sequenced" means a polymer comprising at least 2 different sequences, preferably at least 3 sequences different.

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

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

According to one embodiment, the polymer sequencing of the composition according to the invention is a polymer film forming By "film-forming" polymer, a polymer is understood suitable for training, alone or in the presence of an auxiliary agent film formation, a continuous and adherent film on a support, especially on keratin matters.

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

By "non-elastomeric polymer" is understood a polymer that, when subjected to a tension destined 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 the tension ceases.

Even more specifically, by "polymer not elastomeric "means a polymer that has a recovery snapshot R_ {i} <50% and delayed recovery R_ {2h} <70% after suffering an elongation of 30%. Preferably, R i is <30% and R 2h <50%.

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

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A spilling polymer film is prepared a solution of the polymer in a teflon matrix and then drying for 7 days in a controlled environment at 23 ± 5 ° C and 50 ± 10% relative humidity.

You then get a movie of approximately 100 µm thick in which samples are trimmed rectangular (for example with the punch) of a width of 15 mm and a length of 80 mm.

A request for traction with the aid of an apparatus marketed under the reference Zwick, in the same temperature and humidity conditions as for drying

The samples are stretched at a speed of 50 mm / min and the distance between the jaws is 50 mm, which corresponds to the initial length (l_ {0}) of the sample.

Instant recovery R_ {i} is determined as follows:

-

be stretch the sample by 30% (ε max), that is, in approximately 0.3 times its initial length (10);

-

be relaxes the tension by imposing a return speed equal to the tensile speed, that is, 50 mm / min, and the elongation is measured residual of the sample in percentage, after returning to tension null (\ varepsilon_ {i}).

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Instant recovery in% (R_ {i}) comes given by the following formula:

R_ {i} = ((\ varepsilon_ {max} - \ varepsilon_ {i}) / \ varepsilon_ {max}) x 100

To determine the delayed recovery, you measure the residual elongation of the sample in percentage (\ varepsilon_ {2h}) 2 hours after returning to tension void

Delayed recovery in% (R_ {2h}) comes given by the following formula:

R_ {2h} = ((\ varepsilon_ {max} - \ varepsilon_ {2h}) / \ varepsilon_ {max}) x 100

For purely indicative purposes, a polymer according to one embodiment of the invention has a recovery instantaneous R_ {i} of 10% and a delayed recovery R_ {2h} of 30%.

According to another embodiment, the polymer sequencing of the composition according to the invention has no unit of styrene By polymer free of styrene unit, a polymer having 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 (C 6 H 5) - CH 2 - or ii) of unit of substituted styrene, such as methylstyrene, chlorostyrene or chloromethylstyrene.

According to one embodiment, the polymer sequencing of the composition according to the invention comes from aliphatic ethylenic monomers. By aliphatic monomer, it is understood 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 atom of
nitrogen.

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

By "at least" a sequence, it is understood One or more sequences.

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

According to one embodiment, the polymer sequencing comprises at least a first sequence and at least one second sequence that have glass transition temperatures (Tg) different.

In this embodiment, the first and second sequences can be linked together by an intermediate segment which has a glass transition temperature between the glass transition temperatures of the first and second sequences

Preferably, the intermediate sequence proceeds essentially of constituent monomers of the first sequence and of the second sequence.

By "essentially", at least at 85%, preferably at least 90%, better at 95% and still 100% better.

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

By "sequences incompatible with each other," understands 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 organic liquid by weight contained in the organic liquid medium of the composition, to ambient temperature (25 ° C) and atmospheric pressure (10 5 Pa), for a polymer mixture content greater than or equal to 5% by weight with respect to the total weight of the mixture (polymers and liquid organic majority), understanding 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 have a mean molecular mass (weighted or numerical) equal to that of the sequenced polymer +/- fifteen%.

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In case the organic liquid medium it consists of 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.

In case the organic liquid medium it consists of a single organic liquid, the latter constitutes very obviously the majority liquid by weight.

By "organic liquid medium" is understood a medium containing at least one organic liquid, that is, at minus a liquid organic compound at room temperature (25 ° C) and atmospheric pressure (10 5 Pa). According to one embodiment, the majority liquid of the organic liquid medium is an oil (body fatty) volatile or nonvolatile. Preferably, the organic liquid is Cosmetically acceptable (tolerance, toxicology and touch acceptable). 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 liquid The majority of the organic liquid medium is the solvent or one of the polymerization solvents of the sequenced polymer, such as described below.

By polymerization solvent, a solvent or a mixture of solvents. The polymerization solvent it can be specially selected from ethyl acetate, the butyl acetate, alcohols such as isopropanol or ethanol, aliphatic alkanes such as isododecane and its mixtures 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 content in matter dry, typically greater than 10%, greater than 20% and preferably still greater than 30%, and preferably even greater than 45%, by weight with respect to the total weight of the composition, being easy to formulate.

Preferably, the sequenced polymer does not It contains silicon atoms in its skeleton. By "skeleton", it understands the polymer's main chain, as opposed to side chains pending.

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

According to one embodiment, the polymer sequencing has a polydispersity index I greater than 2.8.

Advantageously, the sequenced polymer used in the compositions according to the invention has an index of polydispersity I from 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 mass numerical mean Mn.

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

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

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

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

This means that each sequence can be constituted by a homopolymer or by a copolymer; East copolymer constituting the sequence can be in turn Statistical or alternate.

The indicated glass transition temperatures of the first and second sequences can be theoretical Tg determined from the theoretical Tg of the monomers constitutive 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 the Law of Fox:

one

where \ omega_ {i} is the fraction mass of monomer i in the sequence considered and where Tg_ {i} the glass transition temperature of the monomer homopolymer i.

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

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

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

"between ... and ..." an interval of values where the mentioned limits are excluded, and

"from ... to ..." and "going from ... to ..." a range of values where limits are included.

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

The sequence that has 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 from 50 ° C to 120 ° C and better greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C.

The sequence that has a Tg greater than or equal to 40 ° C can be a homopolymer or a copolymer.

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

In case this sequence is a homopolymer, comes from monomers such that homopolymers prepared from these monomers have temperatures of glass transition greater than or equal to 40 ° C. This first sequence can be a homopolymer, consisting of a single type of monomer (where the Tg of the corresponding homopolymer is higher or equal to 40 ° C).

In case the first sequence is a copolymer, this can proceed in whole or in part from one or more monomers, whose nature and concentration are selected from so that the Tg of the resulting copolymer is greater than or equal to 40 ° C The copolymer may for example include:

- 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 from 50 ° C to 120 ° C, and better greater than or equal to 60 ° C, for example from 60 ° C to 120 ° C, and

- monomers such that homopolymers prepared from these monomers have Tg below 40 ° C, selected from the monomers that have a Tg comprised between 20 and 40 ° C and / or monomers that have a Tg lower or equal at 20 ° C, for example a Tg of -100 to 20 ° C, preferably lower at 15ºC, especially from -80ºC to 15ºC, and better below 10ºC, for example from -50 ° C to 0 ° C, such as those described below.

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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 main monomers:

-

the formula methacrylates CH 2 = C (CH 3) - COOR 1,

where R_ {1} represents a linear or branched unsubstituted alkyl group of 1 at 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl, or R 1 represents a C 4 cycloalkyl group at C 12;

-

the formula acrylates CH 2 = CH-COOR 2,

where R2 represents a C4 to C12 cycloalkyl group, such as the isobornyl acrylate, or a group tert-butyl;

-

the (meth) acrylamides of the formula:

2

where R_ {7} and R 8, identical or different, each represents an atom of hydrogen or a linear or branched C 1 to C 12 alkyl group, such as an n-butyl group, t-butyl, isopropyl, isohexyl, isooctyl or isononyl; or R 7 represents H and R 8 represents a group 1,1-di-methyl-3-oxobutyl,

and R 'designates H or methyl. As an example of monomers, the N-Butylacrylamide, the N-t-butylacrylamide, the N-isopropyl-acrylamide, the N, N-dimethylacrylamide and the N, N-dibutyl acrylamide,

-

and their mixtures

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They are principal monomers particularly Preferred are methyl methacrylate, (meth) acrylate isobutyl, isobornyl (meth) acrylate and mixtures thereof.

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

The sequence that has 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 15ºC, especially from -80ºC to 15ºC, and better less than or equal to 10 ° C, for example from -50 ° C to 0 ° C.

The sequence that has a Tg less than or equal to 20 ° C can be a homopolymer or a copolymer.

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

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

In case the sequence has a Tg less than or equal to 20 ° C be a copolymer, this can proceed in all or part of one or more monomers, whose nature and concentration are selected so that the Tg of the copolymer resulting is less than or equal to 20 ° C.

It can for example include:

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

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

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

The monomers whose homopolymer has a Tg less than or equal to 20 ° C are preferably selected from among following monomers, or main monomers:

-

the acrylates of formula CH 2 = CHCOOR 3,

representing R 3 a linear C 1 to C 12 unsubstituted alkyl group or branched, except for the tert-butyl group, where one or more heteroatoms are eventually interspersed selected from O, N and S;

-

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

representing R 4 a linear C 6 to C 12 unsubstituted alkyl group or branched, where one or more are eventually interspersed heteroatoms selected from 0, N and S;

-

the formula vinyl esters R 5 -CO-O-CH = CH 2,

where R_ {5} represents a linear C4 to C12 alkyl group or branched;

-

the vinyl and C4 to C12 alkyl ethers;

-

the N-alkyl (C4 a C 12) acrylamides, such as the N-octylacrylamide,

-

and their mixtures

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The main monomers particularly preferred for the sequence that has a Tg less than or equal to 20 ° C are alkyl acrylates whose alkyl chain has 1 at 10 carbon atoms, except for the group tert-butyl, such as methyl acrylate, the isobutyl acrylate, 2-ethylhexyl acrylate and their mixtures

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

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

The sequence that has a Tg between 20 and 40 ° C can proceed in whole or in part of one or more monomers such that the homopolymer prepared from these monomers has a glass transition temperature comprised between 20 and 40 ° C.

The sequence that has a Tg between 20 and 40 ° C can proceed in whole or in part 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.

In case this sequence is a homopolymer, comes from monomers (or major 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 only one type of monomer (where the Tg of the corresponding homopolymer goes from 20 ° C to 40 ° C).

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

In case the sequence has a Tg between 20 and 40 ° C is a copolymer, it proceeds in all or in part of one or more monomers (or major monomers) whose nature and concentration are selected in such a way that the Tg of the resulting copolymer is between 20 and 40 ° C.

Advantageously, the sequence that has 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 from 40 ° C to 150 ° C, preferably greater than or equal to 50 ° C, per example of 50 to 120 ° C, and better 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 less than or equal to 20 ° C, for example a Tg from -100 to 20 ° C, preferably less than or equal to 15 ° C, especially from -80ºC to 15ºC, and better than or equal to 10ºC, by example from -50 ° C to 0 ° C, such as those described with anteriority,

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

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

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

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

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, acid esters (met) acrylic and mixtures thereof.

Each of the sequences can, however, contain in minority at least one constitutive monomer of the other sequence.

Thus, the first sequence can contain the minus a constituent monomer of the second sequence and at the inverse

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

The nature and quantity of this or these additional monomers are selected so that the sequence in which are found to have the glass transition temperature desired.

This additional monomer is, for example, selected from:

a) hydrophilic monomers, such as:

-

the monomers with ethylenic unsaturation (s) that have at least one carboxylic or sulfonic acid function, as per example:

the acid Acrylic, methacrylic acid, crotonic acid, anhydride maleic acid, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, acid vinyl phosphorus and salts thereof;

-

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

-

the formula methacrylates CH 2 = C (CH 3) - COOR 6,

where R_ {6} represents a linear or branched alkyl group of 1 to 4 atoms of carbon, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents selected from hydroxyl groups (such as methacrylate 2-hydroxypropyl and methacrylate 2-hydroxy-ethyl) and the atoms of halogens (Cl, Br, I and F), such as methacrylate trifluoroethyl;

-

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

representing R 9 a linear or branched C 6 to C 12 alkyl group, in which are eventually interspersed with one or more heteroatoms selected from 0, N and S, said group being alkyl substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F);

-

the acrylates of formula CH 2 = CHCOOR 10,

representing R 10 a linear or branched C 1 to C 12 alkyl group replaced by one or more substituents selected from among hydroxyl groups and halogen atoms (Cl, Br, I and F), such such as 2-hydroxypropyl acrylate and acrylate of 2-hydroxyethyl, or R 10 represents a (C 1 -C 12) alkyl - O-POE (polyoxyethylene) with repeating the oxyethylene unit from 5 to 30 times, for example methoxy-POE, or R 10 represents a polyoxyethylene group having 5 to 30 oxide units of ethylene;

b) monomers with ethylenic unsaturation that they have one or more silicon atoms, such as the methacryloxypropyltrimethoxysilane and the methacryloxypropyltris (trimethylsiloxy) silane;

-

and their mixtures

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They are additional monomers particularly preferred acrylic acid, methacrylic acid, methacrylate of trifluoroethyl and mixtures thereof.

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

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

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 represent generally an amount less than or equal to 30% by weight, per example of 1 to 30% by weight, preferably 5 to 20% by weight and preferably even 7 to 15% by weight of the total weight of the first and / or second sequences.

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

- a part of the solvent of polymerization in an adapted reactor and heated to reach the right temperature for polymerization (typically between 60 and 120 ° C),

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

- after a time T corresponding to a maximum conversion rate of 90%, monomers are introduced constitutive of the second sequence and the other part of the initiator,

- the mixture is allowed to react during a time T '(which goes from 3 to 6 h), after which the mix at room temperature, and

- the polymer in solution is obtained in the polymerization solvent.

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First mode of realization

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

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

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

Preferably, the proportion of the sequence which has 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 which has a Tg 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 it 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 acrylate of methyl, and

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

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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 70 to 100 ° C, which is a methacrylate copolymer methyl / 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 acrylate of methyl, and

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

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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 85 to 115 ° C, which is an acrylate copolymer of isobornyl / isobutyl methacrylate;

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

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

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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 85 to 115 ° C, which is an acrylate copolymer of isobornyl / methyl methacrylate;

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

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

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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 95 to 125 ° C, which is an acrylate copolymer of isobornyl isobornyl / methacrylate;

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

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

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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 85 to 115 ° C, which is a methacrylate copolymer of isobornyl / isobutyl methacrylate;

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

- an intermediate sequence, which is a copolymer isobornyl methacrylate / methacrylate statistic isobutyl / isobutyl acrylate.

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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 95 to 125 ° C, which is an acrylate copolymer of isobornyl isobornyl / methacrylate;

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

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

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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 60 to 90 ° C, which is an acrylate copolymer of isobornyl / isobutyl methacrylate;

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

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

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The following examples illustrate not limiting polymers corresponding to this first mode of realization.

The amounts are expressed in grams.

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Example 1 Preparation of a poly (acrylate polymer) isobornyl / methyl methacrylate / acrylate 2-ethylhexyl

100 g of isododecane are introduced into a reactor of 1 liter and then the temperature is increased to pass from the room temperature (25ºC) at 90ºC in 1 hour. They are then added to 90 ° C and in 1 hour, 150 g of isobornyl acrylate, 60 g of methyl 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.

They are then introduced into the previous mixture, always at 90ºC and in 30 minutes, 90 g of acrylate 2-ethylhexyl, 90 g of isododecane and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane.

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

A 50% solution in active matter is obtained of polymer in isododecane.

A polymer is obtained comprising a first poly (isobornyl acrylate / methacrylate acrylate) sequence or block of methyl) having a Tg of 100 ° 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 / methyl methacrylate / acrylate 2-ethylhexyl.

This polymer has a weight average mass of 76,500 and a numerical average mass of 22,000, that is, an index of polydispersity I of 3.48.

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Example 2 Preparation of a poly (acrylate polymer) isobornyl / isobornyl methacrylate / acrylate 2-ethyl-hexyl)

100 g of isododecane are introduced into a reactor of 1 liter and then the temperature is increased to pass from the room temperature (25ºC) at 90ºC in 1 hour. They are then added to 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.

They are then introduced into the previous mixture, always at 90ºC and in 30 minutes, 90 g of acrylate 2-ethylhexyl, 90 g of isododecane and 1.2 g of 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane.

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

A 50% solution in active matter is obtained of polymer in isododecane.

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A polymer is obtained comprising a first poly (isobornyl acrylate / methacrylate acrylate) sequence or block of isobornyl) 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 / acrylate 2-ethylhexyl.

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

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Example 3 Preparation of a poly (acrylate polymer) isobornyl / isobutyl methacrylate / isobutyl acrylate)

100 g of isododecane are introduced into a reactor of 1 liter and then the temperature is increased to pass from the room temperature (25ºC) at 90ºC 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® 141 from Akzo Nobel).

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

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

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

A 50% solution in active matter is obtained of polymer in isododecane.

A polymer is obtained comprising a first poly (isobornyl acrylate / methacrylate acrylate) sequence or block of isobutyl) 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 acrylate of isobornyl / isobutyl methacrylate / isobutyl acrylate.

This polymer has a weight average mass of 144,200 and a numerical average mass of 49,300, that is, an index of polydispersity I of 2.93.

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Second mode of realization

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

Preferably, the proportion of the first sequence that has a Tg between 20 and 40 ° C goes 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, is preferably present in a proportion of 10 to 85% by weight of the polymer, better than 20 to 70% and even better from 30 to 70%.

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

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

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

- an intermediate sequence that includes at least a monomer of methyl acrylate, methyl methacrylate, and

- an intermediate sequence that includes methyl methacrylate, at least one acrylic acid monomer and at less a methyl acrylate monomer.

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

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

- 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 copolymer statistic of isobornyl acrylate / methacrylate 2-ethylhexyl isobutyl / acrylate.

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

- a first sequence of Tg 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 a homopolymer of acrylate of isobornyl, and

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

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

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Film forming agent

The composition of the invention contains also at least one film forming agent, which can be a polymer Organic or mineral The film forming agent, when it is a polymer organic, it is not a linear sequencing polymer ethylenic as described above.

In one embodiment, the organic polymer film forming is at least one polymer selected from the group consisting of:

- soluble film-forming polymers in the medium organic liquid, in particular fat-soluble polymers when the Organic liquid medium includes at least one oil;

- the dispersible film-forming polymers in the organic solvent medium, in particular polymers in the form of non-aqueous dispersions of polymer particles, preferably dispersions in silicone or hydrocarbon oils; in a mode of embodiment, the non-aqueous polymer dispersions contain polymer particles stabilized on their surface by at least a stabilizing agent; these non-aqueous dispersions are often referred to as "NAD [non-aqueous dispersions] ";

- aqueous dispersions of particles of film-forming polymers, often referred to as "latex"; in In this case, the composition must include, apart from the liquid medium organic, an aqueous phase;

- water-soluble film-forming polymers; in In this case, the composition must include, apart from the liquid medium Organic, an aqueous phase.

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In one embodiment, the film forming agent It is a film-soluble organic polymer soluble in the liquid medium organic.

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I / Polymers soluble in the organic liquid medium

When the organic liquid medium of the composition includes at least one oil, the film forming agent can be a polymer soluble in said oil. In this case, we talk about fat soluble polymer. The fat soluble polymer can be of one type Any chemical and can be specially selected from:

a) Homopolymers and copolymers liposoluble and amorphous olefins, cycloolefins, butadiene, isoprene, styrene, ethers, esters or vinyl amides and esters or acid amides (meth) acrylic containing an alkyl group C_ {4-50} linear, branched or cyclic, and preferably amorphous. Homopolymers and copolymers Preferred fat-soluble are obtained from monomers selected from the group consisting of (meth) acrylate of isooctyl, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, the (meth) lauryl acrylate, the (meth) acrylate of isopentyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, the (meth) acrylate of methyl, tert-butyl (meth) acrylate, (meth) tridecyl acrylate, the (meth) acrylate of stearyl or mixtures thereof. For example, the copolymer will be mentioned. of alkyl acrylate / cycloalkyl acrylate marketed by PHOENIX CHEM. under the name GIOVAREZ AC-5099 ML and vinyl pyrrolidone copolymers, such as copolymers of a C 2 to C 30 alkene, such as C 3 to C 22, and You can use associations of these. As examples of copolymers of VP that can be used in the invention, the VP / vinyl laurate copolymer, VP / vinyl stearate, the butylated polyvinylpyrrolidone (PVP), from VP / hexadecene, from VP / triacontene or VP / acrylic acid / lauryl methacrylate.

As particular fat soluble copolymers, it is They can quote:

i) polymers of grafted silicone-acrylic having a skeleton silicone and acrylic grafts or that have an acrylic skeleton and silicone grafts, such as the product marketed under the designation SA 70.5 by 3M and described in US Pat. 5,725,882, USA 5,209,924, USA 4,972,037, USA 4,981,903, USA 4,981,902 and US 5,468,477 and in US Pat. 5,219,560 and EP 0.388,582.

ii) the fat soluble polymers carrying fluorinated groups belonging to one of the classes described in the previous text, in particular those described in US Pat. 5,948,393, and the (meth) acrylate copolymers of perfluoroalkyl / (meth) acrylate described in EP patents 0.815.836 and US 5,849,318.

iii) polymers or copolymers resulting from polymerization or copolymerization of an ethylenic monomer that they have one or more ethylenic bonds, preferably conjugated (or die). As polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer, is they can use vinyl, acrylic or methacrylic copolymers.

In one embodiment, the film forming agent it is a block copolymer comprising at least one block consisting of units of styrene or styrene derivatives (by example methylstyrene, chlorostyrene or chloromethylstyrene). The copolymer comprising at least one styrene block can be a diblock or triblock copolymer, even a copolymer multiblock, star or radial. The copolymer comprising the less a styrene block may also include, for example, a alkyl styrene block (AS), an ethylene / butylene block (EB) a ethylene / propylene block (EP), a butadiene block (B), a isoprene block (I), an acrylate block (A), a block of methacrylate (MA) or an association of these blocks. The copolymer comprising at least one block consisting of units of styrene or styrene derivatives may be a triblock copolymer, and in particular of the polystyrene / polyisoprene type or polystyrene / polybutadiene, such as those marketed or manufactured under the name "Luvitol HSB" by BASF, and polystyrene / copoly (ethylene-propylene) type, or alternatively of the type polystyrene / copoli (ethylene / butylene), such as marketed or manufactured under the brand "Kraton" by Shell Chemical Co. or Gelled Permethyl 99A by Penreco. Can be also use copolymers of styrene-methacrylate.

The copolymer comprising at least one block consisting of styrene units or styrene derivatives can be, for example, the Kraton G1650 (SEBS), the Kraton G1651 (SEBS), the Kraton G1652 (SEBS), the Kraton G1657X (SEBS), the Kraton G1701X (SEP), the Kraton G1702X (SEP), the Kraton G1726X (SEB), the Kraton D-1101 (SBS), the Kraton D-1102 (SBS), Kraton D-1107 (SIS), Gelled Permethyl 99A-750, the Gelled Permethyl 99A-753-58 (polymer blend of star blocks and polymer triblock), the Gelled Permethyl 99A-753-59 (polymer blend of star blocks and polymer triblock), the Versagel 5970 and the Versagel 5960 of the Penreco house (mixture of polymer in star and of tribloque polymer in isododecane) and OS 129880, OS 129881 and OS 84383 of the Lubrizol house (copolymer of styrene-methacrylate).

In one embodiment, the film forming agent is selected from vinyl ester copolymers (the vinyl group directly attached to the group's oxygen atom ester and the vinyl ester having a hydrocarbon radical saturated, linear or branched, from 1 to 19 carbon atoms attached to the carbonyl of the ester group) and of at least one other monomer, which can be a vinyl ester (different from the vinyl ester already present), an α-olefin (from 8 to 28 carbon atoms), an alkyl vinyl ether (whose alkyl group carries from 2 to 18 atoms of carbon) or an allyl or metalyl ester (which has a radical saturated, linear or branched hydrocarbon, from 1 to 19 atoms of carbon attached to the carbonyl of the ester group).

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These copolymers can be partially crosslinked by crosslinkers, which may be either vinyl type, or of the allylic or metalyl type, such as the tetraaliloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate and divinyl octadecanedioate.

As examples of these copolymers, one can cite the copolymers: vinyl acetate / allyl stearate, acetate Vinyl / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecyl vinyl ether, vinyl propionate / allyl laurate, vinyl / vinyl laurate, stearate vinyl / octadecene-1, acetate vinyl / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate allyl vinyl / acetate, 2,2-dimethyloctanoate vinyl / vinyl laurate, 2,2-dimethylpentanoate allyl / vinyl laurate, vinyl dimethylpropionate / stearate vinyl, allyl dimethylpropionate / vinyl stearate, propionate vinyl / vinyl stearate, crosslinked with 0.2% of divinylbenzene, vinyl dimethylpropionate / vinyl laurate, crosslinked with 0.2% divinylbenzene acetate vinyl / octadecyl vinyl ether, crosslinked with 0.2% of tetraaliloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinylbenzene acetate vinyl / octadecene-1, crosslinked with 0.2% of divinylbenzene, and allyl propionate / allyl stearate, crosslinked with 0.2% divinylbenzene.

As fat-soluble film-forming polymers, it they can also mention the fat-soluble copolymers, and in particularly those resulting from ester copolymerization vinyl of 9 to 22 carbon atoms or acrylates or of alkyl methacrylates, having alkyl radicals of 10 to 20 carbon atoms

Such fat soluble copolymers can be selected from the copolymers of vinyl polystearate or Vinyl polyestearate crosslinked with divinylbenzene, with ether diallyl or with diallyl phthalate, or the copolymers of poly (meth) stearyl acrylate, polylaurate vinyl or poly (meth) lauryl acrylate, being able to these poly (meth) acrylates be crosslinked with ethylene glycol or tetraethylene glycol dimethacrylate.

The fat-soluble copolymers defined above are known and are especially in the application FR-A-2.232.303; they can have a weight molecular weight average of 2,000 to 500,000 and preferably of 4,000 to 200,000. As examples of fat soluble polymers that can be used in the invention, polyalkylenes and the C 2 -C 20 alkene copolymers, in Particularly polybutene.

b) Amorphous and fat-soluble polycondensates, preferably they don't have donor groups of interactions of hydrogen, in particular the aliphatic polyesters that have C 4-50 alkyl side chains, or polyesters resulting from the condensation of acid dimers fatty, including polyesters that include a siliconized segment in the form of a sequence, graft or terminal group, solids at ambient temperature, as defined in the patent application FR 0.113.920, not yet published.

c) The amorphous and fat-soluble polysaccharides that they have alkyl side chains (ether or ester), in particular alkylcelluloses having a C 1 to C 8 alkyl radical saturated or unsaturated, linear or branched, such as the ethyl cellulose and propyl cellulose.

The film forming polymer can be selected, in in particular, among cellulosic polymers, such as the nitrocellulose, cellulose acetate, cellulose acetobutyrate, cellulose acetopropionate and ethyl cellulose, or also polyurethanes, acrylic polymers, vinyl polymers, polyvinylbutyral, alkyd resins, resins from of aldehyde condensation products, such as resins of arylsulfonamide formaldehyde, such as toluenesulfonamide resin formaldehyde, and epoxy arylsulfonamide resins.

As a film forming polymer, they can be used especially nitrocellulose RS 1/8 sec., RS ¼ sec., ½ sec., RS 5 sec., RS 15 sec., RS 35 sec., RS 75 sec., RS 150 sec., AS ¼ sec., AS ½ sec., SS ¼ sec., SS ½ sec. and SS 5 sec., especially marketed by the company HERCULES; the resin of toluensulfonamide formaldehyde "Ketjentflex MS80" of the AKZO society or "Santolite MHP" and "Santolite MS 80" of the FACONNIER or "RESIMPOL 80" company of PAN company AMERICAN; alkyd resin "BECKOSOL ODE 230-70-E "of the company DAINIPPON; the acrylic resin "ACRYLOID B66" of the company ROHM &HAAS; and the polyurethane resin "TRIXENE PR 4127" of the BAXENDEN company.

d) Soluble or inflatable silicone resins by silicone oils. These resins are polyorganosiloxanes partially crosslinked which, depending on the rate of cross-linking, will be soluble or inflatable by the oils of silicone of the oily phase of the organic liquid medium. These resins of silicones can be selected from the non-limiting list next: MQ resins or trimethylsiloxysilicates, polysilsesquioxane or crosslinked dimethicone / vinyldimethicone polymers.

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II / Non-aqueous particle dispersions polymeric

The composition may contain an agent film-forming selected among the non-aqueous dispersions of polymer particles. The particles are generally spherical. Before incorporation into the composition of the invention, the particles are generally dispersed in a liquid fatty phase physiologically acceptable, such as hydrocarbon oils or Silicone oils According to one embodiment, you are dispersions are generally known as "NAD" (non-aqueous dispersions) of polymer, as opposed to nets, which are aqueous dispersions of polymer. These dispersions they can be especially in the form of polymer nanoparticles in stable dispersion in said fatty phase. In a mode of embodiment, the nanoparticles have a size between 5 nm and 600 nm. However, it is possible to obtain polymer particles of a size up to 1 µm.

One of the advantages of polymer dispersion of the composition of the invention is the possibility of varying the glass transition temperature (Tg) of the polymer or system polymer (more additive polymer of the plasticizer type), and so both from a hard polymer to a more or less soft polymer, which makes it possible to adjust the mechanical properties of the composition, according to the intended application and in particular according to the deposited film

The dispersion polymers that can be used in the composition of the invention preferably have a molecular weight ranging from approximately 2,000 to 10,000,000 and a Tg that goes from -100ºC to 300ºC and better still from -50ºC to 50ºC, and preferably from -10 ° C to 100 ° C.

It is possible to use film-forming polymers that preferably have a low Tg, less than or equal to skin temperature and especially less than or equal to 40 ° C. Be thus obtain a dispersion that can form a film when Applies to a support.

They can be cited among film-forming polymers homopolymers or acrylic or vinyl copolymers of radicals preferably having a Tg less than or equal to 40 ° C and especially from -10 ° C to 30 ° C, used alone or in a mixture.

By the expression "radical polymer", it is understood a polymer obtained by polymerization of monomers that contain unsaturation, especially unsaturation ethylenic, each monomer being capable of homopolymerization (at opposite of polycondensates). Radical polymers can be especially vinyl polymers or copolymers, especially acrylic polymers

Vinyl polymers can result from the polymerization of ethylenically unsaturated monomers containing at least one acidic group and / or esters of these acidic monomers and / or of amides of these acids.

As carrier monomers of an acidic group, it is possible to use unsaturated carboxylic acids α, β-ethylenic, such as acid Acrylic, methacrylic acid, crotonic acid, maleic acid or itaconic acid. (Meth) acrylic acid and acid Crotonic are preferably used, and more preferably the (meth) acrylic acid.

The esters of acidic monomers are advantageously selected from the acid esters (met) acrylic (also known as (meth) acrylates), for example the (meth) acrylates of alkyl, in particular of an alkyl C 1 -C 20 and preferably C 1 -C 6, the (meth) aryl acrylates, in particular of a C 6 -C 10 aryl, and the (meth) hydroxyalkyl acrylates, in particular of a C 2 -C 6 hydroxyalkyl. The Methyl alkyl acrylates that may be mentioned include the (meth) methyl, ethyl, butyl, isobutyl acrylate, of 2-ethylhexyl and lauryl. The Methyl hydroxyalkyl acrylates that may be mentioned include the hydroxyethyl (meth) acrylate and the (meth) acrylate 2-hydroxypropyl. The aryl (meth) acrylates which may be cited include benzyl or phenyl acrylate.

The esters of (meth) acrylic acid Particularly preferred are the (meth) acrylates of I rent.

The radical polymers preferably used are the copolymers of (meth) acrylic acid and of an alkyl (meth) acrylate, especially an alkyl C_ {1} -C_ {4}. More preferably, they can be use methyl acrylates, optionally copolymerized with Acrylic Acid

The amides of the acidic monomers that can cited include (meth) acrylamides, and especially those N-alkyl (meth) acrylamides, in particular of a C2-C12 alkyl, such such as N-ethylacrylamide, the N-t-butylacrylamide and the N-octylacrylamide, and N-dialkyl (C 1 -C 4) - (meth) acrylamides.

Vinyl film-forming polymers can result from polymerization of monomers with unsaturation ethylenic having at least one acidic group and / or esters of these acidic monomers and / or amides of these acidic monomers.

As an acid group carrier monomer, they can be use unsaturated carboxylic acids α, β-ethylenic, such as acid Acrylic, methacrylic acid, crotonic acid, maleic acid and itaconic acid. The acid is preferably used (meth) acrylic and crotonic acid, and more preferably the (meth) acrylic acid.

The esters of acidic monomers are advantageously selected from the esters of the acid (meth) acrylic (also called (meth) acrylates), especially alkyl (meth) acrylates, in particular of C 1 -C 30 alkyl, preferably C 1 -C 20, (meth) aryl acrylates, in particular of aryl C 6 -C 10, and (meth) hydroxyalkyl acrylates, in particular of C 2 -C 6 hydroxyalkyl.

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

Among the (meth) aryl acrylates, there may be mentioned benzyl acrylate and phenyl acrylate.

The esters of (meth) acrylic acid Particularly preferred are the (meth) acrylates of I rent.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, it is say, that part or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

As amides of acidic monomers, they can be cite, for example, the (meth) acrylamides, and especially the N-alkyl (meth) acylamides, in particular of C2-C12 alkyl. Between the N-alkyl (meth) acrylamides, can be cite N-ethylacrylamide, the N-t-butylacrylamide, the N-t-octylacrylamide and the N-undecylacrylamide.

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

As an example of vinyl esters, you can cite vinyl acetate, vinyl neodecanoate, pivalate vinyl, vinyl benzoate and the t-butyl vinyl benzoate. How styrene monomers, styrene and alpha-methylstyrene.

In a non-limiting manner, the polymers in dispersion of the invention can be selected from among polymers or the following copolymers: polyurethanes, polyurethanes-acrylics, polyureas, polyurea-polyurethanes, the polyester polyurethanes, the polyether polyurethanes, polyesters, polyester-amides, fatty chain polyesters, alkalis, polymers or copolymers and / or copolymers vinyl, acrylic-silicone copolymers, polyacrylamides, silicone polymers, for example siliconized polyurethanes or siliconized acrylics, and fluorinated polymers, and mixtures thereof.

The oil dispersion polymer (s) may represent (in dry matter or active matter) from 0.1% to 60% of the weight of the composition, preferably from 2% to 40% and better yet from 4% to 25%. For a solid stabilizer a room temperature, the amount of dry matter in the dispersion represents the total amount of polymer and stabilizer.

Fat-soluble or dispersible polymers in the composition of the invention can also be used in a amount from 0.01% to 20% (in active matter) with respect to weight total composition, such as, for example, from 1% to 10%, according to be the case

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III) Aqueous dispersions of polymer particles

According to another embodiment, the polymer film forming can be selected among the aqueous dispersions of polymeric particles, in case the composition according to the Invention include an aqueous phase.

The aqueous dispersion containing one or more film-forming polymers can be prepared by the expert in the technique based on your general knowledge, particularly by a emulsion or polymer dispersion polymerization before formed.

Among the film-forming polymers that can be used in the composition according to the present invention, can be cite synthetic polymers of the polycondensate type or the type of radicals, polymers of natural origin and mixtures thereof.

Among the polycondensates, one can cite also anionic, cationic, non-ionic or polyurethanes amphoteric, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester polyurethanes, the polyether polyurethanes, polyureas, polyurea / polyurethanes and mixtures thereof.

The polyurethanes can be, for example, a aliphatic, cycloaliphatic or aromatic polyurethane copolymer of polyurea / polyurethane or polyurea comprising, alone or as mixture:

- at least one sequence of polyester origin linear or branched, aliphatic and / or cycloaliphatic and / or aromatic, I

- at least one sequence of polyether origin aliphatic and / or cycloaliphatic and / or aromatic, and / or

- at least one silicone sequence, substituted or unsubstituted, branched or unbranched, for example of polydimethylsiloxane or polymethylphenylsiloxane, and / or

- at least one sequence that has groups fluoridated

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Polyurethanes such as those defined in the invention can also be obtained from polyesters branched or unbranched or from alkalis that have mobile hydrogens that are modified by means of a polyaddition with a diisocyanate and a belt compound organic bifunctional (for example, dihydro, diamino or hydroxyamino), which also include either a carboxylate or carboxylic acid group, either a sulfonate or sulfonic acid group, even an amine group neutralizable tertiary or a quaternary ammonium group.

You can also cite the polyesters, the polyester-amides, fatty chain polyesters, polyamides and epoxy ester resins.

Polyesters can be obtained in a manner known by polycondensation of aliphatic diacids or aromatic with aliphatic or aromatic diols or with polyols. Be they can use succinic acid, glutaric acid, acid adipic acid, pimelic acid, subic acid or sebacic acid as aliphatic diacids. Terephthalic acid or isophthalic acid, even a derivative, such as anhydride phthalic, such as aromatic diacids. You can use the ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol and 4,4-N- (1-methylpropylidene) bisphenol as aliphatic diols. You can use glycerol, the pentaerythritol, sorbitol and trimethylolpropane as polyols

The polyester amides can be obtained analogously to polyesters, by means of polycondensation of diacids with diamines or amino alcohols. Be they can use ethylenediamine, hexamethylenediamine and meta- or para-phenylenediamine as diamine. It can be used monoethanolamine as amino alcohol.

As a carrier monomer of an anionic group that can be used during polycondensation, can be cited, for example, dimethylolpropionic acid, trimellitic acid or a derivative, such as trimellitic anhydride, the sodium salt of 3-sulfopentanediol acid and sodium salt of acid 5-sulfo-1,3-benzenedicarboxylic. Polyesters that have a fatty chain can be obtained by means of using diols that have a fatty chain during polycondensation. Epoxy ester resins can be obtained by polycondensation of fatty acids with a condensate at end level α, ome-diepoxy.

The radical polymers can be, in in particular, acrylic or / or vinyl polymers or copolymers. Polymers with anionic radical are preferred. As monomer carrier of an anionic group that can be used during radical polymerization, acrylic acid, the methacrylic acid, crotonic acid, maleic anhydride and acid 2-acryl-amido-2-methylpropanesulfonic acid.

Acrylic polymers may result from the copolymerization of monomers selected from esters and / or the amides of acrylic acid or methacrylic acid. As examples of monomers of the ester type, the methacrylate of methyl, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, methacrylate 2-ethylhexyl and lauryl methacrylate. How Examples of monomers of the amide type, the N-t-butylacrylamide and the N-t-octylacrylamide.

Polymers are preferably used Acrylics obtained by copolymerization of monomers with ethylenic unsaturation containing hydrophilic groups, preferably of a non-ionic nature, such as the acrylate of hydroxyethyl, 2-hydroxypropyl acrylate, the hydroxyethyl methacrylate and methacrylate 2-hydroxypropyl.

Vinyl polymers can result from the homopolymerization or copolymerization of monomers selected from vinyl esters, styrene or butadiene. As examples of vinyl esters, one can cite the vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate and t-butylbenzoate from vinyl.

Copolymers of acrylic / silicone, even copolymers of nitrocellulose / acrylic.

Polymers of natural origin, eventually modified, can be selected from shellac, gum sandáraca, the daughters, the elemíes, the copales, the derivatives cellulosics and mixtures of these.

The polymers can also be cited resulting from radical polymerization of one or more radical monomers, inside and / or partially in the surface of preexisting particles of at least one polymer selected from the group consisting of polyurethanes, the polyureas, polyesters, polyester amides and / or the alkyd These polymers are generally called "hybrid polymers".

When an aqueous dispersion of polymeric particles, the dry matter content of said aqueous dispersion can be of the order of 5-60% in weight and preferably 30-50%.

The size of the polymer particles in aqueous dispersion can be between 10 and 500 nm and is preferably between 20 and 150 nm, allowing Obtaining a film that has a remarkable brightness. However, particle sizes of up to one micron can be used.

As an aqueous dispersion of film-forming polymer, it is they can use the acrylic dispersions sold under the designations "Neocryl XK-90®", "Neocryl A-1070® "," Neocryl A-1090® ",  "Neocryl BT-62®", "Neocryl A-1079® "and" Neocryl A-523® " by the company AVECIA-NEORESINS, "Dow Latex 432® "by DOW CHEMICAL," Daitosol 5000 AD® "or "Daitosol 5000 SJ" by the company DAITO KASEY KOGYO and "Syntran 5760" by the Interpolymer company, or also the aqueous polyurethane dispersions sold under the denominations "Neorez R-981®" and "Neorez R-974® "by society AVECIA-NEORESINS, the "Avalure UR-405® "," Avalure UR-410® ", "Avalure UR-425®", "Avalure UR-450® "," Sancure 875® "," Sancure 861® "," Sancure 878® "and" Sancure 2060® "by society GOODRICH, "Impranil 85®" by the company BAYER and "Aquamere H-1511® "by the HYDROMER company, the sulfopolyesters sold under the brand name "Eastman AQ®" by the company EASTMAN CHEMICAL PRODUCTS, the dispersions vinyl like the "Mexomère PAM" and its mixtures.

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IV) Water soluble polymers

In case the composition includes a phase aqueous, the film-forming polymer can be a water-soluble polymer. The water-soluble polymer is thus solubilized in the aqueous phase. of the composition.

Among the water-soluble film-forming polymers, the following cationic polymers may be mentioned:

(1) Acrylic polymers or copolymers, such such as polyacrylates or polymethacrylates; the copolymers of the family (1) may also contain one or more units derived from comonomers that can be selected from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted in nitrogen by lower alkyls, of acrylic or methacrylic acids or of esters of these, of vinylactams such as the vinylpyrrolidone or vinylcaprolactam and esters Vinyl

Thus, among these copolymers of the family (1), can be cited:

-

the copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized by dimethyl sulfate or by a halide of dimethyl, such as that sold under the name HERCOFLOC by the company HERCULES;

-

he acrylamide and chloride chloride copolymer methacryloxyethyltrimethylammonium described, for example, in the patent application EP-A-0.809.76 and marketed under the name BINA QUAT P 100 by the company CIBA GEIGY;

-

he acrylamide and methosulfate copolymer of methacryloxyethyltrimethylammonium marketed under the designation RETAIN for the company HERCULES;

-

the vinylpyrrolidone / acrylate or methacrylate copolymers of dialkylaminoalkyl, quaternized or non-quaternized, such as Products marketed under the name "GAFQUAT" by the ISP company, such as, for example, "GAFQUAT 734" or "GAFQUAT 755", or the products designated by "COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573;

-

the methacrylate terpolymers of dimethylaminoethyl / vinylcaprolactam / vinyl pyrrolidone, such as product marketed under the name GAFFIX VC 713 by the ISP society, and

-

he copolymer of vinyl pyrrolidone / dimethyl-aminopropyl methacrylamide quaternized, such as the product marketed under the denomination "GAFQUAT HS 100" by the company ISP.

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(2) The quaternized polysaccharides described more particularly in US Pat. 3,589,578 and US 4,031,307, such as guar gums containing groups cationic trialkylammonium. Such products are marketed, in particular, under the trade names JAGUAR C13 S, JAGUAR C 15 and JAGUAR C 17 by MEYHALL.

(3) The copolymers of vinylpyrrolidone and of quaternary vinylimidazole.

(4) The chitosans or their salts.

(5) Cationic cellulose derivatives, such such as cellulose or cellulose derivatives copolymers grafted by a water-soluble monomer that has an ammonium quaternary and described, in particular, in US Pat. 4,131,576, such as hydroalkylcelluloses, such as hydroxymethyl-, hydroxyethyl- or grafted hydroxypropyl celluloses, in particular, by a methacryloxyethyltrimethylammonium salt of methacrylamidopropyltrimethylammonium or dimethyldiallylammonium. The marketed products corresponding to this definition are more particularly products marketed under the name "CELQUAT L 200" and "CELQUAT H 100" by the National Starch Company

Among the water-soluble film-forming polymers, may cite the following amphoteric polymers:

(1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound which carries a carboxylic group, such as more particularly the Acrylic acid, methacrylic acid, maleic acid or acid alpha-chloroacrylic, and from a basic monomer derived of a substituted vinyl compound containing at least one atom base, such as more particularly a methacrylate and acrylate of dialkylaminoalkyl and a dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in the patent. No. 3,836,537.

(2) Polymers containing units derivatives:

to)

from to minus a monomer selected from acrylamides or methacrylamides substituted in nitrogen by a radical I rent,

b)

from to less an acidic comonomer containing one or more carboxylic groups reagents and

C)

from to minus a basic comonomer, such as esters, which has primary, secondary, tertiary and quaternary amine substituents, of acrylic and methacrylic acids, and the quaternization product of dimethylaminoethyl methacrylate by dimethyl sulfate or diethyl

(3) Cross-linked alkylpolyaminoamides totally or partially derived from polyaminoamides.

(4) Polymers that have units Zwitterionic

(5) The polymer derived from chitosan.

(6) Polymers derived from the N-carboxy-alkylation of chitosan, such as the N-carboxymethyl-chitosan or the N-carboxybutyl chitosan marketed under the denomination "EVALSAN" by the company JAN DEKKER.

(7) The copolymers of (C 1 -C 5) alkyl vinyl ether / anhydride maleic partially modified by semi-amidation for an N, N-dialkylaminoalkylamine, such as the N, N-dimethylaminopropylamine, or by semi-esterification by an N, N-dialkanolamine. These copolymers can also carry other vinyl comonomers such like vinylcaprolactam.

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Water-soluble film-forming polymers are preferably selected from the group consisting of:

- proteins such as proteins from plant origin, such as wheat or soy proteins, and proteins of animal origin, such as keratin, for example keratin hydrolysates and sulfonic keratins;

- anionic, cationic polymers, amphoteric or non-ionic chitin or chitosan;

- cellulosic polymers, such as hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylhydroxyethyl cellulose, carboxymethyl cellulose and derivatives quaternized cellulose;

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

- vinyl polymers, such as polyvinyl pyrrhenanes, copolymers of methyl vinyl ether and of maleic anhydride, the copolymer of vinyl acetate and acid Crotonic and copolymers of vinylpyrrolidone and acetate vinyl;

- copolymers of vinyl pyrrolidone and of caprolactam; polyvinyl alcohols;

- possibly modified polymers of natural origin, such as:

?

gum arabic, gum guar, xanthan derivatives and karaya gum;

?

the alginates and the carrageenans;

?

glycoaminoglycans, acid hyaluronic and its derivatives;

?

Shellac, Sandraraca, the daughters, the elemíes and the copales;

?

the acid deoxyribonucleic;

?

mucopolysaccharides, such such as hyaluronic acid, chondroitin sulfate and mixtures of these.

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These polymers will be used, in particular, if a more or less appreciable removal of the film is desired For the water.

In order to improve the film-forming nature of an oily or aqueous polymer, it is possible to add to the system polymeric a coalescing agent, which will be selected from known coalescence agents.

According to an embodiment of the invention, the film forming polymer can be selected from the polymers that they have a non-siliconized organic skeleton grafted by monomers which contain a polysiloxane. These polymers can be liposoluble, lipodispersible, water soluble or dispersible in aqueous medium, as the case may be.

Polymers that have an organic skeleton non-siliconized grafted by monomers containing a polysiloxane they consist of a main organic chain formed by organic monomers that do not include silicone, on which graft, within said chain, as well as eventually over at least one of its ends, at least one macromer of polysiloxane

In what follows, it should be understood that the expression "polysiloxane macromer" designates, as accepted generally, any monomer containing a polymer chain of the polysiloxane type in its structure.

The non-silicone organic monomers that constitute the main chain of the grafted siliconized polymer can be selected from monomers with unsaturation ethylene which can be polymerized by the radical method, the polycondensation polymerizable monomers, such as those they form polyamides, polyesters and polyurethanes, and monomers with opening ring, such as oxazoline type or caprolactone.

Polymers that have an organic skeleton non-siliconized grafted by monomers containing a polysiloxane according to the present invention can be obtained according to any method known to the person skilled in the art, in particular by reaction between (i) a starting polysiloxane macromer correctly functionalized on the polysiloxane chain and (ii) one or more non-silicone organic compounds, also they correctly functionalized by a function capable of reacting with the group or functional groups carried by said silicone forming a covalent bond; A classic example of such a reaction is the reaction of radicals between a vinyl group carried in one of the silicone ends and a double bond of a monomer with ethylenic unsaturation of the main chain.

Polymers that have an organic skeleton non-siliconized grafted by monomers containing a polysiloxane according to the invention they are preferably selected from among described in US Pat. 4,693,935, USA 4,728,571 and USA 4,972,037 and in patent applications EP-A-0.412.704, EP-A-0.412.707, EP-A-0.640.105 and WO 95/00578. Be deals with copolymers obtained by radical polymerization at from monomers with ethylenic unsaturation and from monomers that they have a vinyl terminal group, or of copolymers obtained by reaction of a polyolefin containing functional groups and a polysiloxane macromer that has a reactive terminal function with these functionalized groups.

A particular family of silicone polymers grafts suitable for carrying out the present invention it consists of grafted silicon polymers that they contain:

a) from 0 to 98% by weight of at least one lipophilic low polarity lipophilic monomer (A) with ethylenic unsaturation, polymerizable by the method of radicals;

b) from 0 to 98% by weight of at least one hydrophilic polar monomer (B) with ethylenic unsaturation, copolymerizable with the monomer or monomers of type (A);

c) from 0.01 to 50% by weight of at least one polysiloxane macromer (C) of general formula:

(I) X (Y) n Si (R) 3-m Z m

where:

X designates a vinyl group copolymerizable with monomers (A) and (B);

And designates a group that has a divalent bond;

R designates hydrogen, C 1 -C 6 alkyl or alkoxy or aryl C 6 -C 12;

Z designates a monovalent polysiloxane unit having an average molecular weight numerical of at least 500;

n is 0 or 1 and m is an integer from 1 to 3, the percentages being calculated with with respect to the total weight of the monomers (A), (B) and (C).

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These polymers have an average molecular weight numerical from 10,000 to 2,000,000, and preferably a temperature of glass transition Tg or a crystalline melting temperature Tm of at minus -20 ° C.

As examples of lipophilic monomers (A), you can cite the C 1 -C 18 alcohol esters and of acrylic or methacrylic acid; alcohol esters C 12 -C 30 and methacrylic acid and the styrene; polystyrene macromers; vinyl acetate; he vinyl propionate; alpha-methylstyrene; he tert-butyl styrene; butadiene; the cyclohexadiene; cyclohexadiene [sic]; ethylene; propylene; vinyl toluene; esters of acrylic or methacrylic acid and of 1,1-dihydroperfluoroalkanols or homologs of these; esters of acrylic or methacrylic acid and of omega-hydrofluoroalkanols; acid esters acrylic or methacrylic and fluoroalkyl sulfonamidoalcohols; the esters of acrylic or methacrylic acid and fluoroalkylalcohols; esters of acrylic or methacrylic acid and alcohol fluoroethers; or mixtures of these. Preferred monomers (A) are selected within the group consisting of methacrylate n-butyl, isobutyl methacrylate, acrylate of tert-butyl methacrylate tert-butyl methacrylate 2-ethylhexyl, methyl methacrylate, acrylate from 2- (N-methylperfluorooctanesulfonamido) ethyl, acrylate of 2- (N-Butylperfluorooctanesulfonamido) ethyl or mixtures of these.

As examples of polar (B) monomers, may mention acrylic acid, methacrylic acid, N, N-dimethylacrylamide, methacrylate dimethylaminoethyl, quaternized dimethylaminoethyl methacrylate, the (meth) acrylamide, the N-t-butylacrylamide, the acid maleic, maleic anhydride and their hemiesters, (meth) hydroxyalkyl acrylates, chloride diallyldimethylammonium, vinyl pyrrolidone, vinyl ethers, maleimides, vinylpyridine, vinylimidazole, compounds polar and heterocyclic polar, styrene sulfonate, allyl alcohol, vinyl alcohol, vinylcaprolactam or mixtures of these. The monomers (B) are preferably selected in the within the group consisting of acrylic acid, the N, N-dimethyl acrylamide, the dimethylaminoethyl methacrylate, methacrylate quaternized dimethylaminoethyl, vinyl pyrrolidone and mixtures of these.

Special mention is made of product KP 561 or KP 562 marketed by Shin Etsu, such as monomer (A), and selected from alcohol esters C 18 -C 22 and methacrylic acid.

The macromers of polysiloxane (C) of formula (I) are preferably selected from those corresponding to the following general formula (II):

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3

in the which:

R1 is hydrogen or -COOH (preferably hydrogen);

R2 is hydrogen, methyl or -CH2COOH (preferably methyl);

R 3 is alkyl, alkoxy or alkylamino C 1 -C 6, aryl C 6 -C 12 or hydroxyl (preferably methyl);

R 4 is alkyl, alkoxy or alkylamino C 1 -C 6, aryl C 6 -C 12 or hydroxyl (preferably methyl);

q is an integer from 2 to 6 (preferably 3);

p is worth 0 or 1;

r is an integer from 5 to 700, and

m is an integer from 1 to 3 (preferably one).

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The macromers of polysiloxane of formula:

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4

where n is a number from 5 to 700 and l being an integer between 0 and 3.

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An embodiment of the invention consists of in the use of a copolymer capable of being obtained by radical polymerization from the monomer mixture constituted by:

a) 60% by weight acrylate of tert-butyl;

b) 20% by weight acrylic acid;

c) 20% by weight of siliconized macromer of formula:

5

where n is a number from 5 to 700 and l being an integer between 0 and 3, being calculated the percentages by weight with respect to the total weight of the monomers

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Another particular embodiment of the invention consists in the use of a copolymer capable of being obtained by radical polymerization from the mixture of monomers consisting of:

a) 80% by weight acrylate of tert-butyl;

b) 20% by weight of siliconized macromer of formula:

6

where n is a number from 5 to 700 and l being an integer between 0 and 3, being calculated the percentages by weight with respect to the total weight of the monomers

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Another particular family of silicone polymers grafts that have a non-siliconized organic skeleton suitable for an embodiment of the present invention is constituted by grafted silicone copolymers capable of be obtained by reactive extrusion of a polysiloxane macromer with reactive terminal function on a polyolefin type polymer which has reactive groups capable of reacting with the function terminal of the polysiloxane macromer to form a bond covalent that allows the grafting of the silicone on the chain Main polyolefin. These polymers, as well as their preparation procedure, are described in the application for WO 95/00578.

The reactive polyolefins are selected preferably between polyethylene or monomer polymers ethylene derivatives, such as propylene, styrene, alkylstyrene, butylene, butadiene, (meth) acrylates, vinyl esters or equivalent, which they have reactive functions capable of reacting with the function terminal of the polysiloxane macromer. More are selected particularly among copolymers of ethylene or derivatives of ethylene and the selected monomers among those with a carboxylic function, such as (meth) acrylic acid, which have an acid anhydride function, such as anhydride of maleic acid, those that have an acid chloride function, such as (meth) acrylic acid chloride, which have an ester function, such as acid esters (meth) acrylic, and those that have an isocyanate function.

Silicone macromers are preferably selected from polysiloxanes that have a group functionalized at the end of the polysiloxane chain or in the proximity of the end of said chain, selected within the group consisting of alcohols, thiols, epoxies and primary and secondary amines, and very particularly among corresponding to the general formula:

(III) T- (CH 2) 6 -Si - [- (OSiR 5 R 6) t -R 7] y

where T is selected from the group consisting of NH2, NHRN, an epoxy function, OH or SH; R 5, R 6, R 7 and RN, independently designate alkyl C 1 -C 6, phenyl, benzyl or alkylphenyl C 6 -C 12 or hydrogen; s is a number from 2 to 00 [sic]; t is a number from 0 to 1,000, and y is a number from 1 to 3. They have a number average molecular weight preferably from 5,000 to 300,000, more preferably from 8,000 to 200,000 and more particularly from 9,000 to 40,000

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According to a preferred embodiment, the film forming polymer can be purchased from the Minnesota Mining and Manufacturing Company under the trade names of "Silicone Plus" polymers. For example, him poly (methacrylate isobutyl-co-FOSEA of methyl) -g-poly- (dimethylsiloxane) It is marketed under the commercial name SA 70-5 IBMMF.

According to another preferred form of the invention, the film-forming polymer is selected from siliconized polymers grafted by non-silicone organic monomers. These polymers they can be fat soluble, lipodispersible, water soluble or dispersible in aqueous medium, as the case may be.

Said polymer or said siliconized polymers grafts that have a polysiloxane skeleton grafted by non-silicone organic monomers contain a main chain of silicone (or polysiloxane (/ SiO -) n) on which it is found grafted, inside said chain, as well as eventually in at least one of its ends, at least one organic group that does not It contains silicone.

Polymers that have a skeleton of grafted polysiloxane by non-silicone organic monomers according to the invention can be existing commercial products or can be obtained by any means known to the expert in the technique, in particular by reaction between (i) a silicone of correctly functionalized heading on one or more of these atoms of silicon and (ii) an organic compound not siliconized on its part also correctly functionalized by a function capable of react with the group or functional groups carried by said silicone, forming a covalent bond; a classic example of such reaction is the hydrosilylation reaction between groups / Si-H and vinyl groups CH2 = CH-, including the reaction between thiofunctional groups -SH with these same groups vinyl.

Examples of polymers having a polysiloxane skeleton grafted by non-organic monomers silicones suitable for an embodiment of the present invention, as well as its specific method of preparation, in particular, in patent applications EP-A-0.582.152, WO 93/23009 and WO 95/03776, whose teachings are fully included in the present description by way of non-limiting references.

According to one embodiment particularly preferred of the present invention, the siliconized polymer having a polysiloxane skeleton grafted by non-organic monomers silicones used is constituted by the result of a radical copolymerization between, on the one hand, at least one non-siliconized anionic organic monomer with ethylenic unsaturation and / or a non-silicone hydrophobic organic monomer with unsaturation ethylenic and, on the other, a silicone that presents in its chain less a functional group, and preferably several, capable of react with said ethylenic unsaturations of said monomers non-siliconized, forming a covalent bond, in particular groups thiofunctional

According to the present invention, said monomers anionics with ethylenic unsaturation are preferably selected, alone or as mixtures, between carboxylic acids unsaturated, linear or branched, eventually neutralized partially or totally in the form of salt, this or these may be unsaturated carboxylic acids more particularly the acid acrylic, methacrylic acid, maleic acid, acid Itaconic, fumaric acid and crotonic acid. Salts suitable are, in particular, alkaline salts, alkaline earth and ammonium. It will be noted that, similarly, in the final grafted siliconized polymer, the organic group of nature anionic that is constituted by the result of the (homo) radical polymerization of at least one monomer anionic unsaturated carboxylic acid type can be post-neutralized, after the reaction, by a base (soda, ammonia, etc.) to take it to the salt form.

According to the present invention, the monomers hydrophobic with ethylenic unsaturation are preferably selected, alone or as a mixture, between the esters of the acid acrylic of alkanols and / or esters of methacrylic acid alkanols The alkanols are preferably C_ {1} -C_ {30} and more particularly C_ {1} -C_ {22}. Preferred monomers are selected from the group consisting of (meth) acrylate of isooctyl, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, the (meth) lauryl acrylate, the (meth) acrylate of isopentyl, n-butyl (meth) acrylate, isobutyl (meth) acrylate, the (meth) acrylate of methyl, tert-butyl (meth) acrylate, (meth) tridecyl acrylate and the (meth) acrylate of stearyl, or mixtures thereof.

A family of silicone polymers that have a polysiloxane skeleton grafted by non-organic monomers silicones particularly suitable for the realization of The present invention is constituted by siliconized polymers which have the following unit of formula IV in their structure:

7

where the radicals G_ {{}}, identical or different, they represent hydrogen or an alkyl radical C 1 -C 10, including a phenyl radical; the radicals G2, identical or different, represent represents [sic] a C 1 -C 10 alkylene group; G_ {3} represents a polymeric residue resulting from the (homo) polymerization of at least one anionic monomer with ethylenic unsaturation; G_ {4} represents a polymeric moiety resulting from the (homo) polymerization of at least one monomer of at least one hydrophobic monomer [sic] with unsaturation ethylenic; m and n are equal to 0 or 1; a is an integer from 0 to fifty; b is an integer that can be between 10 and 350, and c is an integer from 0 to 50, provided that one of parameters a and c be different from 0.

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The unit of formula (IV) of the previous text preferably has at least one, and even more preferably the set, of the following characteristics:

- the radicals G_ {1} designate a radical alkyl, preferably a methyl radical;

- n is not zero and the radicals G_ {2} represent a divalent radical C 1 -C 3, preferably a propylene radical;

- G 3 represents a polymer radical resulting from the (homo) polymerization of at least one monomer of the carboxylic acid type with ethylenic unsaturation, preferably acrylic acid and / or methacrylic acid;

- G4 represents a polymeric radical resulting from the (homo) polymerization of at least one monomer of the alkyl (meth) acrylate type C 1 -C 10, preferably the (meth) isobutyl or methyl acrylate.

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Examples of silicone polymers corresponding to formula (IV), in particular, polydimethylsiloxanes (PDMS) on which they are grafted, by means of a secondary bond of the thiopropylene type, polymer units mixed type poly (meth) acrylic acid and type alkyl poly (meth) acrylate.

Other examples of silicone polymers corresponding to formula (IV) are, in particular, polydimethylsiloxanes (PDMS) on which they are grafted, by means of a secondary bond of the thiopropylene type, polymer units of the isobutyl poly (meth) acrylate type.

Such polymers include polymers that They have at least one group of formula:

8

in the which:

a, b and c, which can be identical or different, they are each a number from 1 to 100,000 and the terminal groups, which they can be identical or different, they are each selected from the C 1 -C 20 linear alkyl groups, the branched chain alkyl groups C 3 -C 20, the aryl groups C 3 -C 20, the linear alkoxy groups C 1 -C 20 and branched alkoxy groups C_ {3} -C_ {20}.

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Such polymers are disclosed in the patents. USA No. 4,972,037, 5,061,481, 5,209,924, 5,849,275 and 6,033,650 and WO 93/23446 and WO 95/06078.

Another family of silicone polymers that have a polysiloxane skeleton grafted by non-organic monomers silicones particularly suitable for the realization of The present invention is constituted by siliconized polymers which include in its structure the unit of the formula (V) next:

9

in which the radicals G 1 and G2 have the same meaning as before; G_ {5} represents a polymer residue resulting from the (homo) polymerization of al at least one monomer of at least one hydrophobic monomer [sic] with ethylenic unsaturation or copolymerization of at least one anionic monomer with ethylenic unsaturation and at least one hydrophobic monomer with ethylenic unsaturation; n is equal to 0 or 1; a is an integer from 0 to 50, and b is an integer that can be between 10 and 350, provided it is different from 0.

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The unit of formula (V) of the previous text preferably has at least one, and even more preferably the set, of the following characteristics:

- the radicals G_ {1} designate a radical alkyl, preferably a methyl radical;

- n is not zero and the radicals G_ {2} represent a divalent radical C 1 -C 3, preferably a propylene radical.

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The numerical molecular mass of polymers siliconates having a polysiloxane skeleton grafted by non-silicone organic monomers of the invention vary preferably from about 10,000 to 1,000,000 and even more preferably from about 10,000 to 100,000.

The composition may contain from 2 to 60% by weight, better than 5 to 60%, preferably 2 to 30% by weight in dry matter of film-forming polymer. More generally, the total amount of polymer should be a sufficient amount to form on the skin and / or lips a cohesive film capable of follow the movements of the skin and / or lips without detaching or break.

When the polymer has a temperature of glass transition too high for the desired use, it you can associate a plasticizer to reduce this temperature of The mixture used. The plasticizer can be selected from plasticizers commonly used in the field of application, and especially among the compounds that can be solvents for the polymer.

The composition according to the invention may include a hydrophilic medium consisting of water or a mixture of water and hydrophilic organic solvent (s), such as alcohols and especially linear lower monoalcohols or branched from 2 to 5 carbon atoms, such as ethanol, the isopropanol or n-propanol, and polyols, such as glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols, or also C 2 ethers and C 2 -C 4 hydrophilic aldehydes.

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

The composition according to the invention may contain emulsifying surfactants especially present in a proportion of 2 to 30% by weight with respect to the total weight of the composition, and better from 5% to 15%. These surfactants can be selected from anionic surfactants or not ionic You can refer to the document "Encyclopedia of Chemical Technology, KIRK-OTHMER ", volume 22, pp. 333-432, 3rd edition, 1979, WILEY, for definition of the properties and functions (emulsifiers) of the surfactants, in particular pp. 347-377 of this reference for anionic and non-ionic surfactants.

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

- among non-ionic surfactants: acids fatty, fatty alcohols, polyethoxylated fatty alcohols or polyglycerols such as stearyl or cetyl stearyl alcohols polyethoxylates, esters of fatty acid and sucrose, alkylglucose esters, in particular the fatty esters of (C 1 -C 6) alkyl glucose polyoxyethylene, and mixtures thereof.

- among anionic surfactants: acids C 16 -C 30 fatty acids neutralized by amines, ammonia or alkaline salts, and mixtures thereof.

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According to one embodiment, they are used preferably surfactants that allow obtaining a oil-in-water or emulsion wax-in-water.

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

According to one embodiment particularly preferred, the organic liquid medium of the composition contains the minus an organic solvent, which is the one or one of the solvents of polymerization of the sequenced polymer as described previously. Advantageously, said organic solvent is the liquid majority by weight in the organic liquid medium of the composition Cosmetic

According to one embodiment, the solvent medium Organic contains liquid fatty bodies at room temperature (25 ° C in general) called oils. These liquid fatty bodies They can be of animal, vegetable, mineral or synthetic origin.

As oils usable in the invention, it is may mention: hydrocarbon oils of animal origin, such like the perhidroescualeno; vegetable hydrocarbon oils, such as liquid triglycerides of fatty acids from 4 to 10 carbon atoms, such as triglycerides of heptanoic acids or octanoic, or also sunflower, corn, soybean, oil seeds of grape, sesame, apricot, macadamia, castor or of avocado, triglycerides of caprylic / capric acids and jojoba oil or shea butter; linear hydrocarbons or branched of mineral or synthetic origin, such as oils of paraffin and its derivatives, petrolatum, polydecenes and hydrogenated polyisobutene, such as Parleam; the esters and the synthetic ethers, especially fatty acids, such as Purcellin oil, isopropyl myristate, palmitate 2-ethylhexyl stearate 2-octyldodecyl, the belching of 2-octyldodecyl and isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, the octyl hydroxystearate, octyldodecyl hydroxystearate, diisoestearyl malate, triisocetyl citrate and heptanoates, octanoates and decanoates of fatty alcohols; polyol esters, such as Propylene Glycol Dioctanoate, Diheptanoate neopentyl glycol, diethylene glycol diisononanoate and esters from pentaerythritol; fatty alcohols of 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, the 2-undecylpentadecanol and oleic alcohol; the partially hydrocarbon and / or silicone fluorinated oils; the silicone oils, such as volatile polymethylsiloxanes (PDMS) or no, linear or cyclic, such as cyclomethicones and dimethicones, which eventually carry a phenyl group, such as phenyltrimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenylmethyldimethyltrisiloxanes, diphenyl dimethicones, phenyldimethicones and polymethylphenylsiloxanes; and their mixtures.

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

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

These solvents can usually be present in a content of 0.1 to 90%, preferably even 10 at 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 can be cited, apart from organic solvents hydrophilic cited above, liquid ketones a room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone; temperature liquid propylene glycol ethers environment, such as propylene glycol monomethyl ether, the propylene glycol monomethyl ether acetate and ether dipropylene glycol mono-n-butyl; short chain esters (from 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, acetate propyl, n-butyl acetate and acetate isopentyl; liquid ethers at room temperature, such as diethyl ether, dimethyl ether or dichlorodyethyl ether; liquid alkanes at room temperature, such as dean, heptane, dodecane, isododecane and cyclohexane; the liquid aromatic cyclic compounds at room temperature, such as toluene and xylene; liquid aldehydes to room temperature, such as benzaldehyde and acetaldehyde; and their mixtures.

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

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

Waxes can be hydrocarbon, fluorinated and / or silicone and be of plant, mineral, animal and / or origin synthetic. In particular, the waxes have a temperature of melting above 25 ° C and better above 45 ° C. As usable wax in the composition of the invention, the wax of bees, Carnauba or Candelilla wax, paraffin, waxes microcrystalline, ceresin or ozocerite and synthetic waxes, such as polyethylene or Fischer Tropsch waxes and waxes from silicones, such as the alkyl- or alkoxy-dimethicone of 16 at 45 carbon atoms.

The gums are generally polydimethylsiloxanes (PDMS) of high molecular weight or cellulose gums or polysaccharides. The pasty bodies are generally hydrocarbon compounds, such as lanolines and their derivatives, or also PDMS.

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The nature and quantity of the bodies solid fats are a function of the mechanical properties and the Textures searched. By way of indication, the composition may contain from 0 to 50% by weight of waxes with respect to weight total composition, and better from 1 to 30% by weight. He polymer can be associated with one or more auxiliary forming agents of movie. Such a film forming agent can be selected from all the compounds known to the expert in the technique as capable of fulfilling the function sought, and especially between plasticizers and agents coalescence

The composition according to the invention can also include one or more selected coloring materials among the water-soluble dyes and powdery dyes, such as pigments, mother of pearl and sequins, well known by the person skilled in the art. The coloring matters 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% at 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, we must understand particles of any way iridescent, especially produced by some shellfish in its shell or synthesized.

The pigments can be white or colored, minerals and / or organic. They can be cited, among the pigments minerals, titanium dioxide, eventually treated in surface, and zirconium or cerium oxides, as well as oxides zinc, iron (black, yellow or red) or chrome, violet manganese, ultramarine blue, chromium hydrate and blue ferric and metal powders, such as aluminum powder and dust coppermade. Among the organic pigments, the black of carbon, D&C type pigments and carmine-based lacquers of cochineal or barium, strontium, calcium or aluminum.

You can also mention pigments with effect, such as particles that carry an organic substrate or mineral, natural or synthetic, for example glass, resins Acrylics, polyester, polyurethane, terephthalate polyethylene, ceramics or aluminas, said coating being coated substrate or not by metallic substances, such as aluminum, gold, silver, platinum, copper or bronze, or by metal oxides, such as titanium dioxide, iron oxide or chromium oxide, and their mixtures.

Pearly pigments can be selected among white pearly pigments, such as mica coated with titanium or bismuth oxychloride, and pigments pearly colored, such as oxide-coated titanium mica Iron, titanium mica specially coated with ferric blue or of chromium oxide and mica titanium coated with a pigment organic of the aforementioned type, as well as pearly pigments to bismuth oxychloride base. You can also use the interferential pigments, especially with liquid crystals or multilayer

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

The composition according to the invention may contain also one or more charges, especially in a content of 0.01% at 50% by weight with respect to the total weight of the composition, preferably from 0.01% to 30% by weight. For charges, you have to understand particles of any shape, colorless or white, mineral or synthetic, insoluble in the middle of the composition whatever the temperature at which the composition is manufactured. These charges are especially useful for modifying rheology or texture of the composition.

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

The composition according to the invention can specially presented in the form of a bar, of suspension, of dispersion, solution, gel, emulsion, especially oil-in-water emulsion (Ac / Ag) or water-in-oil (Ag / Ac) or multiple (Ag / Ac / Ag or polyol / Ac / Ag or Ac / Ag / Ac), cream, paste, foam, of vesicle dispersion, especially of ionic lipids or not, biphasic or multiphasic lotion, spray, powder, paste, especially flexible pasta (especially pasta 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 paste.

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

The composition according to the invention may be a makeup composition, such as complexion products (bases of makeup), blushes or eye shadows, bars lipstick, concealer products, mascaras, eye profilers, eyebrow makeup products, lip or eye pencils, nail products, such such as nail polishes, body makeup products and hair makeup products (mask or hairspray for hair)

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

The composition according to the invention can be also a hair product, especially for the maintenance of Hair styling or hair modeling. The hair compositions are preferably shampoos, gels, marking lotions, lotions for hand drying and fixing and styling compositions, such like lacquers or sprays.

According to one embodiment, the invention has per object a fiber coating composition keratin (such as eyelashes, eyebrows and hair) consisting of an organic liquid medium, at least one aqueous phase and at least one film-forming linear sequential ethylenic polymer and a dispersion of film-forming polymer particles such as described above.

Advantageously, the film-forming polymer water dispersible is selected from polyurethanes, the polyurethane-acrylics, polyacrylics, polyesters of (meth) acrylics, polyvinylpyrrolidone, polyurethane-polyvinylpyrrolidones, polyester polyurethanes, the polyether polyurethanes, polyureas, poly-urea / polyurethanes and mixtures thereof, as has been defined above.

Advantageously, the composition includes at least a second film forming agent selected from the polymers water-soluble, such as cationic cellulose derivatives and / or optionally modified polymers of natural origin, such Like gum arabic.

Preferably, said composition includes a wax and preferably still includes a surfactant.

Such a composition may be presented in forms. different: for example, in the form of diphasic emulsions of wax-in-water or of water-in-wax or dispersion aqueous or anhydrous.

Advantageously, the composition is a coating composition of eyelashes or mascara.

The present invention also has object a cosmetic set comprising:

- a vessel that defines at least one compartment, said container being closed by an element of close, and

- a composition as described previously arranged inside said compartment.

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The container can have any shape adequate. It can be especially shaped like a bottle, tube, boat, case, box, envelope or briefcase.

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

The container may be associated with a applicator, especially in the form of a brush that carries a arrangement of hairs maintained by a braided thread. Such a brush braided 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, specially obtained by molding. Such Combs are described, for example, in FR 2,796,529. He Applicator may be in the form of a brush, as described, for example, in patent FR 2,722,380. The applicator can be in shape of a foam or elastomer block, a marker or A spatula. The applicator can be free (tassel or sponge) or integral with a rod carried by the closure element, such as It is described, for example, in US Pat. 5,492,426. He Applicator may be integral to the container, as described, by example, patent FR 2,761,959.

The product can be directly contained in the container or indirectly. As an example, the product it can be arranged on an impregnated support, especially in shape of a wipe or a tampon, and arranged (unitary or as a plurality) in a box or in an envelope. Such support that incorporates the product is described, for example, in the WO application 01/03538.

The closure element may be coupled to the screwing container. Alternatively, the coupling between the closing element and the container is carried out in another way that by screwing, especially by a bayonet mechanism, by ratchet, pressure, welding or glueing or by attraction magnetic "Ratchet" means, in particular, everything system that involves the passage of a weatherstrip or a cord of matter by elastic deformation of a portion, especially of the element of closing, and then by return to the position of no tension elastically of said portion after the passage of the weatherstrip or the cord.

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

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

The container can be of rigid walls or of deformable walls, especially in the form of a tube or a tube jar.

The container may include means intended for provoke or facilitate the distribution of the composition. By way of example, the container can be deformable walls for 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. Alternatively, especially when the product is in the form of a bar, the latter can be dragged by a mechanism piston Always in the case of a bar, especially of makeup product (lipstick, makeup base, etc.), the container can carry a mechanism, especially of zipper, or with a threaded rod, or with a helical ramp, suitable for moving a bar in the direction of said opening. Such mechanism is described, for example, in FR 2,806,273 or in FR 2,775,566. Such a mechanism for a liquid product It is described in patent FR 2,727,609.

The container may consist of a briefcase with a fund that defines at least one accommodation that It contains the composition and a lid, specially articulated on the bottom and suitable for at least partially covering said bottom. Such a briefcase is described, for example, in the application WO 03/018423 or in patent FR 2,791,042.

The container may be equipped with a drainer arranged in proximity to the opening of the container. Such drainer allows to dry the applicator and eventually the stem of the That can be supportive. Such drainer is described, for example, in patent FR 2,792,618.

The composition may be under pressure. atmospheric 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 content of patents or applications for patents cited above are incorporated by reference in the present application.

The following examples illustrate not limiting the compositions according to the invention.

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Example 4 Liquid lipstick

10

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Moreover, its application is made without difficulty with a foam applicator and you get a deposit homogeneous of good persistence.

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Example 5 Solar composition

eleven

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Examples 6 to eleven

Emulsion masks

Mask compositions were prepared following according to the invention and the state of the art: composition of example 6 according to the state of the art does not contain sequenced polymer or aqueous dispersion of polymer particles film forming

The composition of example 10 contains a aqueous dispersion of film-forming polymer particles, but not sequenced polymer

The compositions of examples 7 to 9 and 11 according to the invention contain a sequenced polymer and a Aqueous dispersion of film-forming polymer particles.

12

13

For each composition, the dry extract, in vitro loading and persistence were measured, according to the methods described below.

In vitro load is measured by gravimetry on samples of curved Caucasian hair (30 1 cm long hair spread over a distance of 1 cm). The sample is made up by making 3x10 mask passes spaced in 2 minutes with product collection between each series of 10.

The sample is dried for 10 min. at temperature atmosphere and weighs later.

This measurement is performed on 6 samples.

The charge is in fact the amount of matter deposited on the sample = mass of the makeup sample - mass of shows naked.

The average load is the average of the measurements made on the 6 samples.

The dry matter content is measured, that is, the non-volatile content, or dry extract, of the compositions on a scale Mettler Toledo HG 53 (Halogen Moisture Analyzer) A sample of mask is deposited (2-3 g) on an aluminum cup and subjected at a temperature of 120 ° C for 60 minutes. The measure of dry extract corresponds to the monitoring of the sample mass in time function. The final solids content is thus the percentage of the final mass (after 60 min.) with respect to the initial mass: ES = (final mass / initial mass) X 100.

The persistence of the formed film is evaluated by the composition according to the invention by resistance measurement to water, as a function of time, of a composition film extended on a glass plate and subjected to stirring in aqueous medium. The protocol is as follows:

At room temperature (25 ° C), a 300 µm thick composition layer (before drying) and of a surface of 9 cm X 9 cm on a glass plate of a surface of 10 cm X 10 cm and then let dry for 24 hours at 30 ° C and 50% relative humidity. After drying, the plate in a crystallizer with a diameter of 19 cm and a capacity 2 liters filled with a liter of water and placed on a stirrer magnetic heater sold under the name RCT basic by the IKA labor technik society. He then puts on the film a PTFE smooth cylindrical magnet bar (length 6 cm; diameter 1 cm). The stirring speed is regulated in position 5. It is controlled water temperature with a thermometer at a temperature of 20 ° C or 40 ° C. At time t_ {0} = 0, stirring begins. It is measured the time t (expressed in minutes) after which the film begins to peel off or peel off the plate or when observed a hole the size of the magnetic stir bar, that is, when the hole has a diameter of 6 cm. Water resistance of the film corresponds to the time t measured.

The following results are obtained:

14

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It is found that the compositions according to the invention of examples 7 to 9 and 11 comprising the association of an aqueous dispersion of film-forming polymer particles and a sequenced polymer have good persistence, better than that of the composition of example 10, which does not Contains sequenced polymer. In addition, the compositions according to the invention allow a thick make-up of the eyelashes, since they have a dry extract and high in vitro loading values.

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Example 12 Waterproof mascara

16

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The dry extract, in vitro loading and persistence were measured according to the measurement methods described above in the description.

The following results were obtained:

17

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This mascara has a good persistence, having at the same time a good thickening (loading) effect of the tabs.

Claims (102)

1. Cosmetic composition containing a medium organic liquid, at least one linear ethylenic sequenced polymer non-elastomeric film forming agent and at least one other soluble film forming agent or dispersible in said organic liquid medium, whose sequenced polymer contains first and second sequences linked together by an intermediate segment statistic that includes at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence, the first sequence of the polymer between: - a) a sequence that has a higher Tg or equal to 40 ° C, - b) a sequence that has a lower Tg or equal to 20ºC and - c) a sequence that has a Tg comprised between 20 and 40ºC and the second sequence being selected in a category a), b) or c) different from the first sequence, and said sequenced polymer having an index of polydispersity I greater than 2.8.

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2. Cosmetic composition containing a medium organic liquid, at least one aqueous phase, at least one polymer film-forming linear ethylenic sequencing free of styrene unit and at least one other soluble or dispersible film forming agent in said phase watery, whose sequenced polymer contains first and second sequences linked together by an intermediate segment statistic that includes at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence, the first sequence of the polymer between: - a) a sequence that has a higher Tg or equal to 40 ° C, - b) a sequence that has a lower Tg or equal to 20ºC and - c) a sequence that has a Tg comprised between 20 and 40ºC and the second sequence being selected in a category a), b) or c) different from the first sequence, and said sequenced polymer having an index of polydispersity I greater than 2.8.

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3. Cosmetic composition according to claim 1 or 2, characterized in that it is the non-elastomeric sequenced polymer. 4. Cosmetic composition according to one of the preceding claims, characterized in that the sequenced polymer is free of styrene unit. 5. Cosmetic composition according to one of the preceding claims, characterized in that 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-. 6. Cosmetic composition according to one of the preceding claims, characterized in that the polymer is not soluble in 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 carbon atoms, without pH modification, at room temperature (25 ° C). 7. 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. 8. Cosmetic composition according to one of the preceding claims, characterized in that the first and second sequence sequence polymer is incompatible in said organic liquid medium.

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9. 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 such that the homopolymer prepared from these monomers has a transition temperature vitreous greater than or equal to 40 ° C. 10. 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:

-

the formula methacrylates CH 2 = C (CH 3) - COOR 1, where R1 represents a linear unsubstituted alkyl group or branched from 1 to 4 carbon atoms, such as a methyl group, ethyl, propyl or isobutyl, or R1 represents a group C4 to C12 cycloalkyl;

-

the acrylates of formula CH2 = CH-COOR2, where R 2 represents a C 4 to C 12 cycloalkyl group, such such as isobornyl acrylate, or a group tert-butyl;

-

the (meth) acrylamides of the formula:

18

where R_ {7} and R 8, identical or different, each represents an atom of hydrogen or an alkyl group of 1 to 12 linear carbon atoms or branched, such as an n-butyl group, t-butyl, isopropyl, isohexyl, isooctyl or isononyl, or R 7 represents H and R 8 represents a group 1,1-dimethyl-3-oxobutyl, and R 'designates H or methyl;

-

and their mixtures

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Composition according to claim 9 or 10, 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, isobornyl (meth) acrylate and their mixtures. 12. Composition according to the preceding claim, 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 such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C. 13. Composition according to the preceding claim, 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:

-

the acrylates of formula CH 2 = CHCOOR 3,

representing R 3 a linear C 1 to C 12 unsubstituted alkyl group or branched, except for the tert-butyl group, where one or more heteroatoms are eventually interspersed selected from O, N and S;

-

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

representing R 4 a linear C 6 to C 12 unsubstituted alkyl group or branched, where one or more are eventually interspersed heteroatoms selected from 0, N and S;

-

the formula vinyl esters R 5 -CO-O-CH = CH 2, where R 5 represents a linear C 4 to C 12 alkyl group or branched;

-

the vinyl and C4 to C12 alkyl ethers;

-

the N-alkyl (C4 a C 12) acrylamides, such as the N-octylacrylamide,

-

and their mixtures

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14. Composition according to claim 12 or 13, 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, with the exception of tert-butyl group. 15. Composition according to one of claims 1 to 8, characterized in that the sequence having a Tg of 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 temperature glass transition between 20 and 40 ° C. 16. Composition according to one of claims 1 to 8, 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 such monomers that the corresponding homopolymer has a Tg less than or equal to 20 ° C. 17. Composition according to claim 15 or 16, characterized in that the sequence having a Tg comprised between 20 and 40 ° C in all or part of monomers selected from methyl methacrylate, acrylate and isobornyl methacrylate, butyl acrylate , 2-ethylhexyl acrylate and mixtures thereof. 18. Composition according to one of claims 1 to 14, 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) greater than or equal to 40 ° C and the second sequence having a glass transition temperature less than or equal to 20 ° C. 19. 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. 20. 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. 21. Composition according to claim 19 or 20, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between the following monomers:

-

the formula methacrylates CH 2 = C (CH 3) - COOR 1, where R1 represents a linear unsubstituted alkyl group or branched from 1 to 4 carbon atoms, such as a methyl group, ethyl, propyl or isobutyl, or R1 represents a group C4 to C12 cycloalkyl;

-

the acrylates of formula CH2 = CH-COOR2, where R 2 represents a C 4 to C 12 cycloalkyl group, such such as isobornyl acrylate, or a group tert-butyl;

-

the (meth) acrylamides of the formula:

19

where R_ {7} and R 8, identical or different, each represents an atom of hydrogen or an alkyl group of 1 to 12 linear carbon atoms or branched, such as an n-butyl group, t-butyl, isopropyl, isohexyl, isooctyl or isononyl, or R 7 represents H and R 8 represents a group 1,1-dimethyl-3-oxobutyl, and R 'designates H or methyl;

-

and their mixtures

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22. Composition according to one of claims 19 to 21, 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 23. Composition according to one of claims 18 to 22, 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 %. Composition according to one of claims 18 to 23, 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. 25. Composition according to one of claims 18 to 24, 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. 26. Composition according to claim 24 or 25, 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:

-

the acrylates of formula CH 2 = CHCOOR 3,

representing R 3 a linear C 1 to C 12 unsubstituted alkyl group or branched, except for the tert-butyl group, where one or more heteroatoms are eventually interspersed selected from O, N and S;

-

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

representing R 4 a linear C 6 to C 12 unsubstituted alkyl group or branched, where one or more are eventually interspersed heteroatoms selected from 0, N and S;

-

the formula vinyl esters R 5 -CO-O-CH = CH 2, where R 5 represents a linear C 4 to C 12 alkyl group or branched;

-

the vinyl and C4 to C12 alkyl ethers;

-

the N-alkyl (C4 a C 12) acrylamides, such as the N-octylacrylamide,

-

and their mixtures

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27. Composition according to one of claims 24 to 26, 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 one of claims 18 to 27, characterized in that the proportion of the second sequence having a Tg of less than or equal to 20 ° C ranges from 5 to 75% by weight of the polymer, better from 15 to 50% and even better from 25 to 45%. Composition according to one of claims 1 to 17, 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. 30. Composition according to the preceding claim, characterized in that the first sequence having a Tg comprised 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. Composition according to claim 29 or 30, 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 monomers such that the corresponding Homopolymer has a Tg less than or equal to 20 ° C. 32. Composition according to one of claims 29 to 31, 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, butyl acrylate, is obtained. 2-ethylhexyl acrylate and mixtures thereof. 33. Composition according to one of claims 29 to 32, characterized in that the proportion of the first sequence having a Tg of between 20 and 40 ° C ranges from 10 to 85% by weight of the polymer, better from 30 to 80% and even better from 50 to 70%. Composition according to any one of claims 29 to 33, 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 homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C. Composition according to any one of claims 29 to 33, 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 higher glass transition temperature. or equal to 40 ° C.

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36. Composition according to one of claims 34 or 35, characterized by selecting the monomers whose corresponding homopolymer has a glass transition temperature greater than or equal to 40 ° C between the following monomers:

-

the formula methacrylates CH 2 = C (CH 3) - COOR 1, where R1 represents a linear unsubstituted alkyl group or branched from 1 to 4 carbon atoms, such as a methyl group, ethyl, propyl or isobutyl, or R1 represents a group C4 to C12 cycloalkyl;

-

the acrylates of formula CH2 = CH-COOR2, where R 2 represents a C 4 to C 12 cycloalkyl group, such such as isobornyl acrylate, or a group tert-butyl;

-

the (meth) acrylamides of the formula:

twenty

where R_ {7} and R 8, identical or different, each represents an atom of hydrogen or an alkyl group of 1 to 12 linear carbon atoms or branched, such as an n-butyl group, t-butyl, isopropyl, isohexyl, isooctyl or isononyl, or R 7 represents H and R 8 represents a group 1,1-dimethyl-3-oxobutyl, and R 'designates H or methyl;

-

and their mixtures

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37. Composition according to one of claims 34 to 36, 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 38. Composition according to one of claims 34 to 37, 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 of a 30 to 70% by weight of the polymer. 39. Composition according to one of claims 29 to 33, 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. Composition according to one of claims 29 to 33, characterized in that the second sequence has a Tg of less than or equal to 20 ° C and is a homopolymer from monomers such that the homopolymer prepared from these monomers has a lower glass transition temperature or equal to 20 ° C. 41. Composition according to claim 39 or 40, 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:

-

the acrylates of formula CH 2 = CHCOOR 3,

representing R 3 a linear C 1 to C 12 unsubstituted alkyl group or branched, except for the tert-butyl group, where one or more heteroatoms are eventually interspersed selected from O, N and S;

-

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

representing R 4 a linear C 6 to C 12 unsubstituted alkyl group or branched, where one or more are eventually interspersed heteroatoms selected from 0, N and S;

-

the formula vinyl esters R 5 -CO-O-CH = CH 2, where R 5 represents a linear C 4 to C 12 alkyl group or branched;

-

the vinyl and C4 to C12 alkyl ethers;

-

the N-alkyl (C4 a C 12) acrylamides, such as the N-octylacrylamide,

-

and their mixtures

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42. Composition according to one of claims 39 to 41, characterized in that the monomers whose homopolymers have glass transition temperatures of less than or equal to 20 ° C are included between the alkyl acrylates whose alkyl chain has 1 to 10 carbon atoms, with the exception of tert-butyl group. 43. Composition according to one of claims 39 to 42, characterized in that the proportion of the sequence having a glass transition temperature less than or equal to 20 ° C of 10 to 85% by weight of the polymer, better than 20 to 20 70% and even better from 20 to 50%. 44. Cosmetic composition according to one of the preceding claims that depend on it, characterized in that the first sequence and / or the second sequence includes at least one additional monomer. Composition according to the preceding claim, characterized by selecting the additional monomer among the hydrophilic monomers, the monomers with ethylenic unsaturation having one or more silicon atoms and mixtures thereof. 46. Composition according to claim 44 or 45, characterized by selecting the additional monomer from: a) hydrophilic monomers such as:

-

the monomers with ethylenic unsaturation (s) that have at least one carboxylic or sulfonic acid function, as per example:

the acid Acrylic, methacrylic acid, crotonic acid, anhydride maleic acid, itaconic acid, fumaric acid, maleic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, acid vinyl phosphorus and salts thereof;

-

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

-

the formula methacrylates CH 2 = C (CH 3) - COOR 6,

where R_ {6} represents a linear or branched alkyl group of 1 to 4 atoms of carbon, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted by one or more substituents selected from hydroxyl groups (such as methacrylate 2-hydroxypropyl and methacrylate 2-hydroxyethyl) and halogen atoms (Cl, Br, I and F), such as trifluoroethyl methacrylate;

-

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

representing R 9 a linear or branched C 6 to C 12 alkyl group, where one or more are eventually interspersed heteroatoms selected from 0, N and S, said group being alkyl substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F);

-

the acrylates of formula CH 2 = CHCOOR 10,

representing R 10 a linear or branched C 1 to C 12 alkyl group replaced by one or more substituents selected from among hydroxyl groups and halogen atoms (Cl, Br, I and F), such such as 2-hydroxypropyl acrylate and acrylate of 2-hydroxyethyl, or R 10 represents a (C 1 -C 12) alkyl - O-POE (polyoxy-ethylene) with repetition of the unit oxy-ethylene 5 to 30 times, for example methoxy-POE, or R 10 represents a group polyoxyethylene having 5 to 30 units of ethylene oxide, Y

b) monomers with ethylenic unsaturation that they have one or more silicon atoms, such as the methacryloxypropyltrimethoxysilane and the methacryloxypropyltris (trimethylsiloxy) silane,

-

and their mixtures

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47. Composition according to one of claims 44 or 45, 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. 48. Composition according to one of claims 44 or 45, 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 acid ( met) acrylic, and mixtures thereof. 49. Composition according to one of claims 44 or 45, characterized in that each 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 (meth) acrylic acid, and mixtures thereof.

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50. Composition according to one of claims 44 to 49, 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. 51. 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 than 40 ° C. 52. Composition according to any one of the preceding claims, characterized in that the sequenced polymer has a polydispersity index between 2.8 and 6. 53. 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. 54. 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. 55. Composition according to the preceding claim, characterized in that the weight average mass (Mn) is less than or equal to 70,000. 56. Composition according to one of the claims 53 to 55, whose weight average mass (Mn) ranges from 10,000 to 60,000 and better than 12,000 to 50,000. 57. Composition according to one of the preceding claims, characterized in that it includes from 0.1 to 60% by weight in active matter of sequenced polymer, preferably from 5% to 50% by weight and preferably even from 10 to 10 40% by weight. 58. Composition according to any one of claims 1 and 3 to 57, characterized in that the film-forming agent is a film-forming polymer soluble in said organic liquid medium. 59. Composition according to the preceding claim, characterized in that the film-forming agent is a liposoluble film-forming polymer. 60. Composition according to the preceding claim, characterized in that the liposoluble film-forming polymer is selected from the homopolymers and the liposoluble and amorphous copolymers of olefins, cycloolefins, butadiene, isoprene, styrene, ethers, esters or amides vinyl and esters or amides of (meth) acrylic acid containing a linear, branched or cyclic C 4-50 alkyl group, and preferably amorphous. 61. Composition according to claim 59, characterized in that the liposoluble film-forming polymer is selected from homopolymers and copolymers obtained from monomers selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, the ( 2-ethylhexyl methacrylate, lauryl (meth) acrylate, isopentyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, tert-butyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate or mixtures thereof, in particular an alkyl acrylate / cycloalkyl acrylate copolymer and vinyl pyrrolidone / decacene copolymers. 62. Composition according to claim 59, characterized in that the liposoluble film-forming polymer is selected from the amorphous and fat-soluble polycondensates that preferably do not contain hydrogen interaction donor groups, in particular the polyesters having C 4-50 alkyl side chains, or or the polyesters resulting from the condensation of fatty acid dimers, including polyesters having a siliconized segment in the form of a solid sequence, graft or terminal group at room temperature. 63. Composition according to claim 59, characterized in that the liposoluble film-forming polymer is selected from amorphous and fat-soluble polysaccharides having alkyl (ether or ester) side chains, in particular ethyl cellulose, grafted silicone-acrylic polymers having a silicone skeleton , acrylic grafts or having an acrylic skeleton and silicone grafts. 64. Composition according to claim 59, characterized by carrying the liposoluble film-forming polymer fluorinated groups. 65. Composition according to claim 59, characterized in that the liposoluble film-forming polymer is selected from the alkyl (meth) acrylate / perfluoroalkyl acrylate copolymers. 66. Composition according to claim 59, characterized in that the liposoluble film-forming polymer is selected from the polymers or copolymers resulting from the polymerization or copolymerization of an ethylenic monomer having one or more ethylenic bonds, preferably conjugated. 67. Composition according to the preceding claim, characterized by selecting the polymer or copolymer resulting from the polymerization or copolymerization of an ethylene monomer between the polystyrene / copoly (ethylene / butylene). 68. Composition according to claim 59, characterized in that the liposoluble film-forming polymer is selected from polymers having a non-siliconized organic skeleton grafted by monomers containing a polysiloxane. 69. Composition according to claim 59, where said at least one liposoluble film forming polymer is selected from the silicone polymers grafted by non-silicone organic monomers. 70. Composition according to any one of claims 1 and 3 to 57, characterized in that the film-forming agent is a film-forming polymer dispersible in said organic liquid medium. Composition according to the preceding claim, characterized in that the organic liquid medium includes at least one oil, for being the film-forming agent dispersible in said oil and for being the film-forming agent in the form of a non-aqueous dispersion of polymer particles. 72. Composition according to any one of claims 2 to 57, characterized in that the film-forming agent is a film-forming polymer dispersible in the aqueous phase. 73. Composition according to the preceding claim, characterized in that the water dispersible film-forming polymer is selected from polyurethanes, polyurethane-acrylics, polyurethane-polyvinyl pyrrolidones, polyester polyurethanes, polyether polyurethanes, polyureas, polyurea / polyurethanes and their mixtures 74. Composition according to claim 72, characterized in that the water dispersible film-forming polymer is an aliphatic, cycloaliphatic or aromatic polyurethane copolymer, a polyurea / polyurethane or polyurea copolymer comprising, alone or as a mixture: - at least one sequence with polyester origin linear or branched, aliphatic and / or cycloaliphatic and / or aromatic, I - at least one sequence with polyether origin aliphatic and / or cycloaliphatic and / or aromatic, and / or - at least one silicone sequence, substituted or unsubstituted, branched or unbranched, for example of polydimethylsiloxane or polymethylphenylsiloxane, and / or - at least one sequence that has groups fluoridated

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75. Composition according to claim 72, characterized in that the film-forming polymer dispersible in the aqueous phase is selected from polyesters, polyester amides, fatty chain polyesters, polyamides and epoxy ester resins. 76. Composition according to claim 72, characterized in that the film-forming polymer dispersible in the aqueous phase is selected from acrylic polymers, acrylic copolymers and vinyl polymers. 77. Composition according to any one of the preceding claims, characterized in that the proportion of film-forming agent ranges from 2 to 60%, preferably from 5 to 60%, more preferably from 2 to 30%, by weight of dry compound with respect to the total weight of the composition. 78. Cosmetic composition according to any one of the preceding claims, characterized in that it also includes one or more dyes selected from water-soluble dyes and powdery dyes, such as pigments, mother-of-pearls and sequins. 79. 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) or water- emulsion in-oil (Ag / Ac) 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, spray, powder, paste, especially flexible paste or anhydrous paste, stick or emptied solid. 80. Cosmetic composition according to any one of the preceding claims, characterized in that it is presented in an anhydrous form. 81. Cosmetic composition according to any one of the preceding claims, characterized in that it is a make-up or care composition of keratin materials. 82. Composition according to one of the preceding claims, characterized in that it is a lip makeup product. 83. Composition according to one of the preceding claims, characterized in that it is an eye makeup product. 84. Composition according to one of the preceding claims, characterized in that it is a complexion makeup product. 85. Composition according to one of the preceding claims, characterized in that it is a nail makeup product. 86. Fiber coating composition keratin, especially eyelashes and eyebrows, which it contains an organic liquid medium, at least one aqueous phase, at less a film-forming ethylenic sequenced polymer according to one of claims 1 to 56 and at least one other soluble film forming agent or dispersible in said aqueous phase. 87. Composition according to the preceding claim, characterized in that the film-forming agent is a film-forming polymer dispersible in the aqueous phase. 88. Composition according to the preceding claim, characterized in that the water dispersible film-forming polymer is selected from polyurethanes, polyurethane-acrylics, polyurethane-polyvinyl pyrrolidones, polyester polyurethanes, polyether polyurethanes, polyureas, polyurea / polyurethanes and their mixtures 89. Composition according to one of claims 86 to 88, characterized by including a wax. 90. Composition according to one of claims 86 to 89, characterized in that it includes a surfactant. 91. Composition according to one of claims 86 to 90, characterized by including at least a second film-forming agent selected from the water-soluble polymers. 92. Composition according to the preceding claim, characterized by selecting the water-soluble polymers or polymers from cationic cellulose derivatives and / or optionally modified polymers of natural origin, such as gum arabic. 93. Composition according to one of claims 86 to 92, characterized in that it includes a coloring agent. 94. Composition according to one of claims 86 to 93, characterized in that it is a mascara. 95. Cosmetic set consisting of: a) a vessel that delimits at least one compartment, said container being closed by an element of close, and b) a composition arranged inside said compartment, keeping the composition in accordance with a any of the preceding claims.

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96. Cosmetic assembly according to the preceding claim, characterized in that the container is formed, at least in part, in at least one thermoplastic material. 97. Cosmetic assembly according to claim 95, characterized in that the container is formed, at least in part, in at least one non-thermoplastic material, especially in glass or metal. 98. Assembly according to any one of claims 95 to 97, characterized in that the closure element is in the closed position of the container, screwed onto the container. 99. Assembly according to any one of claims 95 to 97, characterized in that the closure element is in the closed position of the container, coupled to the container in a manner other than screwing, especially by ratchet, glueing or welding. 100. Assembly according to any one of claims 95 to 99, characterized in that the composition is sensitive to atmospheric pressure inside the compartment. 101. Assembly according to any one of claims 95 to 99, characterized in that the pressurized composition is inside the container. 102. Cosmetic procedure of makeup or care of keratin materials, consisting of the application on the keratin materials of a cosmetic composition according to one of claims 1 to 94.