EP2373284A2

EP2373284A2 - Cosmetic composition for makeup and/or keratin material care, based on a mixture of resins mq and t-pr, and makeup method

Info

Publication number: EP2373284A2
Application number: EP09801489A
Authority: EP
Inventors: Claudia Barba; Roberto Cavazzuti; Véronique Ferrari; Audrey Ricard
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2008-12-02
Filing date: 2009-12-02
Publication date: 2011-10-12
Also published as: WO2010063959A2; US20120003167A1; US20120064019A1; WO2010063955A3; EP2373285A2; US20120014899A1; US9017705B2; US8747828B2; EP2358346A2; WO2010063959A3; WO2010063968A2; WO2010063957A3; WO2010063966A2; WO2010063954A3; US20110236342A1; WO2010063958A2; WO2010063965A3; WO2010063966A3; WO2010063961A3; WO2010063966A9

Abstract

The present invention relates to a composition that includes, in a physiologically acceptable medium: A) a siloxane resin containing at least 80 mol % of the following units: (i) (R'3SiO1/2)a and (ii) (SiO4/2)b where R' is, independently, an alkyl grouping having 1 to 8 carbon atoms, an aryl grouping, a carbinol grouping, or an amino grouping with the proviso that at least 95 mol % of the R' groups are alkyl groups; a and b have values strictly greater than 0; and the ratio of a to b is between 0.5 and 1.5; B) a propyl silsesquioxane resin containing at least 80 mol % of (R"SiC>3/2) units where R" is, independently, an alkyl grouping having 1 to 8 carbon atoms, an aryl grouping, a carbinol grouping, or an amino grouping with the proviso that at least 80 mol % of the R" groups are propyl groups, the weight ratio between the resins a) and b) being between 1/99 and 99/1, but particularly between 85/15 and 15/85 the resins a) and b) not being bonded to each other by covalent bonds, and the number of M units in the final mixture being strictly less than the number of (T+Q) units; and C) at least one film-forming polymer selected from among the group including: an ethylene sequential copolymer (also called an ethylene sequential polymer) containing at least one first sequence having a vitreous transition temperature (Tg) greater than or equal to 400°C and derived, in whole or in part, from one or more first monomers, such that the homopolymer prepared from said monomers at a vitreous transition temperature less than or equal to 400°C, and from at least one second sequence having a vitreous transition temperature less than or equal to 20°C and derived, in whole or in part, from one or more second monomers, such that the homopolymer prepared from said monomers has a vitreous transition temperature less than or equal to 200°C, said first sequence and said second sequence being bonded together by an intermediate statistical segment that contains at least one of said first monomers that constitutes the first sequence and at least one of said second monomers that constitutes the second sequence, and said copolymer sequence having a polydispersity index I greater than 2; and a vinyl polymer containing at least one pattern derived from dendrimer carboxilane, a dispersion of radical, acrylic, or vinyl homopolymer or copolymer particles being dispersed in said liquid fatty phase.

Description

The invention relates to a cosmetic composition for keratin materials, especially the lips and skin, hair and nails. The invention relates in particular to makeup compositions of said keratin materials, comprising at least one siloxane resin and at least one film-forming polymer.

One of the objectives of the application is to make makeup compositions for keratin materials (skin, mucous membranes, fiber, eyelashes and integuments), for depositing a total non-transfer film, and having a good comfort and a good level of gloss, especially in the case of a lipstick.

In the field of lipsticks and makeup in general, the formulator is looking for compositions that have good holding properties to meet the expectations of consumers. These compositions must also be without transfer, while offering good comfort properties.

The formulator is therefore in search of raw materials and / or systems for obtaining compositions whose deposition is characterized by improved performance and a good level of comfort. By comfort, is meant comfort at the application, that is to say a composition that is easily deposited in terms of slipperiness and amount deposited, without the film being deposited too thick and / or tights. For comfort, we also mean the comfort after the application, so that the user does not feel tugging or desiccation in particular.

It is known to one skilled in the art to use polymers to obtain these holding properties during the day.

These polymers are of very different chemical natures and are carried either in a fatty phase or in an aqueous phase.

Mention may be made, by way of example, of silicone resins, in particular of the MQ type, polyacrylates, latices, etc.

If these polymers actually provide holding properties, particularly non-transfer, they are usually accompanied by discomfort either during the application of the product (difficult spreading, sticky ....) or during the day (tugging, mask effect ...).

It is therefore necessary to seek a technical solution to obtain these holding properties while maintaining a comfortable use. This object is achieved thanks to the compositions according to the invention.

The subject of the present invention is indeed a composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units: (i) (R'3SiOi / ₂ ) _a (hereinafter units "M") and

(ii) (SiO _4/2) b (hereinafter "Q" units) wherein

R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 95 mol% of the R' groups are alkyl groups,

• a and b have values strictly greater than 0;

• and the ratio a / b is between 0.5 and 1, 5, and b) a propyl silsesquioxane resin comprising at least 80 mole% of units (R "SiO _3/2) (hereinafter" T "units) wherein R" independently represents an alkyl group having 1 to 8 carbon atoms , an aryl group, a carbinol group or an amino group, with the proviso that at least 80 mol% of the R "groups are propyl groups, the weight ratio of the resins a) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, the resins a) and b) not being bonded to one another by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one film-forming polymer, preferably selected from the group comprising: a block ethylenic copolymer (also called sequence ethylenic polymer), containing at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ^° C. and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least one second sequence having a temperature glass transition less than or equal to 20 ° C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ^{° C} C, said first sequence and said second sequence being connected to each other by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second constituent monomers of the second block, and said block block copolymer having an index of polydispersity I greater than 2, a vinyl polymer comprising at least a unit derived from a carbosiloxane dendrimer, a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase.

The compositions according to the invention may also comprise an additional ingredient preferably chosen from pasty compounds of non-animal origin, rheological thickening agents or gelling agents of the fatty phase, waxes, hydrophilic gelling agents, fillers, ionic surfactants. , fibers, and mixtures thereof.

Preferably, the compositions according to the invention may comprise at least one additional ingredient preferably chosen from pasty compounds of non-animal origin, rheological thickening agents or gelling agents of the fatty phase, with the exception of dimethicone crosspolymers, with the exception of candelilla wax, ozokerite and silicone waxes, hydrophilic gelling agents, fillers, ionic surfactants with the exception of lauryl ether sulfate, fibers, and mixtures thereof.

In particular, according to one embodiment, the waxes are chosen from beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis, waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains, fluorinated waxes, wax obtained by hydrogenation of olive oil esterified with stearyl alcohol, the waxes obtained by hydrogenation of castor oil esterified with cetyl alcohol and sticky waxes.

Preferably, the ionic surfactants are chosen from cationic surfactants, amphoteric surfactants, carboxylates, taurates and N-acyl N-methyltaurates, alkylsulfoacetates, polypeptides, alkyl polyglycoside anionic derivatives and fatty acid salts. C16-C30 derivatives derived from amines, polyoxyethylenated fatty acid salts, phosphoric esters and their salts, sulfosuccinates, alkyl sulphates, isethionates and N-acylisethionates, acylglutamates, soya derivatives, citrates, derivatives proline, lactylates, sarcosinates, sulfonates and glycinates. Preferably, the rheological thickeners or gelling agents of the fatty phase are chosen from crystalline polymers, mineral lipophilic structuring agents, lipophilic polyamides, lipophilic polyureas and polyurethanes, and silicone polymers optionally comprising at least one hydrocarbon-based unit comprising two groups. capable of establishing hydrogen interactions selected from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino and combinations thereof, organogelators, block polymers, cholesteric liquid dimethicone / vinyldimethicone copolymers, and vinyldimethicone / alkyl dimethicone copolymers, such as vinyldimethicone / lauryl dimethicone copolymers.

The subject of the present invention is also a composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units:

(i) (R'3SiOi / ₂ ) _a (hereinafter "M" units) and (N) (SiO _4/2 ) b (hereinafter "Q" units) in which

• a and b have values strictly greater than 0;

And the ratio a / b is between 0.5 and 1.5, and b) a film-forming propyl silsesquioxane resin comprising at least 80 mol% of units (R "SiO _3/2 ) (hereinafter" units "). T ") in which R" independently represents an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol% of the R "groups are propyl groups, the weight ratio between the resins a) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, the resins a) and b) not being bound by one with the other by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one film-forming polymer, preferably chosen from the group comprising : a block ethylenic copolymer (also called sequence ethylenic polymer), containing at least a first sequence having a temperature glass transition (Tg) greater than or equal to 40 ⁰ C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least one second block having a glass transition temperature of less than or equal to 20 ^° C. and originating in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C, said first sequence and said second sequence being interconnected by a random intermediate segment comprising at least one of said first constituent monomers of the first block and at least one of said second monomers constituting the second block, and said block copolymer having a polydispersity index I greater than 2; a vinylic polymer comprising at least one unit derived from a carbosiloxane dendrimer; homopolymer or radical copolymer, acrylic o u vinylic dispersed in said liquid fatty phase.

The siloxane resin a), hereinafter referred to as "MQ resin", preferably comprises residual silanol (-SiOH) groups. In this case, preferably the amount of -OH groups is between 2 and 10% by weight of the MQ resin, preferably between 2 and 5% by weight of the MQ resin. Preferably, the groups R 'of the resin MQ are methyl groups.

Resin b), hereinafter referred to as "propyl T resin", preferably comprises silanol residual groups (-SiOH) and / or alkoxy groups. In this case, preferably the amount of -OH groups is between 2 and 10% by weight of the propyl T resin, and / or the amount of alkoxy groups is less than or equal to 20% by weight of the propyl T resin. Preferably, the amount of -OH groups is between 6 and 8% by weight of the propyl T resin, and / or the amount of alkoxy groups is less than or equal to 10% by weight of the propyl T resin. The propyl T resin according to the invention is such that at least 40 mol% of the R "groups are propyl groups, preferably at least 50 mol%, and more preferably at least 90 mol%.

By covalent bond is meant a chemical bond between at least 2 atoms (carbon, silicon, oxygen, etc.) in which each of the bonded atoms pools an electron of one of its outer layers to form a doublet of electrons linking the two atoms.

The MQ resin according to the invention comprises at least 80 mol% of units: (i) (R'3SiOi / ₂ ) _a (hereinafter "M" units) and (N) (SiO _4/2 ) b ( hereinafter "Q" units) in which

• a and b have values strictly greater than 0;

And the ratio a / b is between 0.5 and 1.5.

The radical R of the resin MQ independently represents an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group.

The alkyl groups can in particular be chosen from methyl, ethyl, propyl, butyl, pentyl, hexyl and octyl groups. Preferably, the alkyl group is a methyl group. The aryl groups may be chosen from phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups, the aryl group being preferably a phenyl group.

In the present invention, the term "carbinol group" means any group containing at least one hydroxyl radical bonded to a carbon (COH). The carbinol groups may thus contain more than one COH radical, such as, for example

If the carbinol group is free of aryl groups, it has at least 3 carbon atoms. If the carbinol group comprises at least one aryl group, it comprises at least 6 carbon atoms.

As examples of a carbinol group containing no aryl groups containing at least 3 carbon atoms, mention may be made of the groups of formula R ¹ OH in which R ¹ represents a divalent hydrocarbon radical containing at least 3 carbon atoms or a divalent hydrocarbonoxy radical having at least 3 carbon atoms. minus 3 carbon atoms. Examples of the group R ¹ include alkylene radicals such as - (CH ₂ ) χ-, the value of x being between 3 and 10, -CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH 2) ₃ ) CH ₂ -, - CH ₂ CH ₂ CH (CH ₂ CH ₃ ) CH ₂ CH ₂ CH ₂ - and -OCH (CH ₃ ) (CH ₂ ) _X -, the value of x being between 1 and 10.

As examples of a carbinol group comprising aryl groups having at least 6 carbon atoms, mention may be made of the groups of formula R ² OH in which R ² represents an arylene radical such that - (CH ₂ ) _X C ₆ H ₄ -, x having a value between 0 and 10, -CH ₂ CH (CH ₃ ) (CH ₂ ) χC ₆ H ₄ -, x having a value between 0 and 10, - (CH ₂ ) _X C ₆ H ₄ (CH ₂₎ ) _X -, x having a value between 1 and 10. The carbinol groups containing aryl groups generally comprise from 6 to 14 atoms.

The term "amino group" according to the invention is understood to mean in particular groups of formula -R ³ NH ₂ or -R ³ NHR ⁴ NH ₂ , R ³ representing a divalent hydrocarbon radical having at least 2 carbon atoms and R ⁴ representing a hydrocarbon radical bivalent having at least 2 carbon atoms. The group R ³ generally represents an alkylene radical having from 2 to 20 carbon atoms. Examples of groups R ³ include ethylene, propylene, -CH ₂ CHCH ₃ -, butylene, -CH ₂ CH (CH ₃ ) CH ₂ -, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene and decamethylene groups. . The R ⁴ group generally represents an alkylene radical having 2 to 20 carbon atoms. Examples of groups R ⁴ include ethylene, propylene, -CH ₂ CHCH ₃ -, butylene, -CH ₂ CH (CH ₃ ) CH ₂ -, pentamethylene, hexamethylene, 3-ethyl-hexamethylene, octamethylene and decamethylene groups. . The amino groups are generally -CH ₂ CH ₂ CH ₂ NH ₂ and -CH ₂ (CH ₃ ) CHCH ₂ (H) NCH ₃ , -CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ , (CH ₂ CH ₂ NH) ₃ H and -CH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₄ H ₉ .

MQ resins suitable for use as component a) and their manufacturing processes are known in the art. U.S. Patent 2,814,601, owned by Currie et al., Dated November 26, 1957, incorporated herein by reference, discloses a process for making MQ resins by converting a water-soluble silicate to a silicic acid monomer. or an oligomer of silicic acid using an acid. Once the appropriate polymerization has been carried out, trimethylchlorosilane ends are introduced to obtain the MQ resin. Another method of preparing MQ resins is described in Goodwin's US Pat. No. 2,857,356, dated October 21, 1958. incorporated herein by reference. Goodwin describes a method of manufacturing a MQ resin by cohydrolysis of a mixture of an alkyl silicate and a hydrolyzable organopolysiloxane trialkylsilane with water.

MQ resins suitable as component a) in the present invention may contain D and T units, provided that at least 80 mol%, or even 90 mol%, of the total siloxane units are M and Q units. The MQ resins may also contain residual hydroxyl groups as mentioned above. The MQ resins may also comprise additional ends, residual hydroxyl groups being for this reason reacted with appropriate M groups.

T propyl resin b) according to the invention comprises at least 80 mole% of units (R "SiO _{_3/2)} wherein R" independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol% of the R "groups are propyl groups.

Preferably, the propyl T-resin according to the invention is such that at least 50 mol% of the R "groups are propyl groups, preferably at least 90 mol%, and preferably the propyl T resin b) is film-forming. By "film-forming resin" is meant a resin capable of forming on its own or in the presence of an auxiliary film-forming agent, a macroscopically continuous and adherent film on the keratinous materials, and preferably a cohesive film, and better still a film whose cohesion and mechanical properties are such that said film can be isolatable and manipulable in isolation, for example when said film is made by casting on a non-stick surface such as a Teflon or silicone surface.

The definition of the radical R "is the same as that of the radical R. The above-mentioned definitions applicable to R 'are therefore applicable to R".

The propyl T resin b) according to the invention is a silsesquioxane resin. Silsesquioxane resins are well known in the state of the art and are generally obtained by hydrolysis of an organosilane comprising three hydrolysable groups, such as halogen or alkoxy groups, present in the molecule. The propyl T resin b) can thus be obtained by hydrolysis of propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, or by cohydrolysis of the above-mentioned propylalkoxysilanes with various alkoxysilanes. Examples of such alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, dimethyldimethoxysilane and phenyltrimethoxysilane. Propyltrichlorosilane may also be hydrolyzed alone, or in the presence of alcohol. In this case, the cohydrolysis can be carried out by adding methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane or similar chlorosilanes and methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane or similar methylalkoxysilanes. Suitable alcohols for this purpose include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butanol, methoxy ethanol, ethoxy ethanol or similar alcohols. Examples of hydrocarbon-type solvents that can be used simultaneously include toluene, xylene or similar aromatic hydrocarbons, hexane, heptane, isooctane or similar linear or partially branched saturated hydrocarbons; as well as cyclohexane or similar aliphatic hydrocarbons. The propyl T resins b) according to the invention may contain M, D and Q units, provided that at least 80 mol% or even 90 mol% of the total siloxane units are T units. propyl T may also contain residual hydroxy and / or alkoxy groups, as mentioned above. The composition according to the invention also comprises a physiologically acceptable medium. By physiologically acceptable medium is meant a medium compatible with the skin, mucous membranes and integuments. This medium may comprise at least one volatile silicone or organic solvent, this solvent being preferably compatible with the resins a / and b / and compatible with a cosmetic use.

Silicone volatile solvents that may be mentioned include cyclic polysiloxanes, linear polysiloxanes and mixtures thereof. Volatile linear polysiloxanes that may be mentioned include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, tetradecamethylhexasiloxane and hexadecamethylheptasiloxane.

Cyclic volatile polysiloxanes that may be mentioned include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane.

The organic solvent may also be an alcohol such as ethanol, isopropanol, butanol, n-propanol; a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an aliphatic hydrocarbon such as heptane, hexane, octane or isododecane; a glycol ether such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, ethylene glycol n-butyl ether.

The resin mixture a / and b / can be obtained from each of the resins in solution in a solvent. In general, at the end of synthesis of the MQ resin according to the invention, this resin is obtained directly in solution in xylene.

Similarly, at the end of synthesis of the propyl T resin b) according to the invention, this resin is obtained in solution in toluene. Each of these resins in solution is mixed with the other according to the following protocol:

1) stirring mixture of the two resin solutions, and then heating, in particular in a reactor or in an autoclave (in order to possibly operate under pressure or, on the contrary, by establishing a partial vacuum), or even in an extruder equipped or not with a system of "devolatilization" of the solvents, under the following specific conditions: homogeneously heated: the heating temperature must be greater than 90 ^° C., and less than or equal to 250 ^° C., and preferably between 90 ° C. and 190 ^° C.

Either one can heat to a single temperature, between 90 ° C and 250 ° C,

Either one can heat by making successive temperature steps: first between 90 ⁰ C and T1 ⁰ C,

TTC being a temperature of intermediate value between 90 ° C and T2 ° C which is the final temperature for a period of between 10 minutes to 2 hours, then between TTC and T2 ° C for a period of between 10 minutes to 4 hours , the temperature T2 ° C corresponding to the maximum temperature chosen for the reaction.

This value of T2 ° C is variable according to the operating mode chosen and the type of reactor chosen: conventional reactor or autoclave or extruder, but T2 ° C remains lower than or equal to 250 ^° C. It is also possible to make intermediate temperature levels between TTC and T2 ° C; the heating time is at least one hour in a reactor or in an autoclave and at least 10 minutes in an extruder, preferably between 1 h and 5 h in a reactor or in an autoclave, and preferably between 10 minutes and 2 hours in an extruder; - provided that these heat treatments are performed without the presence of a chemical condensation catalyst between the 2 resins MQ and propyl T. Such a catalyst is in particular a mineral base, in particular NaOH, KOH or ammonia. 2) Optionally, after, or even during, step 1) of heat treatment of the 2 resins in the indicated temperature range, a partial or total distillation of the aromatic solvents is carried out, replacing them with a cosmetically acceptable volatile solvent . Such a volatile solvent may especially be a volatile or non-volatile silicone, preferably decamethylcyclopentasiloxane, or a volatile or nonvolatile organic solvent, preferably isododecane.

3) Optionally again, after mixing the initial two solutions of each resin in a volatile solvent, the mixture of solutions is treated in a "devolatilization" extruder type screw or twin-screw kneader at a temperature range of between 90.degree. ° and 250 ⁰ C, to volatilize the volatile solvents by establishing a partial vacuum, working continuously, then to pass through a die the molten mixture and without solvent. The molten mixture is then cooled at the die outlet and cut into solid granules or in powder form. In this case, the mixture is directly in solid form and will be redissolved in the solvents chosen at the time of formulation.

Also the subject of the present invention is also a composition as described above comprising, in a physiologically acceptable medium:

1) the mixture between a siloxane resin a) and a propyl silsesquioxane resin b), the mixture being as described above, and

2) at least one film-forming polymer, preferably chosen from the group comprising: a block ethylenic copolymer (also called a sequential ethylenic polymer), containing at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ^° C. and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ° C, and at least one second sequence having a glass transition temperature less than or equal to 20 ⁰ C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ⁰ C, said first sequence and said second sequence being interconnected by an intermediate segment st atistique comprising at least one of said first monomers constituting the first block and at least one of said second constituent monomers of the second block, and said block copolymer having a polydispersity index I greater than 2, a vinylic polymer comprising at least one derived unit carbosiloxane dendrimer, a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase,

the siloxane resins a) and propyl silesquioxane b) being formulated in the composition via a mixture that can be obtained according to the following process:

Mixing, preferably with stirring, a solution of siloxane resin with a solution of propyl silsesquoxane resin, the solvent present in each of the solutions being preferably volatile, then Heating, especially in a reactor or in an autoclave or in an extruder, under the following specific conditions: homogeneously heated to a temperature greater than 90 ^° C., and less than or equal to 250 ^° C., preferably between 90 ^° C. ° C and 190 ⁰ C; the heating can be done at a single temperature, or at temperature levels, as indicated above; the heating time is at least 1 hour in a reactor or in an autoclave and at least 10 minutes in an extruder, preferably between 1 hour and 5 hours in a reactor or in an autoclave and preferably between 10 minutes and 2 hours in an extruder; provided that these heat treatments are carried out without the presence of a chemical condensation catalyst between the 2 resins MQ and propyl T. Such a catalyst is in particular a mineral base, in particular NaOH, KOH or ammonia.

This process may comprise, after or even during the mixing step, an additional step of partial or total distillation of the aromatic solvents, replacing them with a cosmetically acceptable volatile solvent. In the case where an extruder is used, this process may comprise, after or even during the mixing step, an additional step of partial or total distillation of the aromatic solvents, by leaving the mixture directly in the solid state.

The final stage of the heat treatment, or even the heat treatment itself, can be carried out in a kneader intended for stirring very viscous media such as:

A "Zigma blender" type mixer, in particular a Brabender mixer,

An extruder screw kneader, in particular a single-screw extruder or a twin-screw extruder (with or without a "devolatilization" step of the volatile solvents of departure) or in a knider which makes it possible to devolatilize by establishing a thin film on the walls.

The resin mixtures 1) that can be used according to the invention are in particular those described in application WO 2005/075567, the contents of which are incorporated herein by reference, in particular those described in Tables 1 and 3 of said application. It is also possible to use the resin mixtures 1) described in the application WO2007 / 145765, in particular those described in Examples 12 to 14 of this application, in which the weight ratio between the resins a) and b) are respectively 50 / 50, 60/40 and 71/29 (70/30).

According to one particular embodiment, the resin mixture 1) described in Example 22 of said application WO2005 / 075567 is used, in which the weight ratio between the resins a) and b) is 85/15. According to one particular embodiment, the resin mixture 1) described in Example 13 of said application WO2007 / 145765 is used, in which the weight ratio between the resins a) and b) is 60/40.

Preferably, the siloxane resin is present in the composition in a total resin solids content ranging from 1% to 80% by weight relative to the total weight of the composition, preferably ranging from 5% to 70% by weight. weight, and better ranging from 6% to 60% by weight.

The compositions according to the invention may be in various forms, in particular in the form of powder, anhydrous dispersion, water / oil emulsion or water / wax, oil / water, multiple or wax / water, or gel. Preferably, the composition according to the invention comprises less than 3%, or better, less than 1% water by weight relative to the total weight of the composition. More preferably the composition is completely anhydrous. By anhydrous is meant in particular that the water is preferably not deliberately added to the composition but may be present in trace amounts in the various compounds used in the composition.

Film-forming polymers

The composition according to the invention comprises at least one film-forming polymer.

The compositions according to the invention can thus comprise at least one film-forming polymer, and the mixture 1) described above. In the present invention, the term "film-forming polymer" is intended to mean a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a film which is macroscopically continuous and adheres to the keratin materials, and preferably a cohesive film. and more preferably a film whose cohesion and mechanical properties are such that said film can be isolable and manipulable in isolation, for example when said film is produced by casting on a non-stick surface such as a Teflon or silicone surface.

The film-forming polymer (s) used, in combination with the mixtures of MQ and T-propyl resins, may be carried in the oily phase (liposoluble or lipodispersible polymers) or conveyed in an aqueous phase (water-soluble polymers or latex).

Preferably, the composition according to the invention comprises at least one polymer chosen from the group comprising: a block ethylenic copolymer (also called sequence ethylenic polymer), containing at least a first block having a higher glass transition temperature (Tg) or equal to 40 ⁰ C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least a second block having a glass transition temperature of less than or equal to 20 ^° C. and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20 ° C, said first sequence and said second sequence being connected to one another s by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second constituent monomers of the second block, and said block copolymer having a polydispersity index I of greater than 2, a vinylic polymer comprising at least less a carbosiloxane dendrimer-derived unit, a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase.

Ethylene polymer sequence: According to an exemplary embodiment of the invention, the film-forming polymer is a film-forming ethylenic block polymer, which preferably comprises at least a first block and at least a second block having different glass transition temperatures (Tg), said first and second sequences being interconnected by an intermediate sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. Advantageously, the first and second sequences and the block polymer are incompatible with each other. Such polymers are described for example in EP 1411069 or WO04 / 028488. EP141 1069 describes the possibility of preparing block polymers from acrylate monomer or methacrylate monomer.

In particular, according to one embodiment, the composition according to the present invention contains at least one block ethylenic copolymer (also called sequence ethylenic polymer), containing at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ⁰ C and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least one second sequence having a glass transition temperature less than or equal to 20 ⁰ C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to at 20 ⁰ C, said first sequence and said second sequence being connected to each other by a segm random intermediate intermediate comprising at least one of said first monomers constituting the first block and at least one of said second constituent monomers of the second block, and said block copolymer having a polydispersity index I greater than 2.

The block polymer used according to the invention thus comprises at least a first sequence and at least a second sequence.

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

By "block" polymer is meant a polymer comprising at least 2 distinct sequences, preferably at least 3 distinct sequences.

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

The ethylenic block polymer used according to the invention is prepared exclusively from monofunctional monomers.

This means that the block ethylenic polymer used according to the present invention does not contain multifunctional monomers, which make it possible to break the linearity of a polymer in order to obtain a connected or even cross-linked polymer, as a function of the multifunctional monomer content. The polymer used according to the invention also does not contain macromonomers ("macromonomer" means a monofunctional monomer having a pendant group of a polymeric nature, and preferably having a molecular weight greater than 500 g / mol, or a polymer having on one of its ends a polymerizable terminal group (or ethylenically unsaturated)), which are used in the preparation of a graft polymer.

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

The first and second sequences of the polymer used in the invention may be advantageously incompatible with each other.

By "sequences incompatible with each other" it is meant that the mixture formed by a polymer corresponding to the first block and by a polymer corresponding to the second sequence, is not miscible in the polymerization solvent, predominantly by weight, of the block polymer, at ambient temperature (20 ^° C.) and atmospheric pressure (10 ⁵ Pa), for a content of the mixture of said polymers greater than or equal to 5% by weight, relative to the total weight of the mixture of said polymers and of said polymerization solvent, it being understood that: i) said polymers are present in the mixture in a content such that the respective weight ratio ranges from 10/90 to 90 / 10, and ii) each of the polymers corresponding to the first and second blocks has an average molecular weight (by weight or number) equal to that of the +/- 15% block polymer.

In the case of a mixture of polymerization solvents, assuming two or more solvents present in identical mass proportions, said polymer mixture is immiscible in at least one of them. Of course, in the case of a polymerization carried out in a single solvent, the latter is the majority solvent.

The block polymer according to the invention comprises at least a first block and at least a second block bonded together by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block. The intermediate segment (also called intermediate sequence) has a glass transition temperature Tg between the glass transition temperatures of the first and second sequences.

The intermediate segment is a sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer makes it possible to "compatibilize" these blocks.

Advantageously, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer is a random polymer. Preferably, the intermediate sequence is derived essentially from constituent monomers of the first sequence and the second sequence.

By "essentially" is meant at least 85%, preferably at least 90%,

95% and even better 100%. The block polymer according to the invention is advantageously a film-forming ethylenic block polymer.

By "film-forming" polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous deposit on a support, in particular on keratin materials.

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

Preferably, the polymer according to the invention is not water-soluble, that is to say that the polymer is not soluble in water or in a mixture of water and linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, without modification of pH, with an active ingredient content of at least 1% by weight, at ambient temperature (20 ^° C.).

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

By "non-elastomeric polymer" is meant a polymer which, when subjected to a stress aimed at stretching it (for example by 30% relative to its initial length), does not does not return to a length substantially identical to its initial length when the stress ceases.

More specifically, "non-elastomeric polymer" denotes a polymer having an instantaneous recovery R ₁ <50% and a delayed _recovery R _2h <70% after undergoing a 30% elongation. Preferably, R ₁ is <30%, and R _2h <50%.

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

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

A film approximately 100 μm thick in which are cut rectangular specimens (for example by punch) of a width of 15 mm and a length of 80 mm are then obtained.

This sample is imposed a tensile stress using an apparatus marketed under the reference Zwick, under the same conditions of temperature and humidity as for drying.

The specimens are stretched at a speed of 50 mm / min and the distance between the jaws is

50 mm, which corresponds to the initial length (I ₀ ) of the test piece.

The instantaneous recovery R 1 is determined as follows: the specimen is stretched by 30% (ε _max ), that is to say approximately 0.3 times its initial length (I ₀ )

the stress is released by imposing a return speed equal to the pulling speed, ie 50 mm / min, and measuring the residual elongation of the test piece in percentage, after returning to zero load stress (ε,).

The instantaneous recovery in% (R,) is given by the formula below:

To determine the delayed recovery, after 2 hours the residual elongation rate of the test specimen is measured in percentage (ε _2h ), 2 hours after return to the zero load stress.

The recovery delayed in% (R _2h ) is given by the formula below: x 100 For purely indicative purposes, a polymer according to one embodiment of the invention preferably has an instantaneous recovery R, of 10% and a delayed _recovery R _2h of 30%.

The polydispersity index of the polymer of the invention is greater than 2.

Advantageously, the block polymer used in the compositions according to the invention has a polydispersity index I greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8. and more preferably greater than or equal to 2.8 and in particular ranging from 2.8 to 6. The polydispersity index I of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn.

The weight average (Mw) and number (Mn) molar masses are determined by gel permeation liquid chromatography (THF solvent, calibration curve established with linear polystyrene standards, refractometric detector). The weight average mass (Mw) of the polymer according to the invention is preferably less than or equal to 300,000, it ranges, for example, from 35,000 to 200,000, and more preferably from 45,000 to 150,000 g / mol. The number average mass (Mn) of the polymer according to the invention is preferably less than or equal to 70,000, it ranges, for example, from 10,000 to 60,000, and more preferably from 12,000 to 50,000 g / mol.

Preferably, the polydispersity index of the polymer according to the invention is greater than 2, for example ranging from 2 to 9, preferably greater than or equal to 2.5, for example ranging from 2.5 to 8, and better still or equal to 2.8 and in particular, ranging from 2.8 to 6.

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

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

GJ ₁ being the mass fraction of the monomer i in the sequence in question and Tg, being the glass transition temperature of the homopolymer of the monomer i. Unless otherwise indicated, the Tg values for the first and second sequences in the present application are theoretical Tg.

The difference between the glass transition temperatures of the first and second blocks is generally greater than 10 ° C., preferably greater than 20 ^° C., and better still greater than 30 ° C. In the present invention, the expression "comprised between ... and ..." is intended to denote an interval of values whose mentioned limits are excluded, and "from ... to ..." and "ranging from from ... to ... ", an interval of values whose terminals are included. The sequence having a Tg greater than or equal to 40 ° C may be a homopolymer or a copolymer.

The sequence having a Tg greater than or equal to 40 ^° C. may be issued in whole or in part from one or more monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C. ° C. This sequence can also be called "rigid sequence".

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

In the case where the first block is a copolymer, it may be issued in whole or in part from one or more monomers, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is greater than or equal to 40 ° C. vs. The copolymer may for example comprise:

monomers which are such that the homopolymers prepared from these monomers have Tg greater than or equal to 40 ° C., for example a Tg ranging from 40 ^° C. to 150 ° C., preferably greater than or equal to 50 ° C. ° C, ranging for example from 50 ⁰ C to 120 ° C, and better still or equal to 60 ° C, for example from 60 ⁰ C to 120 ° C, and monomers which are such that the homopolymers prepared from these monomers have Tg values of less than 40 ^° C., chosen from monomers having a Tg of between 20 ^° C. and 40 ^° C. and / or monomers having a Tg of Tg less than or equal to 20 ^° C., for example a Tg ranging from -100 ° C. to 20 ° C., preferably below 15 ° C., in particular ranging from -80 ° C. to 15 ° C. and better still below 10 ^° C. for example from -50 ° C to 0 ° C to, as described below.

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

methacrylates of formula CH ₂ = C (CH ₃ ) -COOR 1 in which R 1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group; or R is cycloalkyl C ₄ to C _2, preferably C ₈ cycloalkyl Ci _2, such as isobornyl methacrylate,

- acrylates of formula CH ₂ = CH-COOR ₂ wherein R ₂ is cycloalkyl C ₄ to C ₂ such as an isobornyl group or a tert-butyl group,

the (meth) acrylamides of formula:

where R ₇ and R _{8, which are} identical or different, each represent a hydrogen atom or a linear or branched C ₁ -C 12 alkyl group, such as a n-butyl, t-butyl, isopropyl, isohexyl, isooctyl or isononyl group; ; or R ₇ is H and R ₈ is 1,1-dimethyl-3-oxobutyl, and R 'is H or methyl. As an example of monomers, mention may be made of

N-butylacrylamide, N-t-butylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide and N, N-dibutylacrylamide,

- and their mixtures.

The first block is advantageously obtained from at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ and at least one methacrylate monomer of formula CH ₂ = C (CH ₃ ) -COOR ₂ in which R ₂ represents cycloalkyl C ₄ to C _2, preferably C ₈ cycloalkyl Ci _2, such as isobornyl. The monomers and their proportions are preferably chosen so that the glass transition temperature of the first block is greater than or equal to 40 ° C. In one implementation mode, the first block is obtained from: i) at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ wherein R ₂ is cycloalkyl C ₄ to C _2, preferably cycloalkyl C ₈ to Ci _2, such as isobornyl,

- ii) and at least one methacrylate monomer of formula CH ₂ = C (CH ₃₎ -COOR _'2 in which R ₂ is cycloalkyl C ₄ to C _2, preferably a cycloalkyl group C ₈ to C ₂ , such as isobornyl

According to one embodiment, the first block is obtained from at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ in which R ₂ represents a group cycloalkyl Cs to Ci _2, such as isobornyl acrylate, and at least one methacrylate monomer of formula CH ₂ = C (CH ₃₎ -COOR _'2 in which R ₂ is cycloalkyl C ₈ to Ci ₂ ,, such as isobornyl

Preferably, R ₂ and R ' ₂ independently or simultaneously represent an isobornyl group.

Preferably, the block copolymer comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acrylic acid. The first block can be obtained exclusively from said acrylate monomer and said methacrylate monomer.

The acrylate monomer and the methacrylate monomer are preferably in mass proposals of between 30:70 and 70:30, preferably between 40:60 and 60:40, in particular of the order of 50:50.

The proportion of the first block is preferably 20 to 90% by weight of the polymer, more preferably 30 to 80% and more preferably 60 to 80%. According to one mode of implementation, the first block is obtained by polymerization of isobornyl methacrylate and isobornyl acrylate.

Second glass transition temperature sequence less than 20 ^° C.

The second sequence preferably has a glass transition temperature Tg less than or equal to 20 ⁰ C, for example a Tg ranging from -100 ⁰ C to 20 ° C, preferably less than or equal to 15 ° C, especially ranging from -8O ⁰ C at 15 ° C and better still less than or equal to 10 ⁰ C, for example ranging from -100 ⁰ C to 10 ⁰ C, in particular ranging from -30 ⁰ C to 10 ⁰ C. The second sequence is issued in whole or in part of one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C.

This sequence can also be called "soft sequence".

The monomer having a Tg of less than or equal to 20 ^° C. (called the second monomer) is preferably chosen from the following monomers:

the acrylates of formula CH ₂ = CHCOOR ₃ ,

R ₃ represents a linear or branched C ₁ to C ₁₂ alkyl group, with the exception of the tert-butyl group, in which one or more heteroatoms chosen from O, N, S are optionally intercalated,

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

R ₄ represents a linear or branched C ₁ -C 12 unsubstituted alkyl group in which one or more heteroatoms selected from O, N and S are optionally intercalated;

- formula of the vinyl esters R ₅ -CO-O-CH = CH ₂ wherein R ₅ represents an alkyl group C ₄ to C ₂ straight or branched;

- vinyl alcohol and alcohol ethers of C ₂ to C _4, - N-alkyl, C ₄ to C ₂ acrylamides, such as N-octylacrylamide,

- and their mixtures.

The monomers having a Tg of less than or equal to 20 ° C are preferred isobutyl acrylate, 2-ethylhexyl acrylate or mixtures thereof in all proportions. Each of the first and second sequences may contain, in a minority proportion, at least one constituent monomer of the other sequence.

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

Each of the first and / or second sequence may comprise, in addition to the monomers indicated above, one or more other monomers called additional monomers, different from the main monomers mentioned above. The nature and amount of this additional monomer (s) are chosen so that the sequence in which they are located has the desired glass transition temperature. This additional monomer is for example chosen from:

ethylenically unsaturated monomers containing at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide and the salts thereof ,

methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₆ in which Re represents a linear or branched alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group being substituted with one or more substituents selected from hydroxyl groups (such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate) and halogen atoms (Cl, Br, I, F), such as methacrylate trifluoroethyl,

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

R ₉ represents an alkyl group of C ₆ to C ₂ linear or branched, in which is (are) optionally intercalated (s) one or more heteroatoms selected from 0, N and S, said alkyl group being substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I, F);

the acrylates of formula CH ₂ = CHCOOR _I0 ,

R ₁₀ represents a linear or branched C ₁ -C 12 alkyl group substituted by one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F), such as 2-hydroxypropyl acrylate acrylate and 2-hydroxyethyl, or R ₀ is alkyl to C ₂ -O-POE (polyoxyethylene) with repetition of the oxyethylene unit 5 to 10 times, for example methoxy-POE, or R represents a polyoxyethylene group comprising from 5 to 10 ethylene oxide units. In particular, the first sequence may comprise, as additional monomer:

- (meth) acrylic acid, preferably acrylic acid,

- tert-butyl acrylate

methacrylates of formula CH ₂ = C (CH ₃ ) -COOR 1 in which R 1 represents a linear or branched, unsubstituted alkyl group containing from 1 to 4 carbon atoms, such as a methyl, ethyl, propyl or isobutyl group; ,

the (meth) acrylamides of formula:

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

The additional monomer can represent 0.5 to 30% by weight of the weight of the polymer. According to one mode of implementation, the polymer of the invention does not contain additional monomer. Preferably, the polymer of the invention comprises at least isobornyl acrylate and isobornyl methacrylate monomers in the first block and isobutyl acrylate and acrylic acid monomers in the second block.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in equivalent proportion by weight in the first block and isobutyl acrylate and acrylic acid monomers in the second block.

Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block, the first block being 70% by weight of the polymer. Preferably, the polymer comprises at least isobornyl acrylate and isobornyl methacrylate monomers in an equivalent proportion by weight in the first block, and isobutyl acrylate and acrylic acid monomers in the second block. Preferably, the Tg sequence greater than 40 ⁰ C representing 70% by weight of the polymer, and acrylic acid representing 5% by weight of the polymer. According to one embodiment, the first sequence does not comprise additional monomer.

According to a preferred embodiment, the second block comprises acrylic acid as additional monomer. In particular, the second block is advantageously obtained from an acrylic acid monomer and from at least one other monomer having a Tg of less than or equal to 20 ^° C.

According to a preferred embodiment, the block ethylenic polymer is a copolymer comprising at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ in which R ₂ represents a C ₅ to C ₁₂ cycloalkyl group and / or at least one methacrylate monomer. formula CH ₂ = C (CH ₃₎ -COOR _'2 in which R ₂ is cycloalkyl C ₈ to Ci _2, at least a second acrylate monomer of formula CH ₂ = CHCOOR ₃ wherein R ₃ represents an alkyl group unsubstituted Ci to Ci ₂ , linear or branched, with the exception of the tert-butyl group, and at least one acrylic acid monomer. Preferably, the copolymer used in the compositions according to the invention is obtained from at least one isobornyl methacrylate monomer, at least one isobornyl acrylate monomer, at least one isobutyl acrylate monomer. and at least one acrylic acid monomer. Advantageously, the copolymer used in the invention comprises from 50 to 80% by weight of methacrylate / isobornyl acrylate mixture, from 10 to 30% by weight of isobutyl acrylate and from 2 to 10% by weight of acid. acrylic.

The block copolymer may advantageously comprise more than 2% by weight of acrylic acid monomers, and especially from 2 to 15% by weight, for example from 3 to 15% by weight, in particular from 4 to 15% by weight, or even from 4 to 15% by weight. 10% by weight of acrylic acid monomers, relative to the total weight of said copolymer.

The constituent monomers of the second block and their proportions are chosen so that the glass transition temperature of the second block is less than or equal to 20 ° C. Intermediate segment

The intermediate segment (also called intermediate sequence) connects the first sequence and the second sequence of the polymer used according to the present invention. The intermediate segment results from the polymerization of: i) the first monomer or monomers, and optionally the additional monomer or monomers, remaining available after their polymerization at a conversion rate of at most 90% to form the first sequence, ii) and the or second monomers, and optionally additional monomer (s) added to the reaction mixture.

The formation of the second sequence is initiated when the first monomers no longer react or become incorporated in the polymer chain either because they are all consumed or because their reactivity no longer allows them to be.

Thus, the intermediate segment comprises the first available monomers, resulting from a conversion rate of these first monomers of less than or equal to 90%, during the introduction of the second monomer or monomers during the synthesis of the polymer. The intermediate segment of the block polymer is a random polymer (can also be called a statistical sequence). That is to say, it comprises a statistical distribution of the first monomer (s) and second monomer (s) and any additional monomer (s) that may be present. Thus, the intermediate segment is a statistical sequence, as are the first sequence and the second sequence if they are not homopolymers (i.e., both are formed from at least two different monomers ).

Process for preparing the copolymer: The ethylenic block copolymer according to the invention is prepared by free radical polymerization, according to the techniques well known in this type of polymerization.

The free radical polymerization is carried out in the presence of an initiator whose nature is adapted, in known manner, depending on the desired polymerization temperature and the polymerization solvent. In particular, the initiator may be chosen from peroxide-functional initiators, oxidation-reduction pairs, or other radical polymerization initiators known to those skilled in the art. In particular, as a peroxide-functional initiator, there may be mentioned, for example: a. peroxyesters, such as terbutylperoxyacetate, tertbutylperbenzoate, tertbutylperoxy-2-ethylhexanoate (Trigonox 21 S from Akzo Nobel), 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane ( Trigonox 141 from Akzo Nobel); b. peroxydicarbonates, such as di-isopropylperoxydicarbonate; vs. peroxycetones, such as methyl ethyl ketone peroxide; d. hydroperoxides, such as hydrogen peroxide (H ₂ O ₂ ), terbutylhydroperoxide; e. diacyl peroxides, such as acetyl peroxide, benzoyl peroxide; f. dialkyl peroxides, such as di-tert-butyl peroxide; boy Wut. inorganic peroxides, such as potassium peroxodisulfate (K ₂ S ₂ O ₈ );

As an initiator in the form of oxidation-reduction pair, mention may be made of the potassium thiosulfate + potassium peroxodisulphate pair, for example.

According to a preferred embodiment, the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms. Preferably, the initiator used is the 2.5- Bis (2-ethylhexanoylperoxy) -2,5-dimethyl hexane sold under the reference Trigonox ^® 141 from Akzo Nobel.

The block copolymer used according to the invention is prepared by free radical polymerization and not by controlled or living polymerization. In particular, the polymerization of the ethylenic block copolymer is carried out in the absence of control agents, and in particular in the absence of control agent conventionally used in living or controlled polymerization processes such as nitroxides, alkoxyamines dithioesters, dithiocarbamates, dithiocarbonates or xanthates, trithiocarbonates, copper catalysts, for example.

As previously indicated, the intermediate segment is a statistical sequence, as is the first sequence and the second sequence if they are not homopolymers (i.e., both are formed from at least two different monomers).

The block copolymer may be prepared by free radical polymerization, in particular by a process comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one glass transition monomer or equal to 40 ⁰ C, the less than a glass transition monomer less than or equal to 20 ⁰ C according to the following sequence: is poured into the reactor, a part of the polymerization solvent and optionally a portion of the initiator and monomers of the first casting mixture that the it is heated to a reaction temperature of between 60 and 120 ^° C., the said at least one first monomer of Tg greater than or equal to 40 ^° C. and, if appropriate, part of the initiator, which is then poured in a first casting. is allowed to react for a time T corresponding to a conversion rate of said monomers of 90% maximum, then poured into the reactor, in a second casting, again water of the polymerization initiator, said at least one second glass transition monomer less than or equal to 20 ^° C., which is allowed to react for a time T 'at the end of which the conversion rate of said monomers reaches a plateau, returns the reaction mixture to room temperature.

Preferably, the copolymer may be prepared by free radical polymerization, in particular by a process consisting of mixing, in one and the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one lower glass transition monomer or equal to 20 ° C, at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ wherein R ₂ is cycloalkyl C ₄ to C _2, and at least one methacrylate monomer of formula CH ₂ = C (CH ₃₎ -COOR _'2 in which R ₂ is cycloalkyl C ₄ to C ₂ according to the following step sequence: pouring into the reactor, part of the polymerization solvent and optionally part of the initiator and monomers of the first casting, which mixture is heated to a reaction temperature of between 60 and 120 ° C., the at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ is then poured in a first casting, and said at least one less methacrylate monomer of formula CH ₂ = C (CH ₃ ) -COOR ' ₂ as monomers with a Tg of greater than or equal to 40 ° C, and optionally a part of the initiator which is allowed to react for a period of time T corresponding to a conversion rate of said monomers of 90% maximum, then poured into the reactor, in a second casting, again the polymerization initiator, the acrylic acid monomer and said at least one glass transition monomer less than or equal to 20 ⁰ C, which is left react for a time T 'after which the conversion rate of said monomers reaches a plateau,

the reaction mixture is brought back to ambient temperature.

By polymerization solvent is meant a solvent or a mixture of solvents. In particular, as usable polymerization solvent include: ketones at room temperature such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone; propylene glycol ethers which are liquid at ambient temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, isopentyl; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes that are liquid at room temperature, such as decane, heptane, dodecane, isododecane, cyclohexane or isohexadecane; aromatic cyclic compounds which are liquid at room temperature, such as toluene and xylene; aldehydes which are liquid at room temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof.

Conventionally, the polymerization solvent is a volatile oil having a flash point of less than 80 ^° C. The flash point is measured in particular according to ISO Standard 3679. The polymerization solvent may be chosen in particular from ethyl acetate, butyl acetate, alcohols such as isopropanol, ethanol, aliphatic alkanes such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

According to another embodiment, the copolymer can be prepared by free radical polymerization according to a preparation process, comprising mixing, in the same reactor, a polymerization solvent, an initiator, at least one lower glass transition monomer or equal to 20 ^° C., and at least one monomer with a Tg of greater than or equal to 40 ^° C., according to the following step sequence: a part of the polymerization solvent and possibly a portion of the initiator and monomers of the first casting, which mixture is heated to a reaction temperature between 60 and 120 ° C, is then poured, in a first casting, said at least one glass transition monomer less than or equal to 20 ⁰ C and optionally a part of the initiator which is allowed to react for a duration T corresponding to a conversion rate of said monomers of 90% maximum, then poured into the reactor, e n a second casting, again of the polymerization initiator, said at least one monomer of Tg greater than or equal to 40 ⁰ C, which is allowed to react for a time T 'after which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought to room temperature.

According to a preferred embodiment, the copolymer can be prepared by free radical polymerization according to a preparation process, comprising mixing, in the same reactor, a polymerization solvent, an initiator, an acrylic acid monomer, at least one monomer of glass transition less than or equal to 20 ⁰ C, at least one monomer of Tg greater than or equal to 40 ⁰ C, and in particular as monomers of Tg greater than or equal to 40 ° C, at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ wherein R ₂ is cycloalkyl C ₄ to C _2, and at least a methacrylate monomer of formula CH ₂ = C (CH ₃ ) -COOR' 2 in which R '2 represents a C ₄ to C ₁₂ cycloalkyl group, according to the following step sequence: a portion of the solvent is poured into the reactor; of polymerization and possibly a portion of the initiator and monomers of the first casting, which mixture is heated to a reaction temperature of between 60 and 120 ^° C., the acrylic acid monomer is then poured in a first casting. and said at least one glass transition monomer less than or equal to 20 ^° C. and optionally a part of the initiator which is allowed to react for a duration T corresponding to a conversion rate of said monomers of 90% maximum, is then poured in the reactor, in a second casting, again of the polymerization initiator, said at least one acrylate monomer of formula CH ₂ = CH-COOR ₂ and said at least one methacrylate monomer of formula CH ₂ = C (CH ₃ ) -COOR ' ₂ , as monomer of Tg greater than or equal to 40 ⁰ C, which is allowed to react for a time T 'at the end of which the conversion rate of said monomers reaches a plateau, the reaction mixture is brought back to room temperature.

The polymerization temperature is preferably of the order of 90 ^° C. The reaction time after the second casting is preferably between 3 and 6 hours.

Block copolymers such as those described above are described in particular in patent applications EP-A-1411069 and EP-A-1882709. The film-forming polymer may be chosen from block or static polymers and / or copolymers comprising, in particular, polyurethanes, polyacrylics, silicones, fluorinated polymers, butyl gums, copolymers of ethylene, natural gums and polyvinyl alcohols, and mixtures thereof. The monomers of the block or static copolymers comprising at least one combination of monomers whose polymer results in a glass transition temperature below room temperature (25 ^° C.) may be chosen from, in particular, butadiene, ethylene, propylene, acrylic, methacrylic, isoprene, isobutene, silicone and mixtures thereof.

Vinyl polymer grafted with a carbosiloxane dendrimer

According to a second embodiment, the composition according to the invention may comprise, as film-forming polymer, a film-forming polymer chosen from vinyl polymers comprising at least one unit derived from a carbosiloxane dendrimer. The vinyl polymer may in particular have a skeleton and at least one side chain, which comprises a carbosiloxane dendrimer structure. The term "carbosiloxane dendrimer structure" in the context of the present invention represents a molecular structure having branched groups having high molecular weights, said structure having a high regularity in the radial direction from the backbone bond. Such carbosiloxane dendrimer structures are described in the form of a highly branched siloxane-silylalkylene copolymer in Japanese Laid-open Patent Application Kokai 9-171,154.

The vinyl polymer contains units derived from carbosiloxane dendrimers which may be represented by the following general formula: wherein R ¹ represents an aryl group or an alkyl group having 1 to 10 carbon atoms, and X ¹ represents a silylalkyl group which, when i = 1, is represented by the formula:

in which R ¹ is the same as defined above, R ² represents an alkylene group having 2 to 10 carbon atoms, R ³ represents an alkyl group having 1 to 10 carbon atoms, X ^{1 + 1} represents an atom hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a 'is an integer of 0 to 3; Y represents a radical-polymerizable organic group selected from the group consisting of an organic group which contains a methacrylic group or an acrylic group and which is represented by the formulas: and and

in which R ⁴ represents a hydrogen atom or an alkyl group, R ⁵ represents an alkylene group having from 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, or a butylene group, the methylene group and the propylene group being preferred; and an organic group which contains a styryl group and which is represented by the formula:

in which R ⁶ represents a hydrogen atom or an alkyl group, R ⁷ represents an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, the methyl group being preferred, R ⁸ represents an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, the ethylene group being preferred, b is an integer of 0 to 4, and c is 0 or 1 so that if c is 0, - (R ⁸ ) _c - represents a bond.

R ¹ represents an aryl group or an alkyl group having 1 to 10 carbon atoms, where the alkyl group is preferably represented by a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a group isopropyl, isobutyl, cyclopentyl, cyclohexyl, and aryl is preferably phenyl and naphthyl, where methyl and all.

The vinyl polymer which contains a carbosiloxane dendrimer structure may be the polymerization product of

(A) from 0 to 99.9 parts by weight of a vinyl monomer; and

(B) from 100 to 0.1 parts by weight of a carbosiloxane dendrimer which contains a radical-polymerizable organic group, represented by the general formula:

wherein Y represents a radical-polymerizable organic group, R ¹ represents an aryl group or an alkyl group having 1 to 10 carbon atoms, and X ¹ represents a silylalkyl group which, when i = 1, is represented by the formula:

in which R ¹ is the same as defined above, R ² represents an alkylene group having 2 to 10 carbon atoms, R ³ represents an alkyl group having 1 to 10 carbon atoms, X ^{1 + 1} represents an atom hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, or the silylalkyl group defined above with i = i + 1; i is an integer from 1 to 10 which represents the generation of said silylalkyl group, and a 'is an integer of 0 to 3; wherein said radical-polymerizable organic group contained in component (B) is selected from the group consisting of organic group which contains a methacrylic group or an acrylic group and which is represented by the formulas:

and and

wherein R ⁴ represents a hydrogen atom or an alkyl group, R ⁵ represents an alkylene group having 1 to 10 carbon atoms; and an organic group which contains a styryl group and which is represented by the formula:

wherein R ⁶ represents a hydrogen atom or an alkyl group, R ⁷ represents an alkyl group having 1 to 10 carbon atoms, R ⁸ represents an alkylene group having 1 to 10 carbon atoms, b is a whole number from 0 to 4, and c is 0 or 1. In the case where c is 0, - (R ⁸ ) _c - represents a bond.

The vinyl monomer component (A) in the vinyl polymer is a vinyl type monomer which contains a radical-polymerizable vinyl group. There is no particular limitation with respect to the type of such monomer. The following are examples of this vinyl type monomer: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, or a lower alkyl analogue methacrylate; glycidyl methacrylate; n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, methacrylic acid, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, or a higher analogous methacrylate; vinyl acetate, vinyl propionate, or a lower analogous fatty acid vinyl ester; vinyl caproate, vinyl 2-ethylhexoate, vinyl laurate, vinyl stearate, or a higher analogous fatty acid ester; styrene, vinyltoluene, benzyl methacrylate, phenoxyethyl methacrylate, vinylpyrrolidone, or analogous aromatic vinyl monomers; methacrylamide, N-methylolmethacrylamide, N-methoxymethylmethacrylamide, risobutoxymethoxymethacrylamide, N, N-dimethylmethacrylamide, or analogous vinyl monomers which contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or monomers vinyl analogues which contain hydroxyl groups; methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or vinyl-like monomers which contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol methacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl ether and vinyl, or a vinyl-like monomer with ether linkages; methacryloxypropyltrimethoxysilane, polydimethylsiloxane having a methacrylic group on one of its molecular ends, polydimethylsiloxane having a styryl group on one of its molecular ends, or a silicone-like compound having unsaturated groups; butadiene; vinyl chloride; vinylidene chloride; methacrylonitrile; dibutylfumarate; anhydrous maleic acid; anhydrous succinic acid; methacryl ether and glycidyl ether; an organic salt of an amine, an ammonium salt, and an alkali metal salt of methacrylic acid, itaconic acid, crotonic acid, maleic acid, or fumaric acid ; an unsaturated monomer polymerizable with radicals having a sulfonic acid group such as a styrene sulfonic acid group; a quaternary ammonium salt derived from methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; and an ester of methacrylic acid of an alcohol having a tertiary amine group such as an ester of methacrylic acid and diethylamine.

The multifunctional vinyl-type monomers can also be used. The following are examples of such compounds: trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-dimethacrylate and the like. hexanediol, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethylmethacrylate, tris (2-hydroxyethyl) isocyanurate dimethacrylate, tris- (2-hydroxyethyl) isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on both ends, or silicone analogs having unsaturated groups.

The carbosiloxane dendrimer, which is component (B), is represented by the following formula:

The following is a preferred example of a radical-polymerizable organic group Y: acryloxymethyl group, 3-acryloxypropyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group , a 4- (2-propenyl) phenyl group, a 3- (2-propenyl) phenyl group, a 2- (4-vinylphenyl) ethyl group, a 2- (3-vinylphenyl) ethyl group, a vinyl group, a allyl group, a methallyl group, and a 5-hexenyl group. R ¹ represents an alkyl group or an aryl group having 1 to 10 carbon atoms, wherein the alkyl group may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, a isobutyl group, cyclopentyl group, or cyclohexyl group; and the aryl group may be a phenyl group or a naphthyl group. The methyl and phenyl groups are particularly preferred, the methyl group being most preferred. X ¹ represents a silylalkyl group which is represented by the following formula, when i is equal to one:

wherein R ² represents an alkylene group having 2 to 10 carbon atoms, such as an ethylene group, a propylene group, a butylene group, a hexylene group, or a similar linear alkylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, a 1,4-dimethylbutylene group, or a similar branched alkylene group. Ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene are most preferred. R ³ represents an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, and isopropyl. R ¹ is the same as defined above. X ^{1 + 1} represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or the silylalkyl group with i = i + 1. a 'is an integer of 0 to 3, and i is an integer from 1 to 10 which indicates the generation number which represents the number of repeats of the silylalkyl group.

For example, when the generation number is one, the carbosiloxane dendrimer may be represented by the first general formula shown below, wherein Y, R ¹ , R ² and R ³ are the same as defined above, R ¹² represents a hydrogen atom or is identical to R ¹ ; a ¹ is identical to a '. Preferably, the total average number of OR ³ groups in a molecule is in the range of 0 to 7. When the generation number is 2, the carbosiloxane dendrimer can be represented by the second general formula shown below, in which Y, R ¹ , R ² , R ³ and R ¹² are the same as defined above; a ¹ and a ² represent the a 'of the indicated generation. Preferably, the total average number of OR ³ groups in a molecule is in the range of 0 to 25. In the case where the generation number is 3, the carbosiloxane dendrimer is represented by the third general formula shown below. wherein Y, R ¹ , R ² , R ³ and R ¹² are the same as defined above; a ¹ , a ² and a ³ represent the a 'of the indicated generation. Preferably, the total average number of OR ³ groups in a molecule is in the range of 0 to 79.

A carbosiloxane dendrimer which contains a radically polymerizable organic group can be represented by the following average structural formulas:



The carbosiloxane dendrimer may be made by the process for making a branched silalkane siloxane described in Japanese Patent Application Hei 9-171,154. For example, it may be produced by subjecting an organosilicon compound containing an atom to a hydrosilylation reaction. hydrogen atom connected to a silicon atom, represented by the following general formula:

and an organosilicon compound that contains an alkenyl group. In the above formula, the organosilicon compound may be represented by 3-methacryloxypropyltris- (dimethylsiloxy) silane, 3-acryloxypropyltris- (dimethylsiloxy) silane, and 4-vinylphenyltris (Dimethylsiloxy) silane. The organosilicon compound which contains an alkenyl group may be represented by vinyltris- (trimethylsiloxy) silane, vinyltris- (dimethylphenylsiloxy) silane, and 5-hexenyltris- (trimethylsiloxy) silane. The hydrosilylation reaction is carried out in the presence of a chloroplatinic acid, a vinylsiloxane and platinum complex, or a transition metal-like catalyst.

In the vinyl polymer which contains a dendrimer structure, the ratio of polymerization between components (A) and (B), in terms of weight ratio between (A) and (B), can be in a range of 0/100. at 99.9 / 0.1, and preferably in a range of 1/99 to 99/1. A ratio between components (A) and (B) of 0/100 means that the compound becomes a homopolymer of component (B).

The vinyl polymer contains a carbosiloxane dendrimer structure and this polymer can be obtained by the copolymerization of the components (A) and (B), or by the polymerization of the single component (B). The polymerization may be free-radical polymerization or ionic polymerization, however radical polymerization is preferred. The polymerization can be carried out by causing a reaction between the components (A) and (B) in a solution for a period of 3 to 20 hours in the presence of a radical initiator at a temperature of 50 ⁰ C to 150 ⁰ C. A suitable solvent for this purpose is hexane, octane, decane, cyclohexane, or a similar aliphatic hydrocarbon; benzene, toluene, xylene, or a similar aromatic hydrocarbon; diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, or similar ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-isobutyl ketone, or similar ketones; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, or analogous esters; methanol, ethanol, isopropanol, butanol, or similar alcohols; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, octamethyltrisiloxane, or a similar organosiloxane oligomer. A radical initiator may be any compound known in the art for conventional radical polymerization reactions. Specific examples of such radical initiators are 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) or compounds azobic analogues; benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, or a similar organic peroxide. These radical initiators can be used alone or in a combination of two or more. The radical initiators may be used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of components (A) and (B). A chain transfer agent can be added. The chain transfer agent may be 2-mercaptoethanol, butyl mercaptan, n-dodecyl mercaptan, 3-mercaptopropyltrimethoxysilane, a polydimethylsiloxane having a mercaptopropyl group or a mercapto-like compound; methylene chloride, chloroform, carbon tetrachloride, butyl bromide, 3-chloropropyltrimethoxysilane, or a similar halogenated compound. In the manufacture of the vinyl polymer, after the polymerization, the unreacted residual vinyl monomer can be removed under vacuum heating conditions.

To facilitate mixing of the cosmetics raw material, the number average molecular weight of the vinyl polymer which contains a carbosiloxane dendrimer may be selected in the range of from 3,000 to 2,000,000, preferably from 5,000 to 800,000. 000. It can be a liquid, an eraser, a paste, a solid, a powder, or any other form. Preferred forms are solutions consisting of dilution in solvents, a dispersion, or a powder.

The vinyl polymer may be a dispersion of a vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain, in a liquid such as a silicone oil, an organic oil, an alcohol, or water.

The vinyl polymer having a carbosiloxane dendrimer structure in its side molecular chain, in this embodiment, is the same as that described above. The liquid can be a silicone oil, an organic oil, an alcohol, or water. The silicone oil may be a dimethylpolysiloxane having both molecular ends capped with trimethylsiloxy groups, a copolymer of methylphenylsiloxane and dimethylsiloxane having both trimethylsiloxy-terminated molecular ends, a copolymer of methyl-3,3,3-trifluoropropylsiloxane and dimethylsiloxane having both trimethylsiloxy-capped molecular ends, or similar non-reactive linear silicone oils, as well as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, or a similar cyclic compound. In addition to the nonreactive silicone oils, modified polysiloxanes having functional groups such as silanol groups, amino groups, and polyether groups on the ends or within the side molecular chains may be used. Organic oils may be paraffin oil, isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate, cetyl myristate, 2-octyldodecyl myristate; isopropyl palmitate, 2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyl oleate, myristyl lactate, cetyl lactate, lanolin acetate, stearic alcohol, cetostearyl alcohol, oleic alcohol, avocado oil, almond oil, olive oil, cocoa oil, jojoba oil, gum, sunflower oil, soybean oil, camellia oil, squalane, castor oil, mink oil, cottonseed oil, coconut oil egg yolk oil, beef tallow, lard, polypropylene glycol monooleate, neopentyl glycol 2-ethylhexanoate, or a similar glycol ester oil; triglyceryl isostearate, triglyceride of a coconut oil fatty acid, or a similar polyhydric alcohol ester oil; polyoxyethylene lauryl ether, polyoxypropylene cetyl ether, or a similar polyoxyalkylene ether.

The alcohol may be of any type suitable for use in conjunction with a raw material of cosmetics. For example, it may be methanol, ethanol, butanol, isopropanol or lower alcohols. A solution or dispersion of the alcohol should have a viscosity in the range of 10 to 10 ⁹ mPa at 25 ° C. To improve the feel properties of use in a cosmetic product, the viscosity should be in the range of 100 to 5 x 10 ⁸ mPa.s.

The solutions and dispersions can easily be prepared by mixing the vinyl polymer having a carbosiloxane dendrimer structure, a silicone oil, an organic oil, an alcohol, or water. The liquids may be present in the polymerization step of the vinyl polymer having a carbosiloxane dendrimer structure. In this case, the unreacted residual vinyl monomer should be completely removed by heat treatment of the solution or dispersion under atmospheric or reduced pressure. In the case of a dispersion, the dispersity of the vinyl polymer can be improved by adding a surfactant. Such an agent may be hexylbenzenesulfonic acid, octylbenzenesulfonic acid, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, cetylbenzenesulfonic acid, myristylbenzenesulphonic acid, or anionic surfactants of the sodium salts of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow trimethylammonium hydroxide, coconut trimethylammonium oil hydroxide, or a similar cationic surfactant; a polyoxyalkylene alkyl ether, a polyoxyalkylenealkylphenol, a polyoxyalkylene alkyl ester, polyoxyalkylene sorbitol ester, polyethylene glycol, polypropylene glycol, a diethylene glycol trimethylnonanol ethylene oxide additive, and surfactants; Nonionic, polyester-type actives, as well as mixtures. In addition, the solvents and dispersions can be combined with iron oxide suitable for use with cosmetics, or a similar pigment, as well as zinc oxide, titanium oxide, silicon oxide, mica, talc or similar inorganic oxides in powder form. In the dispersion, a mean diameter of the vinyl polymer particles may be in the range of 0.001 to 100 microns, preferably 0.01 to 50 microns. Indeed, beyond the recommended range, a cosmetic product mixed with the emulsion will not have a sensation good enough on the skin or to the touch, nor sufficient spreading properties nor a pleasant sensation.

The vinyl polymer contained in the dispersion or solution may have a concentration in a range between 0.1 and 95% by weight, preferably between 5 and 85% by weight. However, for ease of handling and mixing, the range should preferably be from 10 to 75% by weight.

The vinyl polymer may be one of the polymers described in the examples of application EP0963751 or for example the product Tl B-4-200 marketed by Dow Corning. According to one embodiment, the vinyl polymer further comprises at least one fluorinated organic group.

Particularly preferred are structures in which the vinyl polymerized units constitute the backbone and carbosiloxane dendritic structures as well as fluorinated organic groups are attached to side chains.

The fluorinated organic groups may be obtained by substituting with fluorine atoms all or part of the hydrogen atoms of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl and heptyl groups, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl, and other alkyl groups of 1 to 20 carbon atoms, as well as alkyloxyalkylene groups of 6 to 22 carbon atoms.

The groups represented by the formula: - (CH ₂₎ χ- (CF ₂₎ y R ¹³ are suggested as examples of fluoroalkyl groups obtained by substituting fluorine atoms for hydrogen atoms of alkyl groups. In the formula, the index "x" and 0, 1, 2 or 3 and "y" and an integer of 1 to 20. R ¹³ is an atom or a group selected from a hydrogen atom, a fluorine atom , - (CH (CF ₃₎ ₂ -. or CF (CF ₃₎ ₂ such alkyl groups substituted with fluorine are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulas presented below -CF _3,. - C ₂ F ₅ , -NC ₃ F ₇ , -CF (CF ₃ ) ₂ , -NC ₄ F ₉ , CF ₂ CF (CF ₃ ) ₂ , -NC ₅ Fn, -NC ₆ F ₁₃ , -nC ₈ F ₁₇ , -CH ₂ CF ₃ , - (CH (CF ₃ ) ₂ , CH ₂ CH (CF ₃ ) ₂ -CH ₂ (CF ₂ ) ₂ F, -CH ₂ (CF ₂ ) ₃ F, -CH ₂ (CF ₂ ) ₄ F, -CH ₂ (CF ₂ ) ₆ F, -CH ₂ (CF ₂ ) ₈ F, -CH ₂ CH ₂ CF ₃ , -CH ₂ CH ₂ (CF ₂ ) ₂ F, -CH ₂ CH ₂ ( CF ₂₎ ₃ F, -CH ₂ CH ₂ (CF ₂₎ ₄ F,

CH ₂ CH ₂ (CF ₂ ) ₆ F, -CH ₂ CH ₂ (CF ₂ ) ₈ F, -CH ₂ CH ₂ (CF ₂ ) ₁₀ F, -CH ₂ CH ₂ (CF ₂ ) ₁₂ F, -CH ₂ CH ₂ (CF ₂ ) ₁₄ F, - CH ₂ CH ₂ (CF ₂ ) ₁₆ F, -CH ₂ CH ₂ CH ₂ CF ₃ , -CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ F, -CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ H -CH ₂ (CF ₂ ) ₄ H, and -CH ₂ CH ₂ (CF ₂ ) ₃ H. The groups represented by

-CH ₂ CH ₂ - (CF ₂ ) _m -CFR ¹⁴ - [OCF ₂ CF (CF ₃ )] _n -OC ₃ F ₇ are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for hydrogen atoms of alkoxyoxyalkylene groups. In the formula, the index "m" is 0 or 1, "n" is 0, 1, 2, 3, 4, or 5, and R ¹⁴ is a fluorine atom or CF ₃ . Such fluoroalkyloxyfluoroalkylene groups are exemplified by perfluoroalkyloxyfluoroalkylene groups represented by the formulas set forth below. -CH ₂ CH ₂ CF (CF ₃ ) - [OCF ₂ CF (CF ₃ )] _n -OC ₃ F ₇ , -CH ₂ CH ₂ CF ₂ CF ₂ - [OCF ₂ CF (CF ₃ )] _n -OC ₃ F ₇ . The number average molecular weight of the vinyl polymer used in the present invention may range from about 3000 to about 2,000,000, and more preferably from about 5,000 to about 800,000.

This type of fluorinated vinyl polymer can be obtained by adding a vinyl monomer (B) which does not have a fluorinated organic group in the molecule on a vinyl monomer containing fluorinated organic groups in the molecule (A), and a dendrimer carbosiloxane (C) containing radical-polymerizable organic groups represented by the general formula (III): wherein Y is a radical polymerizable organic group and R ¹ and X ¹ are as above and subjecting them to copolymerization. The vinyl monomers (A) containing fluorinated organic groups in the molecule are preferably monomers represented by the general formula: - (CH ₂ ) = CR ¹⁵ COOR ^f . In the formula, R ¹⁵ is a hydrogen atom or a methyl group, R ^f is a fluorinated organic group exemplified by the fluoroalkyl and fluoroalkyloxyfluoroalkylene groups described above. Compounds represented by the formulas presented below are suggested as specific examples of component (A). In the formulas below, "z" is an integer from 1 to 4.

CH ₂ = CCH ₃ COO-CF ₃ . CH ₂ = CCH ₃ COO-C ₂ FS. CH ₂ = ≈CCH ₃ COO-nC ₃ F ₇ . CH ₂ = CCH ₃ COO-CF (CF ₃ ) ₂ . CH ₂ = CCH ₃ COO-nC ₄ F ₉ . CH ₂ = CCH ₃ COO-CF ₂ CF (CF ₃ ) ₂ . CH ₂ = CCH ₃ COO-nC ₅ F ₁₁ . CH ₂ = CCH ₃ COO _n C ₆ F _13. CH ₂ -CCH ₃ COO-nC ₈ F ₁₇ . CH ₂ = CCH ₃ COO-CH ₂ CF ₃ . CH ₂ = CCH ₃ COO-CH (CF ₃ ) ₂ . CH ₂ = CCH ₃ COO-CH ₂ CH (CF ₃ ) ₂ . CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) 2F.

CH ₂ = CCH ₃ COO-CH ₂ (CF ₂₎ ₃ F CH ₂ = CCH ₃ COO-CH ₂ (CFz) ₄ F CH ₂ = CCH ₃ COO-CH ₂ (CF ₂₎ ₆ CH ₂ = F. CCH ₃ COO-CH ₂ (CF ₂ ) ₈ F.CH ₂ = CCH ₃ CCO-CH ₂ CH ₂ CF ₃ . CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CFa) ₂ F.CH ₂ = CCHiCOOCH ₂ CH ₂ (CF ₂ ) ₃ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₄ F . CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂₎ ₆ F CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CFJ) ₈ CH ₂ = F. CCHJCOO-CH ₂ CH ₂ (CF ₂₎ ₁₀ F. CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ )! ₂ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₁₄ F. CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) I 6 _F.CH ₂ CH ₃ COO-CH ₂ CH ₂ CH ₂ CF ₃ . CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ F.CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ H.CH ₂ = CCH ₃ COO-CH ₂ ( CF ₂ ) ₄ H.CH ₂ -CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₃ H.

CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF (CF ₃₎ - [OCF ₂ CF (CF _3)] _z -O-C ₃ F _7. CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF ₂ CF ₂ - [OCF ₂ CF (CF _3)] _z -O-C ₃ F _7. CH ₂ = CHCOO-CF _3. CH ₂ = CHCOO-C ₂ F ₅ . CH ₂ = CHCOO-nC ₃ F ₇ . CH ₂ = CHCOO-CF (CF ₃ ) ₂ . CH ₂ = CHCOO-HC ₄ F ₉ . CH 2 = CHCOO-CF ₂ CF (CF ₃ ) ₂ . CH ₂ -CHCOO-IICSFH. -CHCOO- CH ₂ HC ₆ F _3. CH ₂ = CHCOO-C ₈ F ₁₇ . CH ₂ -CHCOO-CH ₂ CF ₃ . CHrCHCUO-CHCF ₃ ) 2. CH ₂ = CHCOO-CH ₂ CH (CF ₃ ) Z. CH ₂ = CHCOO-CH (CF ₂ ) ₂ F -CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₃ F.CH ₂ = CHCOO-CH ₂ (CF 1) ₄ F, CH ₂ = CHCOO-CH ₂ (CF ₂ ) _O F, CH ₂ = CHCOO-CH ₂ (CF a) ₈ F CH ₂ = CHCOO-CH ₂ CH ₂ CF _3, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂₎ ₂ F.

CH ₂ = CHCOO-CH ₂ CH ₂ (CF _I) F _{_3.} CH ₂ = CHCOO-CH ₂ Cl ₂ (CF ₂ ) ΦF. CH ₃ = CHCOO-CH ₂ CH ₂ (CF ₂ ) _δ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₈ F. CH ₂ -CHCOO-CH ₂ CH ₂ (CF ₂ ) _IO F. CH ₂ -CHCOO-CH ₂ CH ₂ (CF ₂ ) ₁₂ F.CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ J ₁₄ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CFI) ₁₆ F.CH ₂ = CHCOO- CH ₂ CH ₂ CH ₂ CF ₃ , CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ (CF _I ) ₂ F.CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ (CF) ₂ H.CH ₂ = CHCOO-CH ₂ (CF ₂ ) 4H, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) JH.

CH ₂ = CHCOO-CH ₂ CH ₂ CF (CF ₃ HQCF ₂ CF (CF _3)] _z -O-C ₃ F ₇ CH ₂ = CHCOO-CH ₂ CH ₂ CF ₂ CF ₂ -. [OCF ₂ CF (CF ₃₎ ] _Z- OC ₃ F ₇ .

Of these, the vinyl polymers represented by the formulas set forth below are preferable.

CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₆ F CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) SF. CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) β F, CH ₂ = CCH ₃ COO-CH ₃ CH ₂ (CFa) ₈ F. CH ₂ = CHCOO-CH ₂ CF ₃ . CH ₂ -CCH ₃ COO-CH ₂ CF ₃ The vinyl polymers represented by the formulas presented below are particularly preferable.

CH ₂ = CHCOO-CH ₂ CF ₃ , CH ₂ CCCH ₃ COO-CH ₂ CF ₃ .

The vinyl monomers (B) which do not contain fluorinated organic groups in the molecule may be any monomers having radical-polymerizable vinyl groups which are exemplified, for example, by methyl acrylate, methyl methacrylate or acrylate. ethyl, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and other lower alkyl acrylates or methacrylates; glycidyl acrylate, glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl acrylate , n-hexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, and other higher acrylates and methacrylates; vinyl acetate, vinyl propionate, and other lower fatty acid vinyl esters; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate, and other higher fatty acid esters; styrene, vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone, and other vinyl aromatic monomers; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and other amino vinyl monomers, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N methoxymethylacrylamide, N-methoxymethylmethacrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, and other vinyl amide monomers; hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylic acid alcohol, methacrylic acid hydroxypropyl alcohol and other hydroxy vinyl monomers; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and other carboxylic acid vinyl monomers; tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethyleneglycol acrylate, ethoxydiethyleneglycol methacrylate, polyethyleneglycol acrylate, polyethyleneglycol methacrylate, polypropyleneglycol monoacrylate polypropylene glycol monomethacrylate, hydroxybutylvinylether, cetylvinylether, 2-ethylhexylvinylether and other ether-linked vinyl monomers; acryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, polydimethylsiloxanes containing acrylic or methacryl groups at one of the ends, polydimethylsiloxanes containing alkenylaryl groups at one of the ends and other silicone compounds containing unsaturated groups; butadiene; vinyl chloride; vinylidene chloride, acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride; dodecylsuccinic anhydride; acrylglycidyl ether, methacrylglycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, alkali metal salts, ammonium salts and organic amine salts of acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other radical-polymerizable unsaturated carboxylic acids, radical-polymerizable unsaturated monomers containing sulfonic acid groups such as styrene sulfonic acid and their alkali metal salts, their ammonium salts and their organic amine salts; quaternary ammonium salts derived from acrylic acid or methacrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, methacrylic acid esters of a tertiary amine alcohol such as diethylamine ester, methacrylic acid and their quaternary ammonium salts.

In addition, it is also possible to use, as vinyl monomers (B), the polyfunctional vinyl monomers which are exemplified, for example, by trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate and diacrylate. ethylene glycol, ethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, diacrylate 1,6-hexanediol, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl acrylate, trimethylolpropanetrioxyethyl methacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, dimethacrylate tris (2-hydroxyethyl) isocyanur ate, tris (2-hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, polydimethylsiloxane whose both ends of the molecular chain are blocked by alkenylaryl groups, and other silicone compounds with unsaturated groups .

With respect to the above-mentioned ratio in which component (A) and component (B) are copolymerized, the weight ratio of compound (A) to compound (B) should be in the range of 0.1: 99.9 to 100: 0, and preferably in the range 1: 99 to 100: 0. The carbosiloxane dendrimer (C) is represented by the general formula (III) indicated below. above. In formula (III), Y is a radical-polymerizable organic group, the type of which is not subject to any special limitations since it is an organic group capable of undergoing a reaction. radical addition. Acryl and methacryl organic groups, organic alkenyl aryl groups, or alkenyl groups of 2 to 10 carbon atoms represented by the general formulas set forth below are suggested by way of specific examples.

In the formulas, R ⁴ and R ⁶ are hydrogen atoms or methyl groups, R ⁵ and R ⁸ are alkylene groups of 1 to 10 carbon atoms, and R ⁷ is an alkyl group of 1 to 10 carbon atoms. carbon. The index "b" is an integer of 0 to 4, and "c" is 0 or 1. Acryloxymethyl, 3-acryloxypropyl, methacryloxymethyl, 3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl, 4- (2-propenyl) Phenyl, 3- (2-propenyl) phenyl, 2- (4-vinylphenyl) ethyl, 2- (3-vinylphenyl) enyl, vinyl, allyl, methallyl, and 5-hexenyl are suggested as examples of such organic groups. polymerizable radicals. The "i" exponent in formula (II) which is an integer of 1 to 10 is the number of generations of said silylalkyl group, that is the number of times that the silylalkyl group is repeated. Thus, the carboxyloxane dendrimer of this component with a generation number of 1 is represented by the general formula:

(wherein Y, R ¹ , R ² , and R ³ are as above and R ¹² is hydrogen or as R ¹ described above.) The index "a ¹ " is an integer of 0 to 3, the average total of "a ¹ " per molecule being 0 to 7). The carbosiloxane dendrimers of this component with a generation number of 2 are represented by the general formula:

(where Y, R ¹ , R ² , R ³ and R ¹² are as above and the indices "a ¹ " and "a ² " are integers from 0 to 3, the average total of "a ¹ " and "a ² " per molecule being from 0 to 25). The carbosiloxane dendrimers of this component with a generation number of 3 are represented by the general formula:

(wherein Y, R ¹ , R ² , R ³ and R ¹² are as above and the indices "a ¹ ", "a ² " and "a ³ " are integers from 0 to 3, the average total of "a ¹ ", "a ² " and "a ³ " per molecule being from 0 to 79).

Component (C) is exemplified by carbosiloxane dendrimers represented by average composition formulas shown below.

The carbosiloxane dendrimers of component (C) can be prepared using the preparation method for branched siloxane / silakylene copolymers described in EP1055674. For example, they can be prepared by subjecting organic silicone compounds to alkenyl and silicone compounds comprising silicon-bonded hydrogen atoms represented by the general formula:

(wherein R ¹ and Y, are as above) to a hydrosilation reaction. For example, 3-methacyloxypropyltris (dimethylsiloxy) silane, 3-acryloxypropyltris (dimethylsiloxy) silane, and 4-vinylphenyltris (dimethylsiloxy) silane are used as the silicon compounds represented by the above formula. Vinyltris (trimethylsiloxy) silane, vinyltris (dimethylphenylsiloxy) silane, and 5-hexenyltris (trimethylsiloxy) silane are used as organic silicon to alkenyl compounds. In addition, it is best to perform the hydrosilation reaction in the presence of a transition metal catalyst such as chloroplatinic acid and platinum / vinylsiloxane complex.

The copolymerization ratio of the component (C), in terms of its weight ratio relative to the total of the compound (A) and the compound (B), must be in the range of 0.1: 99.9 to 99.9 0.1, and preferably in the range of from 1: 99 to 99: 1, and still more preferably in the range of 5:95 to 95: 5.

Amino groups may be introduced into the side chains of the vinyl polymer using, included in the component (B), vinyl monomers containing amino groups, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, followed by modification with potassium acetate monochloride, ammonium acetate monochloride, monochloroacetic acid aminomethylpropanol salt, monobromoacetic acid triethanolamine salt, sodium monochloropropionate, and other alkali metal salts of halogenated fatty acids; otherwise, carboxylic acid groups can be introduced into the side chains of the vinyl polymer by using, included in component (B), vinyl monomers containing carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid. , crotonic acid, fumaric acid and maleic acid, and the like, then neutralizing the product with triethylamine, diethylamine, triethanolamine, and other amines.

The fluorinated vinyl polymer may be one of the polymers described in the examples of the application WO03 / 045337 or for example the product TIB-4-100 marketed by Dow Corning.

Polymer in dispersion

According to a third embodiment of the invention, the film-forming polymer present in the composition according to the invention is a dispersion of particles of homopolymer or of radical copolymer, acrylic or vinyl dispersed in the liquid fatty phase of the composition.

According to the invention, the polymer in the form of particles dispersed in the volatile liquid fatty phase is an insoluble solid in the liquid fatty phase of the composition even at its softening temperature, unlike a wax of polymeric origin itself. which is it soluble in the liquid organic phase (or fatty phase) at its melting temperature.

The composition according to the invention advantageously comprises at least one stable dispersion of generally spherical polymer particles of one or more polymers, in a volatile liquid fatty phase. These dispersions may in particular be in the form of polymer nanoparticles in stable dispersion in said liquid organic phase.

The nanoparticles are preferably of average size between 5 and 800 nm, and more preferably between 50 and 500 nm. It is however possible to obtain polymer particle sizes of up to 1 μm.

Preferably, the dispersed polymer particles are insoluble in water-soluble alcohols such as, for example, ethanol. The dispersion polymers that can be used in the first composition of the invention preferably have a molecular weight of the order of 2000 to 10,000,000 g / mol, and a Tg of -100 ^° C. at 300 ^° C. and better still -50 ^° C. At 100 ^° C., preferably from -10 ° C. to 50 ° C.

It is possible to use film-forming polymers, preferably having a low Tg, less than or equal to the temperature of the skin and in particular less than or equal to 40 ^° C. Preferably the polymer used is film-forming, that is to say able to form alone or in combination with a plasticizer, an isolatable film. However, it is possible to use a non-film-forming polymer.

The term "non-film-forming polymer" means a polymer that is not capable of forming an isolable film alone. This polymer makes it possible, in combination with a nonvolatile compound of the oil type, to form a continuous and homogeneous deposit on the skin and / or the lips. Among the film-forming polymers that may be mentioned are homopolymers or radical copolymers, acrylic or vinyl, preferably having a Tg of less than or equal to 40 ^° C. and in particular ranging from -10 ° to 30 ^° C., used alone or as a mixture.

Among the non-film-forming polymers, there may be mentioned homopolymers or radical copolymers, vinyl or acrylic, optionally crosslinked, preferably having a Tg greater than 40 ⁰ C and in particular ranging from 45 ° to 150 ° C, used alone or in mixture.

Radical polymer is understood to mean a polymer obtained by polymerization of unsaturated monomers, in particular ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates). The radical polymers may in particular be vinyl polymers or copolymers, especially acrylic polymers.

The acrylic polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acidic monomers and / or amides of these acids.

As monomer bearing an acid group, it is possible to use α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. It is preferable to use (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid.

The acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), such as alkyl (meth) acrylates, in particular C ₁ -C ₂ alkyl, preferably C ₁ -C ₈ , the (meth) acrylates of aryl, in particular of C ₆ -C ₁₀ aryl, hydroxyalkyl (meth) acrylates, in particular of hydroxy C ₂ -C ₆ alkyl. As alkyl (meth) acrylates, there may be mentioned methyl (meth) acrylate, ethyl, butyl, isobutyl, 2-ethylhexyl and lauryl. Hydroxyalkyl (meth) acrylates that may be mentioned include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Aryl (meth) acrylates include benzyl or phenyl acrylate.

Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.

The radical polymer used is preferably copolymers of (meth) acrylic acid and alkyl (meth) acrylate, especially C ₁ -C ₄ alkyl. More preferentially, it is possible to use methyl acrylates optionally copolymerized with acrylic acid.

Amides of the acid monomers, (meth) acrylamides that may be mentioned, and especially N-alkyl (meth) acrylamides, alkyl in particular C ₂ -C ₂ such as N-ethyl acrylamide, Nt-butyl acrylamide N-octyl acrylamide; N-dialkyl (CrC ₄ ) (meth) acrylamides. The acrylic polymers can also result from the polymerization of ethylenically unsaturated monomers having at least one amino group, in free form or partially or completely neutralized, or even partially or totally quaternized. Such monomers may be, for example, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylamide, vinylamine, vinylpyridine or diallyldimethylammonium chloride.

The vinyl polymers may also result from the homopolymerization or copolymerization of at least one monomer chosen from vinyl esters and styrene monomers. In particular, these monomers can be polymerized with acidic monomers and / or their esters and / or their amides, such as those mentioned above. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate, and vinyl t-butyl benzoate. Styrene monomers include styrene and alpha-methyl styrene.

The list of monomers given is not limiting and it is possible to use any monomer known to those skilled in the art falling into the categories of acrylic and vinyl monomers (including monomers modified with a silicone chain).

Other vinyl monomers that can be used include:

N-vinylpyrrolidone, vinylcaprolactam, vinyl N-alkyl (dC ₆ ) pyrroles, vinyl-oxazoles, vinyl-thiazoles, vinylpyrimidines, vinylimidazoles,

olefins such as ethylene, propylene, butylene, isoprene, butadiene.

The vinyl polymer may be crosslinked with one or more difunctional monomers, in particular comprising at least two ethylenic unsaturations, such as ethylene glycol dimethacrylate or diallyl phthalate. The dispersion polymer (s) in the organic liquid phase may represent from 5 to 40% by weight of the solids content of the composition, preferably from 5 to 35% and better still from 8 to 30% by weight.

It is preferable to use a dispersion of particles of film-forming polymer, the particles being dispersed in a volatile oil.

According to one embodiment, the composition contains a solid stabilizer at room temperature. The polymer particles are preferably surface-stabilized by means of a stabilizer which may be a block polymer, a graft polymer, and / or a random polymer, alone or in admixture. The stabilization can be carried out by any known means, and in particular by direct addition of the block polymer, graft polymer and / or random polymer, during the polymerization.

The stabilizer is preferably also present in the mixture before polymerization of the polymer. However, it is also possible to add it continuously, in particular when the monomers are also added continuously.

2-30% by weight of stabilizer can be used in relation to the initial mixture of monomers, and preferably 5-20% by weight.

Among the graft polymers, mention may be made of silicone polymers grafted with a hydrocarbon chain; hydrocarbon polymers grafted with a silicone chain.

Thus graft or block block copolymers comprising at least one polyorganosiloxane type block and at least one block of a radical polymer, such as the graft copolymers of acrylic / silicone type which can be used in particular when the non-aqueous medium is silicone.

It is also possible to use block or graft block copolymers comprising at least one polyorganosiloxane type block and at least one polyether block. The polyorganosiloxane block may especially be a polydimethylsiloxane or a poly (C ₂ -C ₈₎ methyl siloxane; the polyether block may be a poly alkylene C ₂ -C _8, in particular polyoxyethylene and / or polyoxypropylene. In particular, dimethicone copolyols or (C ₂ -C ₈₎ dimethicone copolyols such as those sold under the name "Dow Corning 3225C" by Dow Corning, and lauryl methicone such as those sold under the name " Dow Corning Q2-5200 by the company "Dow Corning".

As graft or block block copolymers, mention may also be made of those comprising at least one block resulting from the polymerization of at least one ethylenic monomer, with one or more optionally conjugated ethylenic bonds, such as ethylene or dienes such as butadiene and isoprene, and at least one block of a vinyl polymer and better styrenic. When the ethylenic monomer comprises several optionally conjugated ethylenic bonds, the residual ethylenic unsaturations after the polymerization are generally hydrogenated. Thus, in known manner, the polymerization of isoprene leads, after hydrogenation, to the formation of ethylene-propylene block, and the polymerization of butadiene leads, after hydrogenation, to the formation of ethylene-butylene block. Among these polymers, mention may be made of block copolymers, in particular of the "diblock" or "triblock" type of the polystyrene / polyisoprene (SI), polystyrene / polybutadiene (SB) type such as those sold under the name 'LUVITOL HSB' by BASF , of the polystyrene / copoly (ethylene-propylene) (SEP) type, such as those sold under the name 'Kraton' by Shell Chemical Co or else from the polystyrene / copoly (ethylene-butylene) (SEB) type. In particular, Kraton G1650 (SEBS), Kraton G1651 (SEBS), Kraton G1652 (SEBS), Kraton G1657X (SEBS), Kraton G1701X (SEP), Kraton G1702X (SEP), Kraton can be used. G1726X (SEB), Kraton D-1 101 (SBS), Kraton D-1 102 (SBS), Kraton D-1 107 (SIS). The polymers are generally called copolymers of hydrogenated dienes or not.

It is also possible to use Gelled Permethyl 99A-750, 99A-753-59 and 99A-753-58 (mixture of triblock and star polymer), Versagel 5960 from Penreco (triblock + star polymer); OS129880, OS129881 and OS84383 from Lubrizol (styrene / methacrylate copolymer).

As graft or block block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with one or more ethylenic bonds and at least one block of an acrylic polymer, mention may be made of two or three-block copolymers poly (methyl methyl acrylate) / polyisobutylene or graft copolymers with poly (methyl methyl acrylate) backbone and polyisobutylene grafts.

As graft or block block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer with one or more ethylenic bonds and at least one block of a polyether such as a C ₂ -C ₈ polylkylene (Polyethylenated and / or polyoxypropylene in particular), mention may be made of polyoxyethylene / polybutadiene or polyoxyethylene / polyisobutylene bi- or triblock copolymers. It is thus possible to employ acrylate based copolymers or alkyl methacrylates derived from alcohols -C _4, and alkyl acrylates or methacrylates derived from alcohols of C ₈ - C ₃ O- can be in mention may be made of the stearyl methacrylate / methyl methacrylate copolymer. When the liquid synthetic solvent comprises at least one silicone oil, the stabilizing agent is preferably chosen from the group consisting of graft or block block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a polymer radical or a polyether or a polyester such as polyoxypropylene and / or oxyethylenated blocks.

When the liquid fatty phase does not comprise silicone oil, the stabilizing agent is preferably chosen from the group consisting of:

(a) graft or block block copolymers comprising at least one block of polyorganosiloxane type and at least one block of a radical polymer or a polyether or a polyester,

(b) copolymers of alkyl acrylates or methacrylates derived from dC ₄ alcohols, and alkyl acrylates or methacrylates derived from C ₈ -C ₃₀ alcohols,

(c) graft or block block copolymers comprising at least one block resulting from the polymerization of at least one ethylenic monomer, with conjugated ethylenic bonds, and at least one block of a vinyl or acrylic polymer or a polyether or polyester, or mixtures thereof.

Diblock polymers are preferably used as the stabilizing agent.

When the polymer has a glass transition temperature too high for the desired application, it can be associated with a plasticizer so as to lower this temperature of the mixture used. The plasticizer may be chosen from plasticizers usually used in the field of application and in particular from compounds that may be solvents of the polymer. Coalescing agents can also be used to help the polymer form a continuous and homogeneous deposit. The coalescing agents or plasticizers that can be used in the invention are especially those mentioned in document FR-A-2782 917. The composition may contain a plasticizer for the polymer, so as to lower the Tg of the polymer film and improve the adhesion of the polymer. polymer film on its support, in particular keratin materials. The plasticizer compound lowers, in particular, the glass transition temperature of the polymer by at least 2, 3 or ^{40 °} C., preferably from 5 ° C. to 20 ^° C. In a preferred embodiment, the plasticizer compound lowers the temperature of the polymer. vitreous transition of the polymer of at least 2, 3 or 4 ⁰ C, preferably 5 ° C to 20 ⁰ C, when the plasticizer compound is at most 10% by weight of the polymer.

According to one embodiment, the compound may be chosen from esters of at least one carboxylic acid comprising 1 to 7 carbon atoms and a polyol comprising at least 4 hydroxyl groups.

The polyol according to the invention may be an ose or a polyol derived from an ose, such as erythritol, xylitol or sorbitol. The polyol may be a mono- or polysaccharide comprising one to 10 monosaccharides, preferably one to four, more preferably one or two monosaccharides. The polyol may be selected from erythritol, xylitol, sorbitol, glucose, and sucrose.

The polyol according to the invention is preferably a disaccharide. Among the disaccharides, mention may be made of sucrose (alpha-D-glucopyranosyl- (1-2) -beta-D-fructofuranose), lactose (beta-D-galactopyranosyl- (1-4) -beta-D-glucopyranose) and maltose (alpha-D-glucopyranosyl- (1-4) -beta-D-glucopyranose).

The plasticizer may consist of a polyol substituted with at least two different monocarboxylic acids, or with at least three different monocarboxylic acids.

The acid is preferably a monocarboxylic acid chosen in particular from acids comprising 1 to 7 carbon atoms, preferably 1 to 5 carbon atoms, examples are acetic, n-propanoic, isopropanoic, n-butanoic, isobutanoic, tert-butanoic, n-pentanoic and benzoic acids.

According to a preferred embodiment, the ester is sucrose diacetate-hexa- (2-methylpropanoate).

Solvent synthesis of polymer particles

The polymer dispersion can be manufactured as described in EP-A-

749747. A mixture comprising the initial monomers and a radical initiator is prepared. This mixture is dissolved in a solvent called, in the remainder of the present description, "synthetic solvent". When the fatty phase is a non-volatile oil, the polymerization can be carried out in an apolar organic solvent (synthetic solvent), then the non-volatile oil (which must be miscible with the said synthesis solvent) is added and the synthesis solvent is selectively distilled off. .

A synthesis solvent is chosen such that the initial monomers and the radical initiator are soluble therein, and the polymer particles obtained are insoluble therein so that they precipitate during their formation. In particular, the synthesis solvent can be chosen from alkanes such as heptane, isododecane or cyclohexane.

When the fatty phase chosen is a volatile oil, the polymerization can be carried out directly in the said oil, which thus also acts as a synthesis solvent. The monomers must also be soluble there, as well as the radical initiator, and the polymer obtained must be insoluble.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5-20% by weight of the reaction mixture. All of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added as the polymerization reaction progresses.

The radical initiator may be in particular azobisisobutyronitrile or tert-butylperoxy-2-ethylhexanoate. The volatile phase of the composition can be constituted by or comprise the synthesis solvent of the dispersed polymer particles.

Examples of non-aqueous dispersions of lipid-dispersible film-forming polymer in the form of non-aqueous dispersions of polymer particles in one or more silicone and / or hydrocarbon oils and which can be stabilized at their surface by at least one stabilizing agent, in particular a block polymer, grafted or statistical, mention may be made of acrylic dispersions in isododecane, such as Mexomère PAP® from Chimex, particle dispersions of a grafted ethylenic polymer, preferably acrylic polymer, in a liquid fatty phase, the ethylenic polymer advantageously being dispersed in the absence of additional stabilizer at the surface of the particles as described in particular in WO 04/055081.

Reactive silicones

According to another embodiment, the composition according to the invention can comprise, as film-forming polymer, two-component systems such as compounds X and Y, defined below, capable of polymerizing in situ, at atmospheric pressure and at room temperature. , and to form films advantageously biocompatible, non-sticky, slightly opalescent or even peelable. Such systems are in part described in WO 01/96450 and GB 2,407,496 to Dow Corning.

According to one particular embodiment, the compounds X and the compounds Y are silicone.

Compounds X and Y may be amino or non-amino. According to another embodiment, at least one of the compounds X and Y is a polymer whose main chain is formed mainly of organosiloxane units.

Among the silicone compounds mentioned below, some may have both film-forming and adhesive properties, for example according to their proportion of silicone or according to whether they are used in admixture with a particular additive. It is therefore possible to modulate the film-forming properties or the adhesive properties of such compounds according to the intended use, this is particularly the case for so-called "room temperature vulcanization" reactive silicone elastomers.

Compounds X and Y may react together at a temperature ranging from room temperature to 180 ^° C. Advantageously, compounds X and Y may react together at room temperature (20 ± 5 ° C.) and atmospheric pressure, or advantageously in the presence of a catalyst, by a hydrosilylation reaction or a condensation reaction, or a crosslinking reaction in the presence of a peroxide.

According to a particular embodiment, compounds X and Y react by hydrosilylation in the presence of a catalyst.

Advantageously, the compounds X and Y are chosen from silicone compounds capable of reacting by hydrosilylation in the presence of a catalyst; in particular, compound X is chosen from polyorganosiloxanes comprising units of formula (I) described below and compound Y is chosen from organosiloxanes comprising alkylhydrogensiloxane units of formula (III) described below.

According to one particular embodiment, the compound X is a polydimethylsiloxane with terminal vinyl groups, and the compound Y is a polymethylhydrogenosiloxane. Compound X is therefore advantageously chosen from polyorganosiloxanes comprising siloxane units of formula:

in which :

R represents a linear or cyclic monovalent hydrocarbon group comprising from 1 to 30 carbon atoms, preferably from 1 to 20, and more preferably from 1 to 10 carbon atoms, for example a short-chain alkyl radical, for example comprising from 1 to 10 carbon atoms, in particular a methyl radical or a phenyl group, preferably a methyl radical, m is equal to 1 or 2 and R 'represents: an unsaturated aliphatic hydrocarbon group comprising from 2 to 10, preferably from 3 to 5 carbon atoms such as for example a vinyl group or a group -R "- CH = CHR" "in which R" is a divalent aliphatic hydrocarbon chain, comprising from 1 to 8 carbon atoms, bonded to the silicon atom and R '"is a hydrogen atom or an alkyl radical comprising 1 to 4 carbon atoms, preferably a hydrogen atom; mention may be made, as group R ', of the vinyl and allyl groups and their mixtures; or o an unsaturated cyclic hydrocarbon group comprising from 5 to 8 carbon atoms, for example a cyclohexenyl group.

Preferably R 'is an unsaturated aliphatic hydrocarbon group, preferably a vinyl group. According to one embodiment, R represents an alkyl radical comprising from 1 to 10 carbon atoms or else a phenyl group, and preferably a methyl radical, and R 'is a vinyl group.

The compound Y may advantageously be chosen from polyorganosiloxanes comprising at least one alkylhydrogenosiloxane unit of the following formula:

in which :

R represents a linear or cyclic monovalent hydrocarbon group comprising from 1 to 30 carbon atoms, for example an alkyl radical having from 1 to 30 carbon atoms, preferably from 1 to 20 and better still from 1 to 10 carbon atoms; , in particular a methyl radical, or else a phenyl group and p is equal to 1 or 2. Preferably R is a hydrocarbon group, preferably methyl. According to one embodiment, the compositions comprising compound X and / or Y may further comprise an additional reactive compound such as:

the organic or inorganic particles comprising on their surface at least 2 unsaturated aliphatic groups, for example silicas surface-treated for example with silicone compounds with vinyl groups such as, for example, cyclotetramethyltetravinylsiloxane treated silica, silazane compounds such as than hexamethyldisilazane.

The hydrosilylation reaction is carried out in the presence of a catalyst which may be present with one or other of the compounds X or Y or may be present in isolation. For example, this catalyst may be present in the composition in an encapsulated form if the two compounds X and Y, whose interaction it is to cause, are present in the same composition in an unencapsulated form or conversely there may be be present in an unencapsulated form if at least one of X and Y is present in the composition in an encapsulated form. The catalyst is preferably based on platinum or tin. The catalyst may be present in a content ranging from 0.0001% to 20% by weight relative to the total weight of the composition comprising it.

Compounds X and / or Y may be combined with polymerization inhibitors or retarders, and more particularly catalyst inhibitors. In a nonlimiting manner, mention may be made of cyclic polymethylvinylsiloxanes, and in particular tetravinyl tetramethylcyclotetrasiloxane, and acetylenic alcohols, which are preferably volatile, such as methylisobutynol.

The presence of ionic salts, such as sodium acetate may influence the rate of polymerization of the compounds. By way of example of a combination of compounds X and Y reacting by hydrosilylation in the presence of a catalyst, mention may be made of the following references proposed by Dow Corning: DC 7-9800 Soft Skin Adhesive Parts A & B, and the combination of the following A and B mixtures prepared by Dow Corning: MIXTURE A:

MIXING B:

The compound X may represent from 0.1% to 95% by weight relative to the total weight of the composition containing it, preferably from 1% to 90%, and better still from 5% to 80%. Compound Y may represent from 0.1% to 95% by weight relative to the total weight of the composition containing it, preferably from 1% to 90% and better still from 5% to 80%.

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

Other film-forming polymers:

Polymer dispersed or in solution in an oily phase:

According to another embodiment, the composition according to the invention may also comprise, as film-forming polymers, a film-forming polymer in dispersion or in a solution other than those mentioned above. // check that there are no duplicates with those mentioned above

Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, polymers of natural origin, and mixtures thereof.

By radical-forming film-forming polymer is meant a polymer obtained by polymerization of unsaturated monomers, especially ethylenic monomers, each monomer being capable of homopolymerizing (unlike polycondensates).

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

The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acidic group and / or esters of these acidic monomers and / or amides of these acidic monomers. As monomer bearing an acid group, it is possible to use α, β-ethylenic unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. It is preferable to use (meth) acrylic acid and crotonic acid, and more preferably (meth) acrylic acid.

The acidic monomer esters are advantageously chosen from esters of (meth) acrylic acid (also called (meth) acrylates), in particular alkyl (meth) acrylates, in particular C 1 -C 30 alkyl, preferably C1-C20, (meth) acrylates of aryl, in particular of C6-C10 aryl, hydroxyalkyl (meth) acrylates, in particular of C2-C6 hydroxyalkyl.

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

Among the hydroxyalkyl (meth) acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.

Among the aryl (meth) acrylates, mention may be made of benzyl acrylate and phenyl acrylate.

Particularly preferred (meth) acrylic acid esters are alkyl (meth) acrylates.

According to the present invention, the alkyl group of the esters can be either fluorinated or perfluorinated, ie some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

Amides of the acidic monomers include, for example, (meth) acrylamides, and especially N-alkyl (meth) acrylamides, in particular C 2 -C 12 alkyl. Among the N-alkyl (meth) acrylamides, mention may be made of N-ethyl acrylamide, N-t-butyl acrylamide, N-t-octyl acrylamide and N-undecylacrylamide.

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

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

Among the film-forming polycondensates, mention may be made of polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas. The polyurethanes may be chosen from anionic, cationic, nonionic or amphoteric polyurethanes, polyurethane-acrylics, poly-urethanes-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and their polyurethanes. mixtures. The polyesters can be obtained, in known manner, by polycondensation of dicarboxylic acids with polyols, especially diols.

The dicarboxylic acid can be aliphatic, alicyclic or aromatic. Examples of such acids are: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-acid. - dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers may be used alone or in combination with at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen. The diol may be chosen from aliphatic, alicyclic and aromatic diols. A diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol and 4-butanediol is preferably used. As other polyols, it is possible to use glycerol, pentaerythritol, sorbitol, trimethylolpropane. The polyester amides can be obtained in a similar manner to the polyesters by polycondensation of diacids with diamines or amino alcohols. As the diamine, there can be used ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine. As aminoalcohol, monoethanolamine can be used. According to an exemplary composition according to the invention, the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising organic oils or solvents (it is said that the film-forming polymer is a liposoluble polymer). Preferably, the liquid fatty phase comprises a volatile oil, optionally mixed with a non-volatile oil.

As an example of a fat-soluble polymer, mention may be made of vinyl ester copolymers (the vinyl group being directly connected to the oxygen atom of the ester group and the vinyl ester having a saturated hydrocarbon radical, linear or branched, from 1 to 19 carbon atoms, linked to the carbonyl ester group) and from at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which contains 2 to 18 carbon atoms), or an allyl or methallyl ester (having a linear or branched, saturated hydrocarbon radical of 1 to 19 carbon atoms, bonded to the carbonyl ester group). These copolymers may be crosslinked using crosslinking agents which may be of the vinyl type, or of the allyl or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and octadecanedioate. divinyl. Examples of such copolymers include copolymers: vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecylvinylether , vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, stearate of vinyl vinyl / allyl acetate, 2,2-dimethyl-2 vinyl octanoate / vinyl laurate, 2,2-dimethyl-2-allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, dimethyl allyl propionate / stearate vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, cross-linked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% of tetraal lyloxyethane, vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / allyl stearate cross-linked with 0 2% divinyl benzene. As further examples of liposoluble film-forming polymers, there may be mentioned vinyl ester copolymers and at least one other monomer which may be a vinyl ester, especially vinyl neodecanoate, vinyl benzoate and vinyl t-butyl benzoate, a α-olefin, an alkyl vinyl ether, or an allylic or methallyl ester.

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

Such liposoluble copolymers may be chosen from copolymers of vinyl polycrystearate, vinyl polystearate crosslinked with divinylbenzene, diallyl ether or diallyl phthalate, copolymers of poly (meth) acrylate of stearyl, of vinyl polylaurate. , poly (meth) acrylate lauryl, these poly (meth) acrylates can be crosslinked using dimethacrylate ethylene glycol or tetraethylene glycol.

The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have a weight average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000.

Liposoluble film-forming polymers that can be used in the invention also include polyalkylenes and especially copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched alkyl radical, saturated or unsaturated, for example ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and of C2 to C40 and better still of C3 to C20 alkene. By way of example of a copolymer of VP which may be used in the invention, mention may be made of the copolymer of VP / vinyl acetate, VP / ethyl methacrylate, polyvinylpyrrolidone (PVP) butylated, VP / ethyl methacrylate / methacrylic acid, VP / eicosene, VP / hexadecene, VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.

Mention may also be made of silicone resins, generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers.

As examples of commercially available polymethylsilsesquioxane resins, mention may be made of those sold by the company Wacker under the reference Resin MK such as Belsil PMS MK, or by the company Shin-Etsu under the references KR-220L. As examples of commercially available polypropylsilsesquioxane resins, mention may be made of those sold under the reference DC670 by Dow Corning.

As siloxysilicate resins, mention may be made of trimethylsiloxysilicate (TMS) resins such as those sold under the reference SR1000 by the company General Electric or under the reference TMS 803 by the company Wacker. Mention may also be made of timethylsiloxysilicate resins sold in a solvent such as cyclomethicone, sold under the name KF-7312J by the company Shin-Etsu, "DC 749", "DC 593" by the company Dow Corning.

Mention may also be made of silicone resin copolymers such as those mentioned above with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers marketed by Dow Corning under the reference BIO-PSA and described in document US 5 162 410 or the silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and a diorganosiloxane as described in document WO 2004/073626. Mention may also be made of acrylic / silicone graft copolymers having a vinyl, methacrylic or acrylic polymeric backbone, and organosiloxane or polyorganoxiloxane pendant grafts. Such polymers are in particular described in US Pat. No. 4,693,935, US Pat. No. 4,981,903 and US Pat. No. 4,981,902. These polymers preferably comprise monomers A, C and optionally B for which:

A is at least one polymerizable monomer vinyl, methacrylate or free radical acrylate;

B, when present, is at least one rigidifying monomer copolymerizable with A;

C is a monomer of the following formula:

X (Y) _n Si (R) ₃ - _m Z _m wherein X is a vinyl group copolymerizable with the A and B monomers;

Y is a divalent linker; n is 0 or 1; m is an integer of 1 to 3;

R is a hydrogen atom, an alkyl radical having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl radical, an alkoxy radical having 1 to 10 carbon atoms;

Z is a monovalent siloxane polymeric group.

Examples of monomers A are lower to intermediate esters of methacrylic acid and linear or branched chain C1-12 alcohols, styrene, vinyl esters, vinyl chloride, vinylidene chloride, or acryloyl monomers. Examples of monomers B are polar acrylic or methacrylic monomers having at least one hydroxyl, amino, ester or ionic group (such as quaternary ammoniums, carboxylate salt or acids such as carboxylic acids, acrylic acids, sulfonic acid or its salts). Monomer C is defined above.

Examples of acrylic / silicone graft copolymers that may be mentioned are those sold by 3M under the reference 3M Silicones "Plus" VS70 Dry Polymer®, INCI name: Polysilicone-6, or KP-561® marketed by SHIN-ETSU and INCI name: Acrylates / Stearyl Acrylate / Dimethicone Methacrylate Copolymer, KP-562® marketed by SHIN-ETSU and INCI name: Acrylates / Behenyl Acrylate / Dimethicone Acrylate Copolymer.

Polymer in aqueous dispersion (latex) or water-soluble

The composition may comprise an aqueous phase and the film-forming polymer may be present in this aqueous phase. In this case it will preferably be a polymer in aqueous dispersion (latex) or water-soluble. Among the film-forming polymers that can be used in the composition of the present invention, mention may be made of synthetic polymers, of free-radical type or of polycondensate type, polymers of natural origin, and mixtures thereof. Examples of water-soluble film-forming polymers that may be mentioned include: proteins such as proteins of plant origin such as wheat and soy proteins; proteins of animal origin such as keratins, for example keratin hydrolysates and keratin sulfonates; cellulose polymers such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, and quaternized cellulose derivatives; acrylic polymers or copolymers, such as polyacrylates or polymethacrylates; vinyl polymers, such as polyvinylpyrrolidones, copolymers of methylvinyl ether and malic anhydride, copolymer of vinyl acetate and crotonic acid, copolymers of vinylpyrrolidone and vinyl acetate; copolymers of vinylpyrrolidone and caprolactam; polyvinyl alcohol; anionic, cationic, amphoteric or nonionic chitin or chitosan polymers, gum arabic, guar gum, xanthan derivatives, karaya gum; alginates and carrageenans; glycosaminoglycans, hyaluronic acid and its derivatives; shellac resin, sandaraque gum, dammars, elemis, copals; deoxyribonucleic acid; mucopolysaccharides such as chondroitin sulfate, and mixtures thereof.

The film-forming polymer may also be present in the composition in the form of particles in dispersion in an aqueous phase, generally known under the name of latex or pseudolatex. The techniques for preparing these dispersions are well known to those skilled in the art.

Aqueous dispersions of film-forming polymer may be used include the acrylic dispersions sold under the names 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 the company Dow Chemical, Daitosol 5000 AD ^® or

Daitosol 5000 SJ ^® by the company DAITO KASEY KOGYO; Syntran 5760 ^® by the company

Interpolymer Allianz Opt ^® by Rohm and Haas, aqueous dispersions of acrylic or styrene / acrylic polymers sold under the name of JONCRYL® by the company Johnson Polymer, or the aqueous dispersions of polyurethane sold under the names Neorez R-981 ^® and Neorez R-974 ^® by the company AVECIA-

NEORESINS, Avalure UR-405 ^® , Avalure UR-410 ^® , Avalure UR-425 ^® , Avalure UR-450 ^® ,

Sancure 875 ^® , Avalure UR-445 ^® and Sancure 2060 ^® by the company NOVEON, Impranil 85 ^® by the company BAYER, Aquamere H-1511 ^® by the company HYDROMER; sulphopolyesters sold under the brand name Eastman AQ ^® by the company Eastman Chemical Products, vinyl dispersions, for instance Mexomer MAP ^® from the company Chimex, aqueous polyvinyl acetate dispersions as the "Vinybran ^®" from Nisshin

Chemical or those marketed by UNION CARBIDE, aqueous dispersions of terpolymer vinyl pyrrolidone, dimethylaminopropyl methacrylamide and lauryldimethylpropylmethacrylamidoammonium chloride such as Styleze W-ISP, aqueous dispersions of polyurethane / polyacrylic hybrid polymers such as those sold under the references "Hybridur ^® " by AIR PRODUCTS or

"Duromer ^® " NATIONAL STARCH, core / shell type dispersions: for example those sold by the company ATOFINA under the reference Kynar (core: fluorinated shell: acrylic) or those described in US 5,188,899 (core; silica - shell: silicone) and mixtures thereof.

According to one particular embodiment, the composition according to the invention comprises, as hydrophilic film-forming polymers, at least the combination of a cationic polymer and an anionic polymer. The cationic polymer may be chosen from quaternary cellulose ether derivatives, cellulose copolymers with a water-soluble quaternary ammonium monomer, cyclopolymers, cationic polysaccharides, silicone cationic polymers, vinylpyrrolidone-acrylate or methacrylate copolymers. dialkylamino-alkyl quaternized or not, quaternary polymers of vinylpyrrolidone and vinylimidazole, polyamidoamines and mixtures thereof.

Preferably, the cationic polymer is a hydroxyalkyl (Ci-C ₄ ) cellulose having quaternary ammonium groups.

The anionic polymer is advantageously chosen from:

A) homo- or copolymers of acrylic or methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts, sodium salts of polyhydroxycarboxylic acids such as copolymers of acrylic acid and of acrylamide sold in the form of their sodium salt under the names Reten ^® by the company Hercules, the sodium polymethacrylate sold under the name Darvan 7 ^® by the company Vanderbilt, polyhydroxycarboxylic acid sodium salts sold under the name HYDAGEN F ^® by the company HENKEL,

B) copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol; copolymers of this type comprising, in their chain, an N-alkylated and / or hydroxyalkylated acrylamide unit, copolymers of acrylic acid and of C 1 -C 4 alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and methacrylate; C1-C20 alkyl;

C) copolymers derived from crotonic acid, such as those comprising in their chain vinyl acetate or propionate units and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a linear or branched saturated carboxylic acid; long hydrocarbon chain such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted;

D) polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters; copolymers of maleic, citraconic and itaconic anhydrides and of an allyl or methallyl ester optionally containing an acrylamide, methacrylamide, an α-olefin group, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain; anhydride functions are monoesterified or monoamidified;

E) polyacrylamides having carboxylate groups,

F) deoxyribonucleic acid; G) copolymers of at least one dicarboxylic acid, at least one diol and at least one bifunctional aromatic monomer carrying a group -SO3M with M representing a hydrogen atom, an ammonium ion NH4 + or a metal ion; - and their mixtures. The most particularly preferred anionic polymers are chosen from non-crosslinked anionic polymers such as the monoesterified methyl vinyl ether / maleic anhydride copolymers sold under the name Gantrez ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers marketed under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, vinyl acetate terpolymers / tert-butyl vinyl benzoate / crotonic acid and the Crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and of ethyl acrylate marketed under the name Luvimer MAEX or MAE by the company B ASF, the vinylpyrrolidone / acrylic acid / lauryl methacrylate terpolymers sold under the name ACRYLIDONE LM by the company ISP and the homopolymers of acrylic or methacrylic acid marketed for example under the name VERSICOL E 5 or the sodium polymethacrylate sold under the name DARVAN 7 by the company VANDERBILT, and their mixtures. Preferably, the anionic polymer is a sodium polymethacrylate.

Pastes of non-animal origin

The compositions according to the invention may comprise at least one pasty of non-animal origin.

The compositions according to the invention may thus comprise at least one pasty of non-animal origin, and the mixture 1) described above.

For the purposes of the present invention, the term "pasty compound" is intended to mean a lipophilic fat compound with a reversible solid / liquid state change and comprising at the temperature of 23 ° C. a liquid fraction and a solid fraction. A pasty compound is at a temperature of 23 ° C, in the form of a liquid fraction and a solid fraction. In other words, the starting melting temperature of the pasty compound is less than 23 ° C. The liquid fraction of the pasty compound, measured at 23 ° C., represents from 20 to 97% by weight of the pasty compound. This liquid fraction at 23 ° C is more preferably 25 to 85%, and more preferably 30 to 60% by weight of the pasty compound.

The liquid fraction by weight of the pasty compound at 23 ° C. is equal to the ratio of the enthalpy of fusion consumed at 23 ° C. to the heat of fusion of the pasty compound.

The heat of fusion consumed at 23 ° C is the amount of energy absorbed by the sample to change from the solid state to the state that it has at 23 ° C consisting of a liquid fraction and a solid fraction.

The heat of fusion of the pasty compound is the enthalpy consumed by the compound to pass from the solid state to the liquid state. The pasty compound is said to be in the solid state when the entirety of its mass is in solid form. The pasty compound is said to be in a liquid state when all of its mass is in liquid form.

The enthalpy of fusion of the pasty compound is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a rise in temperature of 5 or 10 ⁰ C per minute, according to the standard ISO 11357-3: 1999. The enthalpy of fusion of the pasty compound is the amount of energy required to pass the compound from the solid state to the liquid state. It is expressed in J / g.

The liquid fraction of the pasty compound, measured at 32 ° C., preferably represents from 40 to 100% by weight of the pasty compound, more preferably from 50 to 100% by weight of the pasty compound. When the liquid fraction of the pasty compound measured at 32 ° C. is equal to 100%, the temperature of the end of the melting range of the pasty compound is less than or equal to 32 ° C. The liquid fraction of the pasty compound, measured at 32 ° C., is equal to the ratio of the heat of fusion consumed at 32 ° C. to the heat of fusion of the pasty compound. The enthalpy of fusion consumed at 32 ° C. is calculated in the same way as the heat of fusion consumed at 23 ° C.

By "non-animal origin" is meant a pasty compound chosen from synthetic pasty compounds and of plant origin (product or plant derived). The pasty compound preferably has a hardness at 20 ^° C. ranging from 0.001 to 0.5 MPa, preferably from 0.002 to 0.4 MPa.

The hardness is measured according to a method of penetration of a probe into a sample of compound and in particular using a texture analyzer (for example TA-XT2i from Rhéo) equipped with a stainless steel cylinder. 2 mm in diameter. The hardness measurement is carried out at 20 ^° C. in the center of 5 samples. The cylinder is introduced into each sample, the penetration depth being 0.3 mm. The measured value of the hardness is that of the maximum peak.

The pasty compound of non-animal origin is chosen from synthetic compounds and compounds of plant origin. A pasty compound of non-animal origin can be obtained synthetically from starting materials of plant origin. The pasty compound is advantageously chosen from: polymeric or non-polymeric silicone compounds, such as polydimethylsiloxanes of high molecular weight, polydimethylsiloxanes with side and / or terminal chains of the alkyl or alkoxy type having from 8 to 24 carbon atoms, especially stearyl dimethicones, polymeric or non-polymeric fluorinated compounds, vinyl polymers, especially oolefin homopolymers, olefin copolymers, homopolymers and copolymers of hydrogenated dienes, linear or branched oligomers, homo or copolymers of alkyl (meth) acrylates preferably having a C ₈ -C ₃₀ alkyl group; homo and copolymer oligomers of vinyl esters having C ₈ -C ₃₀ alkyl groups, homo- and copolymer oligomers of vinyl ethers; having C ₈ -C ₃₀ alkyl groups, the fat-soluble polyethers resulting from the polyetherification between one or more C ₂ -C ₁₀ O diols, preferably C ₂ -C ₅₀ diols, esters and polyesters, and mixtures thereof.

The pasty compound may be a polymer, in particular a hydrocarbon polymer. A preferred silicone and fluoro pasty compound is polymethyl-trifluoropropyl-methylalkyl-dimethylsiloxane, manufactured under the name X22-1088 by SHIN ETSU.

When the pasty compound is a silicone and / or fluorinated polymer, the composition advantageously comprises a compatibilizing agent such as short chain esters such as isodecyl neopentanoate.

Among the liposoluble polyethers, there may be mentioned copolymers of ethylene oxide and / or propylene oxide with C ₆ -C ₃₀ alkylene oxides. Preferably, the weight ratio of ethylene oxide and / or propylene oxide to the alkylene oxides in the copolymer is from 5:95 to 70:30. In this family, block copolymers comprising blocks of C ₆ -C ₃₀ alkylene oxides with a molecular weight ranging from 1,000 to 10,000, for example a polyoxyethylene / polydodecylene glycol block copolymer such as ethers, are particularly suitable. dodecanediol (22 mol) and polyethylene glycol (45 oxyethylene or OE units) marketed under the trademark ELFACOS ST9 by Akzo Nobel.

Among the esters, the following are particularly preferred: the esters of an oligomeric glycerol, in particular the diglycerol esters, in particular the adipic acid and glycerol condensates, for which part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid, isostearic acid and 12-hydroxystearic acid, such as those sold under the trade name Softisan 649 by the company Sasol; phytosterol esters; pentaerythritol esters; the esters formed from:

• of at least one alcohol C ₁ 6 ₄ 0, at least one of the alcohols being a Guerbet alcohol and

A diacid dimer formed from at least one unsaturated C 18-40 fatty acid, such as the tall oil fatty acid dimer ester comprising 36 carbon atoms and a mixture of i) alcohols; Guerbet comprising 32 carbon atoms and ii) behenyl alcohol; the dimer ester of linoleic acid and a mixture of two Guerbet alcohols, 2-tetradecyl-octadecanol (32 carbon atoms) and 2-hexadecyl-eicosanol (36 carbon atoms); non-crosslinked polyesters resulting from the polycondensation between a linear or branched C ₄ -C ₅ dicarboxylic acid or polycarboxylic acid and a diol or a C ₂ -C ₅ polyol; polyesters which result from the esterification between a polycarboxylic acid and a hydroxylated aliphatic carboxylic acid ester such as Risocast DA-L and Risocast DA-H marketed by the Japanese company KOKYU ALCOHOL KOGYO, which are esters resulting from the reaction esterification of hydrogenated castor oil with dilinoleic acid or isostearic acid; and the ester aliphatic esters resulting from the esterification between an aliphatic hydroxyl carboxylic acid ester and an aliphatic carboxylic acid, for example that sold under the trade name Salacos HCIS (V) -L by the company Nishing

OII.

Guerbet alcohol is the reaction product of the Guerbet reaction well known to those skilled in the art. It is a reaction transforming a primary aliphatic alcohol into its dimer-alkylated alcohol with loss of one equivalent of water.

The aliphatic carboxylic acids described above generally comprise from 4 to 30 and preferably from 8 to 30 carbon atoms. They are preferably chosen from hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid and tridecanoic acid. , tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, hexyldecanoic acid, heptadecanoic acid, octadecanoic acid, isostearic acid, nonadecanoic acid, eicosanoic acid, isoarachidic acid , octyldodecanoic acid, henicosanoic acid, docosanoic acid, and mixtures thereof.

The aliphatic carboxylic acids are preferably branched.

The hydroxylated aliphatic carboxylic acid esters are advantageously derived from a hydroxylated aliphatic carboxylic acid having from 2 to 40 carbon atoms, preferably from 10 to 34 carbon atoms and better still from 12 to 28 carbon atoms, and from 1 to 30 carbon atoms. Hydroxyl groups, preferably from 1 to 10 hydroxyl groups and more preferably from 1 to 6 hydroxyl groups. The hydroxylated aliphatic carboxylic acid esters are in particular chosen from: a) the esters, partial or total, of saturated, monohydroxylated monocarboxylic acid monocarboxylic acids; b) the esters, partial or total, of monocarboxylic acids which are monohydroxylated and unsaturated; c) the esters, partial or total, saturated monohydroxy-substituted aliphatic carboxylic polyacids; d) esters, partial or total, saturated polyhydroxy-substituted aliphatic carboxylic polyacids; e) the esters, partial or total, of C ₂ to C ₁₆ aliphatic polyols reacted with a mono- or polyhydroxylated aliphatic mono- or polycarboxylic acid, f) and mixtures thereof. The aliphatic ester esters are advantageously chosen from:

the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in the proportions 1 to 1 (1/1), which is called hydrogenated castor oil monoisostearate,

the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in the proportions 1 to 2 (1/2), which is called hydrogenated castor oil diisostearate,

the ester resulting from the esterification reaction of hydrogenated castor oil with isostearic acid in proportions 1 to 3 (1/3), which is called hydrogenated castor oil triisostearate,

- and their mixtures.

Preferably, the pasty compound is chosen from compounds of plant origin.

Among these, there may be mentioned isomerized jojoba oil such as trans isomerized partially hydrogenated jojoba oil manufactured or marketed by Desert Whale under the trade name lso-Jojoba-50®, orange wax as, for example, that marketed under the reference Orange Peel Wax by the company Koster Keunen, shea butter, partially hydrogenated olive oil such as, for example, the compound sold under the reference Beurrolive by the company Soliance , cocoa butter, mango oil such as, for example, the Lipex 302 from Aarhuskarlshamn.

The pasty compound (s) are preferably present in an amount greater than or equal to 1% by weight relative to the total weight of the composition, for example from 1 to 15% by weight, better still in an amount of greater than or equal to 2% by weight. weight, for example from 2 to 10% by weight, and even more preferably from 3 to 8% by weight, relative to the total weight of the composition.

Rheological agent thickening or gelling of fatty phase

The composition according to the invention may comprise a thickening rheological agent or gelling agent of fatty phase.

The compositions according to the invention may thus comprise at least one fatty phase thickening or gelling agent, and the mixture of MQ and T-propyl resins described above.

The term "thickening rheological agent or gelling agent of fatty phase" means a compound capable of increasing the viscosity of the fatty phase of the composition. The rheological thickening agent or gelling of fatty phase makes it possible in particular to obtain a composition that can present a texture ranging from fluid to solid textures.

The rheological thickening agent or gelling agent of the fatty phase may be chosen from: crystalline polymers, preferably chosen from semi-crystalline polymers, dextrin and fatty acid esters, hydrophobic modified polysaccharides, crystalline olefin copolymers and crystalline polycondensates; mineral lipophilic structuring agents, such as lipophilic clays and hydrophobic silicas, such as hydrophobic treated fumed silica, lipophilic polyamide polymers, polyureas and lipophilic polyurethanes, the silicone polymers comprising, where appropriate, at least one hydrocarbon unit comprising two groups capable of establishing hydrogen interactions chosen from the ester, amide, sulphonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino and biguanidino groups and their combinations preferably amide groups, organogelators; block polymers; cholesteric liquid crystals; silicone elastomers; - and their mixtures.

Preferably, the rheological agent of the fatty phase is chosen from semi-crystalline polymers, block polymers, lipophilic polyamide-type polymers, and silicone polymers comprising at least one hydrocarbon-based unit comprising two groups capable of establishing hydrogen interactions. selected from amide groups, mineral lipohile structuring agents, in particular lipophilic clays and hydrophobic silicas, and silicone elastomers.

It is specified that, according to the invention, in the case of associations of a rheological agent of fatty phase with an oil, the term "oil" means a fatty substance that is liquid at ambient temperature.

It is furthermore specified that by "volatile compound" for example "volatile oil" is meant, within the meaning of the invention, any compound (or non-aqueous medium) capable of evaporating on contact with the skin or the keratinous fiber. in less than one hour, at room temperature and atmospheric pressure. The volatile compound is a volatile cosmetic compound which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10-3 ^). at 300 mmHg), in particular ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg), and more particularly ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm). By contrast, the term "non-volatile compound" for example "non-volatile oil" means a compound remaining on the skin or keratin fiber at ambient temperature and atmospheric pressure, for at least several hours and having in particular a pressure of steam of less than 10 ^"3 mm Hg (0.13 Pa).

The oil may be chosen from volatile and nonvolatile hydrocarbon and / or silicone and / or fluorinated oils and mixtures thereof. These oils can be of animal, vegetable, mineral or synthetic origin. By "hydrocarbon oil" is meant an oil comprising mainly carbon and hydrogen atoms and optionally one or more functions selected from hydroxyl, ester, ether, carboxylic functions. As an example of an oil that may be used in the invention, mention may be made of: hydrocarbon-based oils of animal origin, such as perhydrosqualene;

vegetable hydrocarbon-based oils such as liquid triglycerides of fatty acids with 4 to 24 carbon atoms, for instance triglycerides of heptanoic or octanoic acids, or sunflower, corn, soybean, squash or grape seed oils, sesame, hazelnut, apricot, macadamia, castor oil, avocado, triglycerides of caprylic / capric acids, such as those sold by Stearineries Dubois or those sold under the names Miglyol 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter;

linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, polybutenes, hydrogenated polyisobutene such as Parleam;

esters and synthetic ethers, in particular of fatty acids, such as the oils of formula R ₁ COOR ₂ in which R 1 represents the residue of a higher fatty acid comprising from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon-based chain containing from 1 to 40 carbon atoms with R 1 + R ₂ > 10 such as, for example, purcellin oil, isononyl isononanoate, isopropyl myristate, ethyl 2-hexyl palmitate, stearate octyl 2-dodecyl, octyl 2-dodecyl erucate, isostearyl isostearate, tridecyl trimellitate; hydroxylated esters such as isostearyl lactate, octyl hydroxy stearate, octyl dodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and pentaerythritol esters such as pentaerythritol tetraisostearate;

fatty alcohols having from 12 to 26 carbon atoms, such as octyl dodecanol, 2-butyloctanol, 2-hexyl decanol, 2-undecyl pentadecanol, and oleic alcohol; fluorinated oils which may be partially hydrocarbon-based and / or silicone-based;

silicone oils, such as volatile or non-linear polydimethylsiloxanes (PDMSs), linear or cyclic; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenylethyl trimethylsiloxysilicates;

- their mixtures.

Preferably, the oil has a molecular mass greater than or equal to 250 g / mol, especially between 250 and 10,000 g / mol, preferably greater than or equal to 300 g / mol, in particular between 300 and 8000 g / mol and better, higher or equal to 400 g / mol, in particular between 400 and 5000 g / mol.

Generally in the fatty phase, the ratio of the oil (s) to the particular compound (s) is 10/90 to 90/10, preferably 20/80 to 80/20 and preferably still from 30/70 to 70/30. This oil can be chosen from:

polybutylenes such as INDOPOL H-100 (of molar mass or MM = 965 g / mol), INDOPOL H-300 (MM = 1340 g / mol), INDOPOL H-1500 (MM = 2160 g / mol) mol) marketed or manufactured by AMOCO;

hydrogenated polyisobutylenes, such as PANALANE H-300 E marketed or manufactured by AMOCO (M = 1340 g / mol), VISEAL 20000 marketed or manufactured by SYNTEAL (MM = 6000 g / mol), REWOPAL PIB 1000 marketed or manufactured by WITCO (MM = 1000 g / mol);

Polydecenes and hydrogenated polydecenes such as: PURESYN 10 (MM = 723 g / mol), PURESYN 150 (MM = 9200 g / mol) marketed or manufactured by the company MOBIL CHEMICALS,

esters such as linear fatty acid esters having a total number of carbon ranging from 30 to 70 such as pentaerythrityl tetrapelargonate (MW = 697.05 g / mol), hydroxylated esters such as diisostearyl malate (MM = 639 g / mol), aromatic esters such as tridecyl trimellitate (MW = 757.19 g / mol), branched fatty alcohol or C24-C28 fatty acid esters such as those described in the application EP-A-0 955 039, and in particular triisocetyl citrate (MM = 865 g / mol), pentaerythrityl tetraisonanoate (MW = 697.05 g / mol), glyceryl triisostearate (MW = 891.51 g / mol), glyceryl 2-decyl tetradecanoate (MM = 1,143.98 g / mol), pentaerythrityl tetraisostearate (MM = 1202.02 g / mol), polyglyceryl tetraisostearate -2 (MM = 1232.04 g / mol). ) or alternatively pentaerythrityl tetra decyl tetradecanoate (MW = 1538.66 g / mol), oils of plant origin such as sesame oil (820.6 g / mol),

- and their mixtures.

Crystalline polymers a) Semi-crystalline polymers

It is specified that, according to the invention, in the case of the aforementioned associations, the term "semi-crystalline polymer", polymers having a crystallizable portion, pendant and / or terminal crystallizable chain or crystallizable block in the backbone and / or at the ends, and an amorphous part in the backbone and having a reversible phase change temperature of the first order, in particular of fusion (solid-liquid transition). When the crystallizable portion is in the form of a crystallizable block of the polymer backbone, the amorphous portion of the polymer is in the form of an amorphous sequence; in this case, the semicrystalline polymer is a block copolymer, for example of the diblock, triblock or multiblock type, comprising at least one crystallizable block and at least one amorphous block. By "sequence" is generally meant at least 5 identical repetition patterns. The crystallizable sequence (s) are then of a different chemical nature from the amorphous sequence (s).

The semi-crystalline polymer according to the invention has a melting point greater than or equal to 30 ^° C. (in particular ranging from 30 ^° C. to 80 ^° C.), preferably ranging from 30 ^° C. to 60 ^° C. This melting temperature is a first-order state change temperature.

This melting temperature can be measured by any known method and in particular using a differential scanning calorimeter (D.S.C.).

Advantageously, the semi-crystalline polymer or polymers to which the invention applies have a number average molecular mass greater than or equal to 1,000.

Advantageously, the semi-crystalline polymer (s) of the composition of the invention have a number-average molecular weight Mn ranging from 2,000 to 800,000, preferably from 3,000 to 500,000, better still from 4,000 to 150,000. , especially less than

100,000, and preferably from 4,000 to 99,000. Preferably, they have a number average molecular weight greater than 5,600, for example from 5,700 to 99,000.

For the purposes of the invention, the term "chain or crystallizable block" means a chain or sequence which, if it were alone, would pass from the amorphous state to the crystalline state, reversibly, depending on whether it is above or below below the melting temperature. A chain within the meaning of the invention is a group of atoms, during or lateral to the backbone of the polymer. A sequence is a group of atoms belonging to the backbone, a group constituting one of the repeating units of the polymer. Advantageously, the "crystallizable pendant chain" can be a chain comprising at least 6 carbon atoms.

Preferably, the crystallizable sequence (s) or chain (s) of the semicrystalline polymers represent at least 30% of the total weight of each polymer and better still at least 40%. The semicrystalline polymers of the invention with crystallizable sequences are polymers, sequential or multisequenced. They can be obtained by reactive (or ethylenic) double bond monomer polymerization or by polycondensation. When the polymers of the invention are crystallizable side chain polymers, the latter are advantageously in random or statistical form.

Preferably, the semi-crystalline polymers of the invention are of synthetic origin. In addition, they do not have a polysaccharide backbone. In general, the crystallizable units (chains or sequences) of the semi-crystalline polymers according to the invention come from monomer (s) with sequence (s) or crystallizable chain (s), used for the manufacture semi-crystalline polymers.

According to the invention, the semi-crystalline polymer may be chosen from block copolymers comprising at least one crystallizable block and at least one amorphous block, homopolymers and copolymers bearing at least one crystallizable side chain per repeating unit, and mixtures thereof.

The semi-crystalline polymers that can be used in the invention are in particular:

the block copolymers of polyolefins with controlled crystallization, in particular those whose monomers are described in EP-AO 951 897. polycondensates, and in particular of polyester, aliphatic or aromatic type or aliphatic / aromatic copolyester copolyester, homopolymers or copolymers bearing at least one crystallizable side chain and homopolymers or polymers containing in the backbone at least one crystallizable block, such as those described in document US Pat. No. 5,156,911,

homopolymers or copolymers carrying at least one crystallizable side chain, in particular with fluorinated group (s) as described in document WO-A-01/19333,

- and their mixtures.

In the latter two cases, the side chain or crystallizable sequences are hydrophobic.

A) Semi-crystalline polymers with crystallizable side chains:

In particular those defined in US-A-515691 and WO-A-01/19333 may be mentioned. These are homopolymers or copolymers comprising from 50 to 100% by weight of units resulting from the polymerization of one or more monomers bearing crystallizable hydrophobic side chain. . These homo- or co-polymers are of any kind as long as they have the conditions indicated above.

They can result:

- Of particular radical polymerization of one or more monomers with double bond (s) reactive (s) or ethylenic vis-à-vis a polymerization, namely vinyl, (meth) acrylic or allyl.

polycondensation of one or more monomers bearing co-reactive groups (carboxylic or sulphonic acid, alcohol, amine or isocyanate), such as, for example, polyesters, polyurethanes, polyethers, polyureas or polyamides.

In general, these polymers are chosen in particular from homopolymers and copolymers resulting from the polymerization of at least one crystallizable chain monomer (s) which may be represented by the formula X:

with M representing an atom of the polymer backbone, S representing a spacer, C representing a crystallizable group.

Crystallizable "-SC" chains may be aliphatic or aromatic, optionally fluorinated or perfluorinated. "S" represents in particular a linear or branched or cyclic (CH ₂ ) _n or (CH ₂ CI-I ₂ O) _n or (CH ₂ O) group, where n is an integer ranging from 0 to 22. Preferably "S" is a linear group. Preferably, "S" and "C" are different.

When the crystallizable "-SC" chains are aliphatic hydrocarbon chains, they contain hydrocarbon-based alkyl chains containing at least 11 carbon atoms and at most 40 carbon atoms and better still at most 24 carbon atoms. These include aliphatic chains or alkyl chains having at least 12 carbon atoms and preferably these are C ₁ -C ₂₄ alkyl chains. When it is fluorinated or perfluorinated alkyl chains, they comprise at least 6 fluorinated carbon atoms and in particular at least 11 carbon atoms of which at least 6 carbon atoms are fluorinated.

As examples of semi-crystalline polymers or copolymers with crystallizable chain (s), mention may be made of those resulting from the polymerization of one or more of the following monomers: alkyl (meth) acrylates saturated with the alkyl group in Ci ₄ -C _24, the perfluoroalkyl (meth) acrylates with a perfluoroalkyl group substituted Cn-Ci _5, the N-alkyl (meth) acrylamides with the alkyl group in Ci to C ₂₄ ₄ with or without a fluorine atom, esters alkyl chain or perfluoro (alkyl) with C ₁ -C ₂₄ alkyl (with at least 6 fluorine atoms for a perfluoroalkyl chain), vinyl ethers with alkyl chains or perfluoro (alkyl) with the alkyl group C ₁ to C ₂₄ and at least 6 fluorine atoms for a perfluoroalkyl chain, C ₁ to C ₂₄ alpha-olefins such as octadecene, para-alkyl styrenes having an alkyl group having from 12 to 24 atoms carbon, their mixtures.

When the polymers result from a polycondensation, the crystallizable hydrocarbon and / or fluorinated chains as defined above are borne by a monomer which may be a diacid, a diol, a diamine or a diisocyanate. When the polymers which are the subject of the invention are copolymers, they contain, in addition, from 0 to 50% of Y or Z groups resulting from the copolymerization:

α) of Y which is a polar or nonpolar monomer or a mixture of both: When Y is a polar monomer, it is either a monomer bearing polyoxyalkylene groups (in particular oxyethylenated and / or oxypropylene), a hydroxyalkyl (meth) acrylate such as hydroxyethyl acrylate, (meth) acrylamide, a alkyl (meth) acrylamide, an N, N-dialkyl (meth) acrylamide such as, for example, N, N-diisopropylacrylamide or N-vinylpyrrolidone (NVP), N-vinyl caprolactam, a monomer carrying at least a carboxylic acid group such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid or carboxylic acid anhydride group such as maleic anhydride, and mixtures thereof.

. When Y is a non-polar monomer it may be a branched or cyclic linear alkyl (meth) acrylate ester, a vinyl ester, an alkyl vinyl ether, an alpha-olefin, styrene or styrene substituted with an alkyl group. Ci-Ci ₀ , such as α-methylstyrene, a macromonomer of the polyorganosiloxane type with vinyl unsaturation.

By "alkyl" is meant within the meaning of the invention a saturated group including C ₈ to C ₂₄ , except express mention, and better C ₁ to C ₂₄ .

β) of Z which is a polar monomer or a mixture of polar monomers. In this case, Z has the same definition as the "polar Y" defined above. Preferably, the crystallizable side chain semi-crystalline polymers are homopolymers α "alkyl (meth) acrylate or α" alkyl (meth) acrylamide with an alkyl group as defined above, and in particular with Ci ₄ -C ₂₄ , copolymers of these monomers with a hydrophilic monomer preferably of a different nature from (meth) acrylic acid such as N-vinylpyrrolidone or hydroxyethyl (meth) acrylate and mixtures thereof.

B) The polymers bearing in the skeleton at least one crystallizable block:

These polymers are especially block copolymers consisting of at least 2 sequences of different chemical nature, one of which is crystallizable. The block polymers defined in US Pat. No. 5,156,911 can be used;

Olefin or cycloolefin block copolymers with a crystallizable chain, such as those resulting from the sequential polymerization of: cyclobutene, cyclohexene, cyclooctene, norbornene (that is to say bicyclo (2,2,1) heptene-2), 5-methylnorbornene, 5-ethylnorbornene, 5,6-dimethylnorbornene, 5,5,6-trimethyl norbornene, 5-ethylidene norbornene, 5-phenyl-norbonene,

5-benzylnorbornene, 5-vinyl norbornene, 1, 4,5,8-dimethano-1,2,3,4,4a, 5,8-octahydronaphthalene, dicyclopentadiene or mixtures thereof,

. with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-eicosene or their mixtures,. and in particular copoly (ethylene / norbornene) blocks and terpolymers

(ethylene / propylene / ethylidene norbornene) blocks. It is also possible to use those resulting from the block copolymerization of at least 2 α-olefins in C ₂ -C ₁₆ and better still in C ₂ -C ₁₂ and better still in C ₄ -C ₁₂ such as those mentioned above and in particular the block bipolymers of ethylene and 1-octene. The copolymers may be copolymers having at least one crystallizable block, the remainder of the copolymer being amorphous (at room temperature). These copolymers may, in addition, have two crystallizable blocks of different chemical nature. The preferred copolymers are those which have both at room temperature, a crystallizable block and an amorphous sequence both hydrophobic and lipophilic distributed sequentially; mention may be made, for example, of polymers having one of the crystallizable blocks and one of the following amorphous blocks:

. Sequence crystallizable by nature: a) polyester such as poly (alkylene terephthalate), b) polyolefin such as polyethylenes or polypropylenes.

. Amorphous and lipophilic sequence such as amorphous polyolefins or copoly (olefins) such as poly (isobutylene), hydrogenated polybutadiene, hydrogenated poly (isoprene).

As examples of such crystallizable block copolymers and distinct amorphous sequence, include: α) poly (ε-caprolactone) -b-poly (butadiene) block copolymers, preferably used hydrogenated, such as those described in the article "Melting behavior of poly (ε-caprolactone) -block-polybutadiene copolymers" from S. Nojima, Macromolecules, 32, 3727-3734 (1999). β) hydrogenated block copolymers poly (butylene terephthalate) -b-poly (isoprene) sequenced or multiséquencées, cited in the article "Study of morphological and mechanical properties of PP / PBT" by B. Boutevin et al., Polymer Bulletin, 34 , 17-123 (1995).

γ) poly (ethylene) -b-copoly (ethylene / propylene) block copolymers cited in the papers "Morphology of semi-crystalline block copolymers of ethylene- (ethylene-propylene)" by P. Rangarajan et al., Macromolecules , 26, 4640-4645 (1993) and "Polymer Aggregates with crystalline cores: the Poly (ethylene) -poly (ethylene-propylene) system of P. Richter et al., Macromolecules, 30, 1053-1068 (1997).

δ) poly (ethylene) -b-poly (ethylethylene) block copolymers cited in the general article "Crystallization in block copolymers" by I. W. Hamley, Advances in Polymer Science, vol 148, 113-137 (1999).

The semi-crystalline polymers of the composition of the invention may or may not be partially crosslinked as long as the degree of crosslinking does not interfere with their dissolution or dispersion in the liquid fatty phase by heating above their melting point. It may then be a chemical crosslinking, by reaction with a multifunctional monomer during the polymerization. It can also be a physical crosslinking which can then be due either to the establishment of hydrogen or dipolar type bonds between groups carried by the polymer such as dipolar interactions between ionomers carboxylates, these interactions being in small amounts and carried by the polymer backbone; or at a phase separation between the crystallizable blocks and the amorphous blocks carried by the polymer.

Preferably, the semi-crystalline polymers of the composition according to the invention are uncrosslinked. According to a particular embodiment of the invention, the polymer is chosen from copolymers resulting from the polymerization of at least one crystallizable chain monomer chosen from saturated C ₁₄ to C ₂₄ alkyl (meth) acrylates, (C ₁ -C) perfluoroalkyl (meth) acrylates, C ₄ -C ₂₄ N (meth) acrylamides with or without fluorine atoms, C ₄ -C ₂₄ alkyl or perfluoroalkyl vinyl esters, vinyl ethers alkyl or perfluoroalkyl chains -C ₄ -C ₂₄ alpha-olefins -C ₄ -C _24, para-alkylstyrenes with an alkyl group having 12 to 24 carbon atoms, with at least one ester or amide of a monocarboxylic acid to C ₁ 0 optionally fluorinated, which may be represented by the following formula:

wherein Ri is H or CH _3, R represents an alkyl group C ₁ -C ₁ 0 optionally fluorinated and X represents O, NH or NR _2, wherein R ₂ represents an alkyl group C ₁ -C ₁ 0 optionally fluorinated.

According to a more particular embodiment of the invention, the polymer is derived from a crystallizable chain monomer chosen from saturated C ₁₄ -C ₂₂ alkyl (meth) acrylates.

As a particular example of a structuring semicrystalline polymer that may be used in the composition according to the invention, mention may be made of the Intelimer® products from Landec, described in the brochure "Intelimer® Polymers", Landec IP22 (Rev. 4-97 ). These polymers are in solid form at ambient temperature (25 ° C.). They carry crystallizable side chains and have the above formula X.

The semi-crystalline polymers can be in particular: those described in Examples 3, 4, 5, 7, 9, 13 of US Pat. No. 5,156,911 to 1 -COOH group, resulting from the copolymerization of acrylic acid and 'alkyl (meth) acrylate, C ₅ to C ₆ and in particular from the copolymerization: . of acrylic acid, hexadecylacrylate and isodecylacrylate in a 1/16/3 weight ratio,

. of acrylic acid and pentadecylacrylate in a weight ratio 1/19, acrylic acid, hexadecylacrylate, ethyl acrylate in a weight ratio of 2.5: 76.5: 20,

. acrylic acid, hexadecylacrylate and methylacrylate in a 5/85/10 weight ratio,

. of acrylic acid and octadecylmethacrylate in a weight ratio of 2.5: 97.5, hexadecyl acrylate, polyethylene glycol methacrylate monomethyl ether with 8 ethylene glycol units, and acrylic acid in a weight ratio 8.5 / 1 / 0.5.

It is also possible to use the "O" structure polymer of National Starch such as that described in document US Pat. No. 5,736,125, with a melting point of 44 ° C., as well as semi-crystalline polymers with crystallizable pendant chains containing fluorinated groups. as described in Examples 1, 4, 6, 7 and 8 of WO-A-01/19333.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of stearyl acrylate and acrylic acid or of NVP as described in document US-A-5 519 063 or EP-A-550745, respectively of melting temperature. 40 ⁰ C and 38 ° C.

It is also possible to use the semi-crystalline polymers obtained by copolymerization of behenyl acrylate and acrylic acid or of NVP as described in documents US-A-5519063 and EP-A-550745, respectively, of melting temperature. 60 ^° C. and 58 ° C.

Preferably, the semi-crystalline polymers do not contain a carboxylic group.

Waxy polymer obtained by metallocene catalysis:

Finally, the semi-crystalline polymers according to the invention may also be chosen from waxy polymers obtained by metallocene catalysis, such as those described in application US2007 / 0031361. These polymers are homopolymers or copolymers of ethylene and / or propylene prepared by metallocene catalysis, that is to say by polymerization at low pressure and in the presence of a metallocene catalyst.

The weight average mass (Mw) of the waxes obtained by metallocene catalysis described in this document is less than or equal to 25,000 g / mol, it ranges, for example, from 2,000 to 22,000 g / mol and better still from 4,000 to 20,000. g / mol.

The number average mass (Mn) of the waxes obtained by metallocene catalysis described in this document is preferably less than or equal to 15,000 g / mol, it ranges, for example, from 1,000 to 12,000 g / mol, and better still 2,000. at 10,000 g / mol.

The polydispersity index I of the polymer is equal to the ratio of the weight average mass Mw to the number average mass Mn. Preferably, the polydispersity index of the waxy polymers is between 1.5 and 10, preferably between 1.5 and 5, preferably between 1.5 and 3, and more preferably between 2 and 2.5.

The homopolymers and the waxy copolymers can be obtained in known manner from ethylene and / or propylene monomers, for example by metallocene catalysis according to the process described in document EP 571 882.

The homopolymers and copolymers of ethylene and / or propylene prepared by metallocene catalysis can be unmodified or "polar" modified (polar modified waxes), that is, modified waxes so that they exhibit the properties of 'a polar wax). Polymerically modified waxy homopolymers and copolymers can be prepared in known manner from homopolymers and unmodified waxy copolymers such as those described above by oxidation with oxygen-containing gases, such as air, or by grafting with polar monomers such as maleic acid or acrylic acid or derivatives of these acids. These two ways Polymeric modifications of polyolefins obtained by metallocene catalysis are described respectively in EP890583 and US5995847, for example, the contents of both of these documents being incorporated by reference.

According to the present invention, the homopolymers and copolymers of ethylene and / or propylene prepared by polarized and especially preferred metallocene catalysis are the modified polymers so that they exhibit hydrophilic properties. By way of example, there may be mentioned homopolymers or copolymers of ethylene and / or propylene modified by the presence of hydrophilic groups such as maleic anhydride, acrylate, methacrylate, polyvinylpyrrolidone (PVP), etc. .

Homopolymers or copolymers of ethylene and / or waxy propylene modified by the presence of hydrophilic groups such as maleic anhydride or acrylate, are particularly preferred.

By way of example, mention may be made of:

maleic anhydride modified polypropylene waxes (PPMA) marketed by Clariant or polypropylene-ethylene-maleic anhydride copolymers, such as those marketed by Clariant under the name LicoCare as LicoCare PP207 LP3349, LicoCare CM401 LP3345, LicoCare CA301 LP 3346, and LicoCare CA302 LP 3347, or

- Unmodified polyethylene waxes marketed by Clariant, such as the product LicoCare PE 102 LP3329.

In the context of a composition for the lips, it is preferred a polystyrene polymer modified with a low degree of crystallinity, preferably less than 40%.

The use of these waxy polymers makes it possible in particular to limit the loss in gloss of the lipstick compositions. (b) Esters of dextrin and fatty acid:

The dextrin and fatty acid esters may in particular be chosen from dextrin mono-or poly-ester and at least one fatty acid, and the compounds corresponding to formula (C):

in which: n is an integer ranging from 3 to 200, in particular ranging from 20 to 150, and in particular ranging from 25 to 50, the radicals R 1, R ₂ and R ₃ , which are identical or different, are chosen from hydrogen or an acyl group (R-CO-) in which the radical R is a hydrocarbon group, linear or branched, saturated or unsaturated, having from 7 to 29, in particular from 7 to 21, in particular from 1 to 19, more particularly from 13 to 17, or even 15, carbon atoms, provided that at least one of said radicals R 1, R ₂ or R ₃ is other than hydrogen.

In particular, R ₁ , R ₂ and R ₃ may represent hydrogen or an acyl group (R-CO-) in which R is a hydrocarbon radical as defined above, under reserve that at least two of said radicals R 1, R ₂ or R 3 are identical and different from hydrogen.

The set of radicals R 1, R ₂ and R ₃ may represent an identical or different acyl group (R-CO) and in particular the same. In particular, n is advantageously from 25 to 50, in particular 38, in the general formula (C) of the ester according to the invention.

In particular, when the radicals R 1, R ₂ and / or R ₃ , which are identical or different, comprise an acyl group (R-CO), these may be chosen from caprylic, capric, lauric, myristic, palmitic, stearic and arachic radicals. behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoaracic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic, asclepine, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic, stearic, and mixtures thereof.

Preferably, at least one dextrin palmitate is used as dextrin ester and fatty acid (s). This can be used alone or mixed with other esters.

Advantageously, the ester of dextrin and of fatty acid has a degree of substitution less than or equal to 2.5 on the basis of a glucose unit, in particular ranging from 1.5 to 2.5, preferably from 2 to 2. 5. The weight average molecular weight of the dextrin ester may be in particular from 10,000 to 150,000, especially from 12,000 to 100,000 and even from 15,000 to

80,000.

Dextrin esters, in particular dextrin palmitates, are commercially available under the name RHEOPEARL TL or RHEOPEARL KL from Chiba Flour. (c) Hydrophobic modified polysaccharides

The polysaccharide used in the present invention is preferably selected from fructans. Fructans or fructosans are oligosaccharides or polysaccharides comprising a sequence of anhydrofructose units optionally associated with a plurality of different saccharide residues of fructose. The fructans can be linear or branched. The fructans can be products obtained directly from a plant or microbial source or products whose chain length has been modified (increased or reduced) by fractionation, synthesis or hydrolysis in particular enzymatic. The fructans generally have a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60.

There are 3 groups of fructans. The first group corresponds to products whose fructose units are mostly linked by β-2-1 bonds. These are essentially linear fructans that inulins. The second group also corresponds to linear fructoses but the fructose units are essentially linked by β-2-6 bonds. These products are levanes. The third group corresponds to mixed frucans, that is to say having sequences β-2-6 and β-2-1. These are essentially branched fructans than graminans.

The fructans used in the compositions according to the invention are inulins. Inulin can be obtained for example from chicory, dahlia or Jerusalem artichokes. Preferably, the inulin used in the composition according to the invention is obtained for example from chicory.

The polysaccharides, in particular inulins, used in the compositions according to the invention are hydrophobic modified. In particular, they are obtained by grafting hydrophobic chains onto the hydrophilic backbone of the fructan.

The hydrophobic chains capable of being grafted onto the main chain of the fructan can in particular be linear or branched hydrocarbon chains, saturated or unsaturated, having 1 to 50 carbon atoms, such as alkyl, arylalkyl, alkylaryl, alkylene; divalent cycloaliphatic groups or organopolysiloxane chains. These hydrocarbon or organopolysiloxane chains may in particular comprise one or more ester, amide, urethane, carbamate, thiocarbamate, urea, thiourea, and / or sulphonamide functions, such as especially methylenedicyclohexyl and isophorone; or divalent aromatic groups such as phenylene.

In particular, the polysaccharide, especially inulin, has a degree of polymerization of from 2 to about 1000 and preferably from 2 to about 60, and a degree of substitution of less than 2 on the basis of a fructose unit. According to a preferred embodiment, the hydrophobic chains have at least one alkyl carbamate group of formula R-NH-CO- in which R is an alkyl group having from 1 to 22 carbon atoms.

According to a more preferred embodiment, the hydrophobic chains are lauryl carbamate groups.

In particular, by way of illustration and without limitation, hydrophobic modified inulins which can be used in the compositions according to the invention, mention may be made of stearoyl inulin such as those sold under the names Lifidrem Inst by the company Engelhard and

Rheopearl INS by the company Ciba; palmitoyl inulin; undecylenoyl inulin such as those sold under the names Lifidrem INUK and Lifidrem INUM by the company

Engelhard; and inulin lauryl carbamate such as that sold under the name INUTEC

SP1 by the company ORAFTI

In particular, the hydrophobic modified polysaccharide is a lauryl carbamate grafted inulin, in particular derived from the reaction of lauryl isocyanate with an inulin, in particular derived from chicory. By way of example of these compounds, mention may be made especially of the product sold under the name INUTEC SP1 by the company ORAFTI. d) Copolymers of crystalline olefins: The crystalline olefin copolymer used in the compositions of the present application can be any olefin copolymer, ie a copolymer having only olefin moieties iq ues, having a controlled and moderate crystalline character, that is to say a crystallinity rate at most equal to 50%, preferably between 5 and 40%, and more preferably between 10 and 35%.

These copolymers are generally elastomers or plastomers and can be synthesized by any known method, in particular by radical route, by Ziegler-Natta catalysis or by metallocene catalysis, preferably by metallocene catalysis.

A first class of crystalline olefin copolymers which can be used in the compositions according to the invention are the copolymers of α-olefin, in particular α-olefin, which is C2-C18 and better still is C2-C12. Preferably, these copolymers are bi- or terpolymers and most particularly bipolymers.

Among the bipolymers recommended for the compositions of the invention include ethylene bipolymers and α-olefin C ^ C _j g, preferably C4-C12 and propylene bipolymers and α - olefin C ^ C _j g, preferably C ^ C - ^ - more preferably, the α-olefin is selected from butene-1, pentene-1, hexene-1, octene 1, nonene-1, decene-1, undecene-1, dodecene-1, 3,5,5-trimethylhexene-1, 3-methylpentene-1, and 4-methylpentene-1.

Among these monomers, butene-1 and octene-1 are particularly preferred. The level of α-olefin in the bipolymer is generally between 2 and 40% by mole, preferably 3 to 30% by mole, and more preferably 4 to 20% by mole.

The recommended ethylene-octene bipolymers are plastomers having an octene content of between 5.2% and 6.2% by mole, a degree of crystallinity between 28 and 38% and elastomers having an octene content of 8 to 14 mol% and a degree of crystallinity of 10 to 28%.

These bipolymers are synthesized by metallocene catalysis.

Such bipolymers are marketed by DOW CHEMICAL under the trade names AFFINITY (plastomers) and ENGAGE (elastomers).

Ethylene-butene bipolymers are marketed by EXXON under the trade name EXACT RESINS.

Amongst the terpolymers include terpolymers of ethylene, propylene and olefin C ^ C _j g, preferably C ^ C - ^ - In these terpolymers, the contents of olefin C ^ C- _j g are as indicated above and the preferred α-olefins are butene, hexene and octene.

A second class of olefin copolymers suitable for the compositions according to the invention are copolymers of ethylene or propylene and a cycloolefin, in particular bipolymers.

Generally, the cycloolefin content of the copolymers is less than 20 mol%.

Among the cycloolefins that may be used, mention may be made of cyclobutene, cyclohexene, cyclooctadiene, norbornene, dimethano-octahydronaphthalene (DMON), ethylidene norbornene, vinyl norbornene and 4-vinylcyclohexene.

The recommended copolymers of this class are copolymers of ethylene and norbornene. The norbornene content of these copolymers is generally less than 18 mol% to exhibit the required crystallinity and these copolymers are synthesized by metallocene catalysis. Suitable ethylene / norbornene copolymers are commercially available from

Companies MITSUI PETROCHEMICAL or MITSUI-SEKKA under the commercial name

APEL and by HOECHST-CELANESE under the trade name

TOPAS.

Other recommended ethylene / cycloolefin copolymers are ethylene / cyclobutene and ethylene / cyclohexene bipolymers with a low cycloolefin content, generally less than 20 mol%.

A third class of suitable olefin copolymers is olefin copolymers of controlled tacticity, i.e., copolymers having patterns of different tacticity.

Among these copolymers of controlled tacticity, mention may be made of propylene isotactic propylene / propylene copolymers and syndiotactic propylene / propylene atactic polypropylene.

The iso- or syndiotactic motifs or sequences impart crystalline character to the copolymer, while amorphous atactic patterns or sequences prevent excessive crystallinity of the copolymer and regulate the degree of crystallinity as well as the morphology and size of the crystallites.

The content of iso- or syndiotactic units, patterns imparting crystallinity to the copolymer, is therefore determined to obtain the desired percentage of crystallinity (≤ 50%) in the copolymer. The content of tactical units is generally between 10 and 80 mol%.

However, preferably, the content of atactic units is less than 30 mol%.

These copolymers are synthesized by metallocene catalysis.

A fourth class of olefin copolymers suitable for the present invention consists of monoolefin and diene copolymers, for example the ethylene / butadiene, propylene / butadiene, ethylene / isoprene and propylene / isoprene bipolymers, and the ethylene terpolymers. propylene / diene, also obtained by metallocene synthesis. The proportion of diene units in the controlled crystallization copolymer is generally between 3 and 20 mol%.

To improve the control of the crystallinity of the copolymer, additives which impede crystallization and favor the formation of small crystals may optionally be added to the composition according to the invention. These additives, although used in a small proportion, constitute

Numerous and small sprouting sites distributed evenly throughout the body. These additives are typically crystals of an organic or mineral substance.

In the case of an organic additive to be crystallized, it must have a melting point higher than the melting zone of the copolymer and preferably form small crystals.

At a temperature above its melting point, this substance is preferably soluble in the mixture of the liquid fatty phase and molten polymer. Thus, during cooling, the initially dissolved additive recrystallizes in the form of small and well-diffused small crystals in the mixture, and then the polymer recrystallizes to give small crystalline domains due to the presence of the additive crystals. This technique of recrystallization of polymers is conventional.

The degree of crystallization, the size and the morphology of the olefin copolymers according to the invention can also be adjusted by mixing a first olefin copolymer according to the invention with a second crystalline polymer or copolymer, partially compatible with the first copolymer olefins. The second polymer or copolymer may be an olefin copolymer according to the invention, but with a crystallinity level different from that of the first copolymer, including a degree of crystallinity higher than the degree of crystallinity of the olefin copolymers according to the invention. invention.

The second crystallizable polymer may also be a polymer of a different nature, for example a copolyethylene / vinyl acetate obtained by radical copolymerization or even a crystallizable polyethylene such as those conventionally used in the cosmetics field.

For more details on this method of adjusting crystallinity, reference should be made to the articles entitled "Elastomeric blends of homogeneous ethylene-octene copolymers (Elastomeric mixtures of homogeneous ethylene-octene copolymers)". Bensason et al. Polymer, Vol 38, No. 15, 1997, pages 391-3-1 9, and "Blends of Homogeneous Ethylene-Octene Copolymers (Mixtures of Ethylene-Octene Homogeneous Copolymers)"; Bensason et al. Polymer, Vol. 38, No. 14, 1997, pp. 351-3. D) Crystalline polycondensates:

The polycondensate that can be used may be obtainable by reaction:

from 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups;

from 30 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and / or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms;

from 0.1 to 10% by weight, relative to the total weight of the polycondensate, of at least one aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, optionally further substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and / or cyclic, which contain 1 to 32 carbon atoms;

from 5 to 40% by weight, relative to the total weight of the polycondensate, of at least one polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH, in particular 2 at 4 COOH groups; and / or a cyclic anhydride of such a polycarboxylic acid.

Preferably, the polycondensate is obtainable by reaction:

- 10% by weight of at least one aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, optionally further substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and / or cyclic, which comprise 1 to 32 carbon atoms; and from 15 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups; and

from 30 to 40% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and / or cyclic, saturated or unsaturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms; and

from 10 to 25% by weight, relative to the total weight of the polycondensate, of at least one polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH, in particular 2 at 4 COOH groups; and / or a cyclic anhydride of such a polycarboxylic acid; these conditions being cumulative, then the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of non-aromatic monocarboxylic acid is between 0.08 and 0.70.

The polycondensate may also be capable of being obtained by reacting: from 10 to 30% by weight, relative to the total weight of the polycondensate, of at least one polyol comprising 3 to 6 hydroxyl groups;

from 45 to 80% by weight, relative to the total weight of the polycondensate, of at least one linear, branched and / or cyclic saturated non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms; from 0.1 to 10% by weight, relative to the total weight of the polycondensate, of at least one aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, optionally further substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and / or cyclic, which contain 1 to 32 carbon atoms;

One of the constituents necessary for the preparation of the polycondensates according to the invention is a compound comprising 3 to 6 hydroxyl groups (polyol), in particular 3 to 4 hydroxyl groups. It is of course possible to use a mixture of such polyols. Said polyol may especially be a hydrocarbon compound, in particular linear, branched and / or cyclic, saturated or unsaturated, comprising 3 to 18 carbon atoms, especially 3 to 12 or even 4 to 10 carbon atoms, and 3 to 6 groups. hydroxy (OH), and may further comprise one or more oxygen atoms intercalated in the chain (ether function). Said polyol is preferably a saturated hydrocarbon compound, linear or branched, comprising 3 to 18 carbon atoms, especially 3 to 12 or even 4 to 10 carbon atoms, and 3 to 6 hydroxyl groups (OH). It can be chosen from, alone or in mixture:

triols, such as 1, 2,4-butanetriol, 1, 2,6-hexanetriol, trimethylolethane, trimethylolpropane, glycerol; tetraols, such as pentaerythritol (tetramethylolmethane), erythritol, diglycerol or ditrimethylolpropane;

pentols such as xylitol,

hexols such as sorbitol and mannitol; or dipentaerythritol or triglycerol.

Preferably, the polyol is chosen from glycerol, pentaerythritol, diglycerol, sorbitol and their mixtures; and even better is pentaerythritol. The polyol, or the polyol mixture, preferably represents 10 to 30% by weight, especially 12 to 25% by weight, and more preferably 14 to 22% by weight, of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is a saturated or unsaturated, linear, branched and / or cyclic non-aromatic monocarboxylic acid comprising 6 to 32 carbon atoms, in particular 8 to 28 carbon atoms, and even better 10 to 24 or even 12 to 20 carbon atoms. It is of course possible to use a mixture of such nonaromatic monocarboxylic acids. By non-aromatic monocarboxylic acid is meant a compound of formula RCOOH, in which R is a saturated or unsaturated hydrocarbon radical, linear, branched and / or cyclic, comprising 5 to 31 carbon atoms, especially 1 to 21 carbon atoms, and still more preferably 9 to 23 carbon atoms, or even 1 1 to 19 carbon atoms. Preferably, the radical R is saturated. Even better, said radical R is linear or branched, and preferably C5-C31, or even C11-C21. In a particular embodiment of the invention, the nonaromatic monocarboxylic acid has a melting point greater than or equal to 25 ° C, especially greater than or equal to 28 ° C, or even 30 ^° C; it has indeed been found that when such an acid is used, in particular in large quantities, it is possible, on the one hand, to obtain a good gloss and the holding of said gloss, and on the other hand to reduce the amount of waxes usually present in the composition envisaged.

Among the nonaromatic monocarboxylic acids that may be used, mention may be made, alone or as a mixture:

saturated monocarboxylic acids such as caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2- heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid); cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid;

unsaturated but nonaromatic monocarboxylic acids, such as caproleic acid, obtusilic acid, undecylenic acid, dodecylenic acid, linderic acid, myristoleic acid, physétérique acid, tsuzuique acid , palmitoleic acid, oleic acid, petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, cetoleic acid, nervonic acid , linoleic acid, linolenic acid, arachidonic acid.

Among the nonaromatic monocarboxylic acids having a melting point greater than or equal to 25 ° C., mention may be made, alone or as a mixture of: - among the saturated monocarboxylic acids: decanoic acid (capric), lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid);

- Of unsaturated but nonaromatic monocarboxylic acids: petroselinic acid, vaccenic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, nervonic acid.

Preferably, it is possible to use 2-ethylhexanoic acid, isooctanoic acid, lauric acid, myristic acid, isoheptanoic acid, isononanoic acid, nonanoic acid, palmitic acid, isostearic acid, stearic acid, behenic acid and mixtures thereof, and even better isostearic acid alone or stearic acid alone. Said nonaromatic monocarboxylic acid, or the mixture of said acids, is preferably 30 to 80% by weight, especially 40 to 75% by weight, or even 45 to 70% by weight, and more preferably 50 to 65% by weight, of the total weight. of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is an aromatic monocarboxylic acid comprising 7 to 11 carbon atoms, optionally further substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and / or cyclic, which comprise 1 to 32 carbon atoms, especially 2 to 12 or even 3 to 8 carbon atoms. It is of course possible to use a mixture of such aromatic monocarboxylic acids. By aromatic monocarboxylic acid is meant a compound of formula

R'COOH, wherein R 'is an aromatic hydrocarbon radical, comprising 6 to 10 carbon atoms, and in particular the benzoic and naphthoic radicals. Said radical R 'may also be substituted with 1 to 3 alkyl radicals, saturated or unsaturated, linear, branched and / or cyclic, comprising 1 to 32 carbon atoms, especially 2 to 12 or even 3 to 8 carbon atoms; and especially selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, terbutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, isoheptyl, octyl or isooctyl. Among the monocarboxylic aromatic acids that may be used, mention may be made, alone or in a mixture, of benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, acid 1 naphthoic acid, 2-naphthoic acid, 4-tert-butyl-benzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid. Preferably, benzoic acid, 4-tert-butyl-benzoic acid, o-toluic acid, m-toluic acid, 1-naphthoic acid can be used alone or in mixtures; and even better, benzoic acid alone. Said aromatic monocarboxylic acid, or the mixture of said acids, is preferably 0.1 to 10% by weight, especially 0.5 to 9.95% by weight, more preferably 1 to 9.5% by weight, or even 1, 5 to 8% by weight, of the total weight of the final polycondensate.

Another constituent necessary for the preparation of the polycondensates according to the invention is a polycarboxylic acid, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic, comprising at least 2 carboxylic groups COOH, especially 2 to 4 COOH groups; and / or a cyclic anhydride of such a polycarboxylic acid. It is of course possible to use a mixture of such polycarboxylic acids and / or anhydrides. Said polycarboxylic acid may in particular be chosen from linear, branched and / or cyclic, saturated or unsaturated or even aromatic polycarboxylic acids, comprising 2 to 50, in particular 2 to 40, carbon atoms, in particular 3 to 36 or even 3 to 18 and still more preferably 4 to 12 carbon atoms, or even 4 to 10 carbon atoms; said acid comprises at least two carboxylic groups COOH, preferably from 2 to 4 COOH groups.

Preferably, said polycarboxylic acid is saturated, linear aliphatic and comprises 2 to 36 carbon atoms, especially 3 to 18 carbon atoms, or even 4 to 12 carbon atoms; or is aromatic and comprises 8 to 12 carbon atoms. It preferably comprises 2 to 4 COOH groups. Said cyclic anhydride of such a polycarboxylic acid may in particular correspond to one of the following formulas:

in which the groups A and B are independently of each other:

a hydrogen atom,

a saturated or unsaturated, linear, branched and / or cyclic, or aromatic, carbon, aliphatic radical; comprising 1 to 16 carbon atoms, especially 2 to 10 carbon atoms, or even 4 to 8 carbon atoms, especially methyl or ethyl; or A and B taken together form a ring comprising in total 5 to 7, in particular 6 carbon atoms, saturated or unsaturated, or even aromatic.

Preferably, A and B represent a hydrogen atom or together form an aromatic ring comprising a total of 6 carbon atoms.

Among the polycarboxylic acids or their anhydrides that may be used, mention may be made, alone or as a mixture:

dicarboxylic acids such as decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid and 2,3-naphthalene acid; dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, itaconic acid, fatty acid dimers (especially C36) such as the products sold under the names Pripol 1006, 1009, 1013 and 1017, by Uniqema; tricarboxylic acids such as cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid;

tetracarboxylic acids such as butanetetracarboxylic acid and pyromellitic acid; cyclic anhydrides of these acids, especially phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride.

Preferably, it is possible to use adipic acid, phthalic anhydride and / or isophthalic acid, and even better isophthalic acid alone.

Said polycarboxylic acid and / or its cyclic anhydride is preferably 5 to 40% by weight, especially 10 to 30% by weight, and more preferably 14 to 25% by weight, of the total weight of the final polycondensate.

The polycondensate according to the invention may further comprise a hydroxyl functional silicone (OH) and / or carboxylic acid (COOH). It can comprise 1 to 3 hydroxyl and / or carboxylic functions, and preferably comprises two hydroxyl functions or two carboxylic functions.

These functions can be located at the end of the chain or in the chain, but advantageously at the end of the chain.

Silicones having a weight average molecular weight (Mw) of between 300 and 20000, in particular 400 and 10,000, or even 800 and 4000, are preferably used.

This silicone can be of formula:

wherein: W and W are, independently of one another, OH or COOH; preferably W = W;

p and q are, independently of one another, equal to 0 or 1,

- R and R 'are, independently of one another, a divalent carbon radical, in particular hydrocarbon, saturated or unsaturated, or even aromatic, linear, branched and / or cyclic; comprising 1 to 12 carbon atoms, especially 2 to 8 carbon atoms, and optionally further comprising 1 or more heteroatoms selected from O, S and N, especially O

(ether); in particular R and / or R 'may be of formula - (CH ₂ ) _a - with a = 1-12, and especially methylene, ethylene, propylene, phenylene; or of formula - [(CH ₂ ) _X O] _Z - with x = 1, 2 or 3 and z = 1-10; in particular x = 2 or 3 and z = 1-4; and better x = 3 and z = 1.

- R1 to R6 are, independently of one another, a linear carbon radical, branched and / or cyclic, saturated or unsaturated or aromatic; comprising 1 to 20 carbon atoms, especially 2 to 12 carbon atoms; preferably, R 1 to R 6 are saturated or aromatic, and may especially be chosen from alkyl radicals, in particular the methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl and octadecyl radicals, and the radicals cycloalkyls, in particular the cyclohexyl radical, aryl radicals, in particular phenyl and naphthyl radicals, arylalkyl radicals, in particular benzyl and phenylethyl radicals, as well as tolyl and xylyl radicals.

m and n are, independently of one another, integers between 1 and 140, and are such that the weight average molecular weight (Mw) of the silicone is between 300 and

20,000, especially between 400 and 10,000, or between 800 and 4000.

Mention may in particular be made of α, ω-diol or α, ω-dicarboxylic polyalkylsiloxanes, and in particular α, ω-diol polydimethylsiloxanes and α, ω-dicarboxylic polydimethylsiloxanes; the α, ω-diol or α, ω-dicarboxylic polyarylsiloxanes, and in particular the α, ω-diol or α, ω-dicarboxylic polyphenylsiloxanes; silanol-functional polyarylsiloxanes such as polyphenylsiloxane; polyalkylsiloxanes with silanol functions such as polydimethylsiloxane; silanol-functional polyaryl / alkylsiloxanes such as polyphenyl / methylsiloxane or else polyphenyl / propylsiloxane.

In particular, the α, ω-diol polydimethylsiloxanes having a weight-average molecular weight (Mw) of between 400 and 10,000, even between 500 and 5,000, and especially between 800 and 4000, will be used.

When present, said silicone may preferably represent 0.1 to 15% by weight, especially 1 to 10% by weight, or even 2 to 8% by weight, of the weight of the polycondensate.

In a preferred embodiment of the invention, the aromatic monocarboxylic acid is present in a molar amount less than or equal to that of the nonaromatic monocarboxylic acid; in particular the ratio between the number of moles of aromatic monocarboxylic acid and the number of moles of nonaromatic monocarboxylic acid is preferably between 0.08 and 0.70, in particular between 0.10 and 0.60, in particular between 0.12 and 0.40. Preferably, the polycondensate according to the invention can be obtained by reaction:

at least one polyol chosen from, alone or as a mixture, 1,2,6-hexanetriol, trimethylolethane, trimethylolpropane and glycerol; pentaerythritol, erythritol, diglycerol, ditrimethylolpropane; xylitol, sorbitol, mannitol, dipentaerythritol and / or triglycerol; preferably present in an amount of 10 to 30% by weight, especially 12 to 25% by weight, and more preferably 14 to 22% by weight, relative to the total weight of the final polycondensate;

at least one nonaromatic monocarboxylic acid chosen from, alone or as a mixture, caproic acid, caprylic acid, isoheptanoic acid, 4-ethylpentanoic acid, 2-ethylhexanoic acid, 4,5-dimethylhexanoic acid, 2-heptylheptanoic acid, 3,5,5-trimethylhexanoic acid, octanoic acid, isooctanoic acid, nonanoic acid, decanoic acid, isononanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, cerotic acid (hexacosanoic acid); cyclopentanecarboxylic acid, cyclopentaneacetic acid, 3-cyclopentylpropionic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, 4-cyclohexylbutyric acid; preferably present in an amount of 30 to 80% by weight, especially 40 to 75% by weight, and more preferably 45 to 70% by weight, relative to the total weight of the final polycondensate;

at least one aromatic monocarboxylic acid chosen from, alone or as a mixture, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, 1-naphthoic acid, 2-naphthoic acid, 4-tert-butyl benzoic acid, 1-methyl-2-naphthoic acid, 2-isopropyl-1-naphthoic acid; preferably present in an amount of 0.1 to 10% by weight, in particular 1 to 9.5% by weight, or even 1.5 to 8% by weight, relative to the total weight of the final polycondensate; and at least one polycarboxylic acid or one of its anhydrides chosen from, alone or as a mixture, decanedioic acid, dodecanedioic acid, cyclopropanedicarboxylic acid, cyclohexanedicarboxylic acid, cyclobutanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, suberic acid, oxalic acid, malonic acid, succinic acid , phthalic acid, terephthalic acid, isophthalic acid, pimelic acid, sebacic acid, azelaic acid, glutaric acid, adipic acid, fumaric acid, maleic acid ; cyclohexanetricarboxylic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid; butanetetracarboxylic acid, pyromellitic acid, phthalic anhydride, trimellitic anhydride, maleic anhydride and succinic anhydride; preferably present in an amount of 5 to 40% by weight, especially 10 to 30% by weight, and more preferably 14 to 25% by weight, relative to the total weight of the final polycondensate.

Preferably, the polycondensate according to the invention is capable of being obtained by reacting: at least one polyol chosen from, alone or as a mixture, glycerol, pentaerythritol, sorbitol and mixtures thereof, and even more preferably pentaerythritol alone; present in an amount of 10 to 30% by weight, especially 12 to 25% by weight, and more preferably 14 to 22% by weight, relative to the total weight of the final polycondensate;

at least one non-aromatic monocarboxylic acid chosen from, alone or as a mixture, 2-ethylhexanoic acid, isooctanoic acid, lauric acid, palmitic acid, isostearic acid and isononanoic acid, stearic acid, behenic acid and mixtures thereof, and even better isostearic acid alone or stearic acid alone; present in an amount of 30 to 80% by weight, especially 40 to 75% by weight, and more preferably 45 to 70% by weight, relative to the total weight of the final polycondensate; at least one aromatic monocarboxylic acid chosen from, alone or as a mixture, benzoic acid, o-toluic acid, m-toluic acid, 1-naphthoic acid, and even more preferably benzoic acid; alone; present in an amount of 0.1 to 10% by weight, especially 1 to 9.5% by weight, or even 1.5 to 8% by weight relative to the total weight of the final polycondensate; and

at least one polycarboxylic acid or one of its anhydrides, chosen from, alone or as a mixture, phthalic anhydride and isophthalic acid, and even better isophthalic acid alone; present in an amount of 5 to 40% by weight, especially 10 to 30% by weight, and more preferably 14 to 25% by weight, relative to the total weight of the final polycondensate.

The polycondensate according to the invention can be prepared by the esterification / polycondensation processes usually employed by those skilled in the art. As an illustration, a general method of preparation consists of:

- mixing the polyol and the aromatic and nonaromatic monocarboxylic acids,

to heat the mixture under an inert atmosphere, first up to the melting temperature (generally 100-130 ^° C.) and then at a temperature of between 150 ^° C. and 220 ^° C. until the monocarboxylic acids have been consumed completely (reached when the acid number is less than or equal to 1), preferably by gradually distilling the water formed, and then

to optionally cool the mixture to a temperature of between 90 and 150 ° C.,

to add the polycarboxylic acid and / or the cyclic anhydride, and optionally the hydroxyl or carboxylic functional silicone, in one go or in a sequenced manner, then

- To heat again at a temperature of less than or equal to 220 ⁰ C, in particular between 170 and 220 ⁰ C, preferably continuing to remove the water formed, until the characteristics required in terms of index are obtained. acid, viscosity, hydroxyl number and solubility. It is possible to add conventional esterification catalysts, for example of the sulphonic acid type (especially at a concentration by weight of between 1 and 10%) or titanate type (in particular at a weight concentration of between 5 and 100 ppm). It is also possible to carry out the reaction, in whole or in part, in an inert solvent such as xylene and / or under reduced pressure, to facilitate the removal of water. Advantageously, no catalyst or solvent is used.

Said preparation process may further comprise a step of adding at least one antioxidant agent to the reaction medium, in particular at a concentration by weight of between 0.01 and 1%, relative to the total weight of monomers, so as to limit any damage caused by prolonged heating.

The antioxidant may be of primary or secondary type, and may be selected from hindered phenols, aromatic secondary amines, organophosphorus compounds, sulfur compounds, lactones, acrylated bisphenols; and their mixtures.

Mineral lipophilic structuring agents

The thickening rheological agent or gelling agent of the fatty phase may be a mineral lipophilic structuring agent. Lipophilic clays, such as optionally modified clays, such as hectorites modified with a C 10 -C ₂₂ fatty acid ammonium chloride, such as hectorite modified with di-stearyl di- methyl ammonium.

It is also possible to mention hydrophobic silicas, such as fumed silica optionally treated with hydrophobic surface, the particle size of which is less than

1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a decrease in the number of silanol groups present on the surface of the silica. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained. The hydrophobic groups can be:

trimethylsiloxyl groups, which are especially obtained by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica Silylate" according to the CTFA (6 ^th edition, 1995). They are for example marketed under the references "AEROSIL R812®" by Degussa, "CAB-O-SIL TS-530®" by Cabot.

- Dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl Silylate" according to the CTFA (6 ^th edition, 1995). They are for example sold under the references "AEROSIL R972®", "AEROSIL R974®" by the company Degussa, "CAB-O-SIL TS-

610® "," CAB-O-SIL TS-720® "by Cabot.

The hydrophobic fumed silica preferably has a particle size that may be nanometric to micrometric, for example from about 5 to 200 nm.

Lipophilic polyamide polymers

For the purposes of the invention, the term "polymer" means a compound having at least 2 repeating units, preferably at least 3 repeating units and more preferably 10 repeating units. As preferred lipophilic structuring polyamide polymers that may be used in the invention, mention may be made of polyamides branched by pendant fatty chains and / or terminal fatty chains having from 12 to 120 carbon atoms and in particular from 12 to 68 carbon atoms, the chains fatty oils being linked to the polyamide backbone by ester groups. These polymers are more especially those described in the document US-A-5783657 of the company Union Camp. Each of these polymers satisfies in particular the following formula (I):

wherein n denotes an integer number of amide units such that the number of ester groups is from 10% to 50% of the total number of ester and amide groups; R is independently at each occurrence an alkyl or alkenyl group having at least 4 carbon atoms; R ² is independently at each occurrence a C ₄ to C ₄₂ hydrocarbon group provided that 50% of the R ² groups are a C 30 to C ₄₂ hydrocarbon group; R ³ independently represents an organic group having at least 2 carbon atoms, hydrogen atoms and optionally one or more oxygen or nitrogen atoms; and R ⁴ represents at each occurrence independently a hydrogen atom, a C ₁ -C ₁₀ alkyl group or a direct bond to R ³ or another R ⁴ such that the nitrogen atom to which both R ³ and R ⁴ are bonded is part of a heterocyclic structure defined by R ⁴ -NR ³ , with at least 50% of the R ⁴ representing a hydrogen atom.

In particular, the ester groups of formula (I), which are part of the terminal and / or pendant fatty chains within the meaning of the invention, represent from 15 to 40% of the total number of ester and amide groups and better still from 20 to 35%. In addition, n advantageously represents an integer ranging from 1 to 5. Preferably, R ¹ is a C ₂ to C ₂₂ alkyl group and preferably C ₆ to C _22. Advantageously, R ² may be a hydrocarbon group ( C ₁ to C ₄₂ alkyl or alkenyl having a polymerized fatty acid or dimer structure from which the carboxylic acid groups have been removed (these groups serving for the formation of the amide). Preferably, at least 50% and more preferably 75% of the R ² are groups having from 30 to 42 carbon atoms. The other R ² are C ₄ to C ₁₉ hydrogenated groups and even C ₄ to C ₁₂ hydrogenated groups. Preferably, R ³ represents a C ₂ to C ₃₆ hydrocarbon group or a polyoxyalkylene group and R ⁴ represents a hydrogen atom. Preferably, R ³ represents a hydrocarbon group, C ₂ to C _2. The hydrocarbon groups may be linear, cyclic or branched, saturated or unsaturated groups. On the other hand, the alkyl and alkenyl groups can be linear or branched groups.

Advantageously, the polymer of the composition of the invention comprises a weight average molecular weight ranging from 2,000 to 20,000 and better still from 2,000 to 10,000. According to the invention, the structuring of the oil is obtained at using one or more polymers of formula (I). In general, the polymers of formula (I) are in the form of polymer mixtures, these mixtures may further contain a synthetic product such that n is 0, that is to say a diester. By way of example of structuring polymers that can be used in the composition according to the invention, mention may be made of the commercial products sold by Bush Boake Allen under the names Uniclear 80, Uniclear 100, Uniclear 80 V, Uniclear 100 V and Uniclear 100 VG. . They are sold respectively in the form of 80% gel (active ingredient) in a mineral oil and 100% (active ingredient). They have a softening point of 88 to 94 ° C. These commercial products are a copolymer mixture of a C ₃₆ di-acid condensed on the ethylene diamine of average molecular weight of about 6000. The remaining acid terminations are further esterified by cetylstearyl alcohol.

As structuring polymer that can be used in the invention, mention may also be made of polyamide resins resulting from the condensation of an aliphatic dicarboxylic acid and a diamine (including compounds having more than 2 carbonyl groups and 2 amino groups), carbonyl and amine groups of adjacent unitary units being fused by an amide bond. These polyamide resins are especially those marketed under the Versamid® brand by General Mills, Inc. and Henkel Corp. (Versamid 930, 744 or 1655) or by ONn Mathieson Chemical Corp., under the name Onamid®, in particular Onamid S or C. These resins have a weight average molecular weight ranging from 6000 to 9000. For more information on these polyamides, reference may be made to US-A-3645705 and US-A-3148125. More specifically, Versamid® 930 or 744 are used.

Polyamides sold by Union Camp Corp. can also be useful. under the references Uni-Rez (2658, 2931, 2970, 2621, 2613, 2624, 2665, 1554, 2623, 2662) and the product sold under the reference Macromelt 6212 by Henkel. For more information on these polyamides, reference may be made to US-A-5500209.

The structuring polymers of the composition of the invention advantageously have a softening temperature greater than 70 ^° C. and up to 190 ^° C. Preferably, it has a softening temperature ranging from 80 to 130 ^° C. These polymers are in particular non-waxy polymers.

Polyuric polymers or lipophilic polyurethanes

As rheological agent of the fatty phase, mention may also be made of polyurethanes and polyureas that are soluble or dispersible in the hydrocarbon oil (s), and comprising:

at least two urethane groups, or at least two urea groups or at least one urethane group and a urea group in the chain,

at least one hydrocarbon or aliphatic polyester long chain or hydrocarbon grafted, preferably branched, chain or graft.

By long hydrocarbon chain is meant a hydrocarbon chain, linear or branched, having at least 8 carbon atoms and preferably 10 to 500 carbon atoms.

The preferred polymers according to the invention are defined by one of the following three formulas:

wherein: n denotes an integer from 1 to 10,000, and preferably from 1 to 1000, x represents, separately or together, -O- or -NH-,

R is a divalent radical chosen from alkylene, cycloalkylene and aromatic radicals, and their mixtures, which may be functionalized,

A- | and A2, which may be identical or different, denote linear, branched or cyclic, saturated or unsaturated monovalent hydrocarbon radicals containing from 1 to 80 carbon atoms,

D is

1) a divalent hydrocarbon aliphatic and / or cycloaliphatic saturated or unsaturated and / or aliphatic polyester long chain hydrocarbon chain, or 2) a graft where Z is a trivalent hydrocarbon radical which may contain one or more heteroatoms, and φ is a linear, branched or cyclic aliphatic chain, 3) mixtures of sequences 1) and grafts 2). Monovalent hydrocarbon radicals A- | and A2 are preferably selected from aliphatic, cycloaliphatic and aromatic, saturated or unsaturated radicals. The radicals A- | and A2 are monoalcohols and / or monoamines optionally used to consume the residual isocyanate groups at the end of polymerization.

In the case where D is an aliphatic and / or cycloaliphatic hydrocarbon sequence, saturated or not, this comes from:

- a natural or synthetic oil, or the addition product (dimer, trimer or polymer) of at least two unsaturated aliphatic chains, such as aliphatic radicals derived from "dimer" fatty acids, such as, for example, addition products between oleic chains, or

polyenes, preferably hydrogenated, such as polybutadiene, hydrogenated polyisoprene, or polyolefins or copolyolefins.

In the case where D is an aliphatic polyester long chain hydrocarbon chain, it is preferably derived from branched polyesters with long hydrocarbon chains, such as poly (12-hydroxystearate).

In the case where D is a graft, φ is an aliphatic chain, linear, branched or cyclic, saturated or unsaturated, having from 8 to 40 carbon atoms. The optional heteroatoms of the trivalent radical Z are preferably -O-, -N-, and -S-.

The structuring polyurethanes and / or polyureas according to the invention result from the polymerization reaction between:

1) at least one aliphatic, cycloaliphatic and / or aromatic diisocyanate of general formula O = C = N-R-N = C = O, where R is as defined above,

2) at least one difunctional derivative HX-D-XH, having two active hydrogens each reactive with an isocyanate group, wherein

X denotes -O- or -NH-, and

- D is as defined above, and 3) optionally, a monofunctional derivative A- | -XH, or two monofunctional derivatives A- | -XH and A2-XH, having a single active hydrogen that can react with an isocyanate group, to consume the residual isocyanate groups which would not have fully reacted with the difunctional reagents HXDXH, the monofunctional derivatives A- | -XH and A2-XH which may be identical or different, and A- | and A2 being as previously defined.

The isocyanates used in the polymerization reaction may be aliphatic, cycloaliphatic or aromatic. Advantageously, hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate will be used. The difunctional derivatives HXDXH may be chosen from diol dimers and their derivatives, alkane diols, polydienes with hydroxyl ends, preferably hydrogenated, polyolefins with hydroxyl ends, branched long chain alkyl polyesters bearing at least two reactive groups, natural or synthetic oils bearing from two to three hydroxyl groups, and finally dimeric diamines and long-chain aliphatic diamines.

Dimers diols are branched, aliphatic and / or alicyclic C36 diols, and / or a mixture of said dimers. These diols are prepared from the corresponding "dimer fatty acids".

The term "corresponding dimer fatty acids" means dimeric fatty acids which have the same structure as these diols, but which have two carboxylic acid ends in place of the diol ends. The conversion of dimeric fatty acids to dimers diols can be carried out either by hydrogenation of methyl esters of dimer fatty acids or by direct dimerization of oleic alcohol. In particular, the dimers diols sold by the company COGNIS under the trade names SOVERMOL 908 (97% purity) and SOVERMOL 650 NS (68% purity) are mentioned.

It is also possible to use the polyether diol oligomers and the polycarbonate diols prepared by the subsequent etherification or esterification of these same C36 branched diol dimers. These oligomers generally have a number-average molecular weight of around 500 to 2000. and have two hydroxyl functions. The polydienes with hydroxyl ends are for example those defined in French patent FR-2782723. They are selected from the group consisting of homo and copolymers of polybutadiene, polyisoprene and poly (1,3-pentadiene). These oligomers have a number-average molecular mass of less than 7000, and preferably from 1000 to 5000. They have an end-of-the-chain functionality of 1.8 to 3, and preferably close to 2. These polydienes with hydroxyl ends are, for example, the hydroxylated polybutadienes sold by ELF ATOCHEM under the trademarks POLY BD-45H® and POLY BD R-20 LM®. These products are preferably used hydrogenated.

It is also possible to use polyolefins, homopolymers or copolymers with α, ω hydroxyl ends, for example:

polyisobutylene oligomers with oc, ω hydroxyl ends, or

the copolymers marketed by MITSUBISHI under the trade name POLYTAIL®, in particular those of structure:

having a melting point of 60 to 70 ^° C.

It is possible to use, as difunctional derivative H-X-D-X-H, a long-chain alkyl branched polyester having at least two reactive groups, for example hydroxyl-terminated poly (12-hydroxystearate). This polyester is obtained by autocondensation of 1, 2-hydroxystearic acid on itself, then reaction with a polyol to consume the residual acid groups. This oligomer of structure

wherein the sum m + n is such that the oligomer has a number average molecular weight of about 2000 and a hydroxyl functionality of about 1, 8.

It is also possible to use, as difunctional derivative H-X-D-X-H, natural or synthetic oils bearing from two to three hydroxyl groups.

In a particular embodiment of the invention, the oils bearing two hydroxyl groups per chain, and preferably the monoglycerides of structure:

Ri is a linear or branched Cs to C30 alkyl chain such as, for example, glycerol monostearate.

Such glycerol monoesters correspond, for example, to the difunctional derivatives H-X-D-X-H, where:

- D represents X represents - O -, and

where R is defined as before.

When these glycerol monoesters are reacted with a diisocyanate, a solubilizing graft is introduced into the polymer chain and not a sequence, as was the case with the difunctional derivatives mentioned above.

In one variant, use will be made of a difunctional derivative H-X-D-X-H chosen from oils bearing three hydroxyl groups per chain, for example castor oil, hydrogenated or otherwise.

In this case, the polymerization reaction is carried out with a diisocyanate defect with respect to the stoichiometry of the reaction, in order to avoid the crosslinking of the polymer and to maintain a good solubility.

Long chain aliphatic diols can also be used. Advantageously, the diols of structure HO-D-OH where D is a linear or branched alkyl chain containing from 8 to 40 carbon atoms, will be used. These diols are marketed by ATOCHEM under the name VIKINOL®. There may also be mentioned 1, 12 dodecane diol and 1, 10 decane diol, the latter being marketed by COGNIS under the trade name SOVERMOL 1 10®.

Structural diols can also be used

Wherein R is an alkyl chain having from 8 to 40 carbon atoms.

These long aliphatic chain diols are preferably used with one or the other of the H-X-D-X-H derivatives mentioned above, to serve as chain couplers during the synthesis of polyurethanes and / or polyureas.

Finally, difunctional derivatives H-X-D-X-H may be dimeric diamines or long-chain aliphatic diamines.

The use of such reagents in the polymerization reaction makes it possible to introduce into the polymer, urea groups instead of urethane groups. According to one particular embodiment of the invention, dimer diamines having the same structure as the dimers-diols described above, that is to say dimer diamines having two primary amine functions in place of the groups, will be used. hydroxyls.

These dimeric diamines can be obtained from the transformation of dimeric fatty acids, such as dimers-diols.

In a variant, it is possible to use diamines of structure H2N-D-NH2 where D is a linear or branched alkyl chain containing from 8 to 40 carbon atoms. These diamines are preferably used in admixture with a difunctional derivative HXDXH chosen from dimers-diols and their derivatives, polydienes and polyolefins with hydroxyl ends, long-chain alkyl branched polyesters, and oils bearing from 2 to 3 hydroxyl groups, previously mentioned.

Among these diamines, mention may be made of: 1, 10-diamino decane and 1,12 diamino dodecane, and the following diamined oils marketed by the company Akzo Nobel: cocopropylene diamine (distilled or not) DUOMEEN® C or CD, hydrogenated tallowpropylene diamine DUOMEEN® HT, C-6-22 alkylpropylene diamine DUOMEEN® M, oleylpropylene diamine DUOMEEN® O, Tallowpropylene diamine DUOMEEN® T. With regard to the monofunctional derivatives A- | -XH and A2-XH, they are advantageously chosen from monoalcohols or monoamines with linear or branched alkyl chains containing from 1 to 80 carbon atoms, natural oils or synthetic having a single hydroxyl group per chain, such as, for example, glycerol diesters or triesters of citric acid and fatty alcohol. The reactions of polycondensations envisaged are conventionally carried out in an organic solvent, capable of dissolving the reagents and the polymer formed. This solvent is preferably easily removed at the end of the reaction, in particular by distillation and does not react with the isocyanate groups.

Generally, each of the reactants is dissolved in a portion of the organic solvent prior to the polymerization reaction.

It is sometimes desired to use a catalyst to activate the polymerization. This will generally be selected from the catalysts commonly used in the chemistry of polyurethanes and polyureas, such as tin 2-ethyl hexanoate.

The molar proportion between the main reactants of the polymerization reaction depends on the chemical structure and the molecular weight of the polymers (polyurethanes and / or polyureas) which it is desired to obtain, as is conventionally the case in the polyurethane and polyurethane chemistry. polyureas. Similarly, the order of introduction of the reagents will be adapted to this chemistry.

Thus, the reaction of two moles of functional derivative H-X-D-X-H with one mole of diisocyanate gives, after total consumption of the reactants, a polymer defined by the formula I:

For this reaction, advantageously proceed as follows:

the initial medium is a solution comprising two moles of H-X-D-X-H derivative, for example two moles of dimer-diol, in a solvent, for example tetrahydrofuran,

a solution comprising a mole of diisocyanate dissolved in the same solvent, for example toluene diisocyanate dissolved in tetrahydrofuran, is added dropwise to this initial solution.

Moreover, the equimolar reaction of a difunctional derivative H-X-D-X-H with a diisocyanate, with the consumption of the residual isocyanates by a monofunctional compound A-XH, gives a polymer defined by the formula III:

This reaction will then preferably be carried out by simultaneous addition, in a reactor, of an organic solution of one mole of HXDXH, such as, for example, a POLYTAIL® previously described, and of an organic solution of one mole of diisocyanate, such as, for example, 4,4'-dicyclohexylmethane diisocyanate. The simultaneous addition of these two organic solutions is also called "double casting". At the end of double casting, the reaction mixture is heated at 60 ^° C. for 5 hours. Then, a sample of the reaction medium is taken to determine the residual isocyanates using a method known from the skilled person. Finally, a solution of a selected monofunctional compound Ai-XH is added to the reaction medium in an amount sufficient to consume the residual isocyanates, this amount having been estimated from the residual isocyanate assay. Advantageously, the monofunctional derivative Ai-XH will be 1-decanol. Finally, the reaction between

one mole of H-X-D-X-H compound, for example a dimer-diol,

three moles of diisocyanate, for example 4,4'-dicyclohexyl methane diisocyanate, and

two moles of structure coupler

where φ is an aliphatic chain, linear, branched or cyclic having from 8 to 20 carbon atoms, leads to the formation of a polymer at the same time sequence and grafted structure:

The optionally residual isocyanates that can be consumed by adding an appropriate amount of monofunctional reagent Al-X-H.

To obtain such a polymer, the procedure is as follows:

the initial reaction medium consists of a solution comprising one mole of a difunctional derivative H-X-D-X-H,

a solution of three moles of diisocyanate is added dropwise to this medium,

- is then allowed to react for 3 hours at 60 ⁰ C:

and then pouring into this medium an organic solution comprising two moles of a coupler, defined by the formula

the optionally residual isocyanates may be consumed by adding an appropriate amount of monofunctional reagent Al-XH.

Lipophilic silicone polymers:

The polymeric silicone lipophilic structuring agents are, for example, polymers of the polyorganosiloxane type, such as those described in US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680. According to the invention, the polymers used as structuring agent can belong to the following two families:

1) polyorganosiloxanes having at least two groups capable of establishing hydrogen interactions, these two groups being located in the polymer chain, and / or

2) polyorganosiloxanes comprising at least two groups capable of establishing hydrogen interactions, these two groups being located on grafts or branches.

Groups capable of establishing hydrogen interactions may be selected from ester, amide, sulfonamide, carbamate, thiocarbamate, urea, urethane, thiourea, oxamido, guanidino, biguanidino and combinations thereof. According to a first variant, the silicone polymers are polyorganosiloxanes as defined above and whose units capable of establishing hydrogen interactions are arranged in the polymer chain.

The silicone polymers may more particularly be polymers comprising at least one unit corresponding to the general formula I:

in which :

1) R ⁴ , R ⁵ , R ⁶ and R ⁷ , which may be identical or different, represent a group chosen from: linear or branched or cyclic hydrocarbon groups containing from 1 to ₄ carbon atoms, saturated or unsaturated, which may contain, in their chain one or more oxygen, sulfur and / or nitrogen, and may be substituted partly or fully by fluorine atoms, aryl groups, C ₆ to C _0, optionally substituted with one or more alkyl groups in C 1 to C ₄ , the polyorganosiloxane chains containing or not one or more oxygen, sulfur and / or nitrogen atoms,

2) the X, which are identical or different, represent a linear or branched C1 to C30 alkylene di-yl group which may contain in its chain one or more oxygen and / or nitrogen atoms,

3) Y is a divalent linear or branched alkylene, arylene, cycloalkylene, alkylarylene or arylalkylene, saturated or unsaturated, C ₁ -C ₅ o group, which may comprise one or more oxygen, sulfur and / or nitrogen atoms, and / or bearing as substituent one of the following atoms or groups of atoms: fluorine, hydroxy, cycloalkyl C ₃ -C ₈ alkyl -C ₄₀ aryl, C ₅ -C ₁ 0, phenyl optionally substituted with 1-3 alkyl groups -C ₃ hydroxyalkyl, Ci to C ₃ alkyl and amino Ci-C _6, or

4) Y represents a group corresponding to the formula:

in which

T represents a trivalent or tetravalent hydrocarbon group, linear or branched, saturated or unsaturated, C ₃ to C ₂₄ optionally substituted by a polyorganosiloxane chain, and which may contain one or more atoms selected from O, N and S, or T represents an atom trivalent chosen from N, P and Al, and - R ⁸ represents a linear or branched C 1 -C ₅₀ alkyl group, or a polyorganosiloxane chain, which may comprise one or more ester, amide, urethane, thiocarbamate, urea, thiourea and or sulfonamide which may or may not be linked to another polymer chain,

5) G, identical or different, represent the divalent groups chosen from:

where R ⁹ represents a hydrogen atom or a linear or branched C 1 to C ₂₀ alkyl group, provided that at least 50% of the R ⁹ of the polymer represents a hydrogen atom and at least two of the groups G of the polymer are another group than:

6) n is an integer ranging from 2 to 500, preferably from 2 to 200, and m is an integer ranging from 1 to 1000, preferably from 1 to 700 and more preferably from 6 to 200. According to the invention , 80% of the R ⁴ , R ⁵ , R ⁶ and R ⁷ , of the polymer are preferably selected from methyl, ethyl, phenyl and 3,3,3-trifluoropropyl.

According to the invention, Y may represent various divalent groups, optionally additionally having one or two free valences to establish bonds with other units of the polymer or copolymer. Preferably, Y represents a group chosen from: a) linear alkylene groups -C _20, preferably Ci-Ci _0, b) branched alkylene groups possibly comprising rings and unconjugated unsaturations, C ₃₀ to C ₅ 6, c) C ₅ -C ₆ cycloalkylene groups, d) phenylene groups optionally substituted by one or more C ₁ -C ₄ alkyl groups, e) C ₁ -C ₂ alkylene groups, comprising 1 to 5 amide groups, f) C ₁ -C ₂ alkylene groups having one or more substituents selected from hydroxyl, C ₃ -C ₈ cycloalkane, C ₁ -C ₃ hydroxyalkyl and C ₁ -C ₄ alkylamines ₆ , g) polyorganosiloxane chains of formula: in which R ⁴ , R ⁵ , R ⁶ , R ⁷ , T and m are as defined above, and h) the polyorganosiloxane chains of formula:

According to the second variant, the polyorganosiloxanes may be polymers comprising at least one unit corresponding to formula (II):

in which

R ⁴ and R ⁶ , which are identical or different, are as defined above for formula (I),

R ¹⁰ represents a group as defined above for R ⁴ and R ⁶ , or represents the group of formula -XGR ¹² in which X and G are as defined above for formula (I) and R ¹² represents a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated C 1 -C ₅₀ hydrocarbon-based group optionally comprising in its chain one or more atoms chosen from O, S and N, optionally substituted by one or more fluorine atoms and / or one or more hydroxyl groups, or a phenyl group optionally substituted by one or more C ₁ -C ₄ alkyl groups,

R ¹¹ represents the group of formula -XGR ¹² in which X, G and R ¹² are as defined above,

0I ₁ is an integer ranging from 1 to 998, and m ₂ is an integer ranging from 2 to 500.

According to the invention, the silicone polymer used as structuring agent can be a homopolymer, that is to say a polymer comprising several identical units, in particular units of formula (I) or of formula (II).

According to the invention, it is also possible to use a silicone polymer constituted by a copolymer comprising several different units of formula (I), that is to say a polymer in which at least one of R ⁴ , R ⁵ and R ⁶ , R ⁷ , X, G, Y, m and n is different in one of the units. The copolymer may also be formed of several units of formula (II), in which at least one of R ⁴ , R ⁶ , R ¹⁰ , R ¹¹ , m 1 and m 2 is different in at least one of the units. It is also possible to use a polymer comprising at least one unit of formula (I) and at least one unit of formula (II), the units of formula (I) and the units of formula (II) possibly being identical to or different from each other. other.

According to a variant of the invention, it is also possible to use a polymer comprising in addition at least one hydrocarbon unit comprising two groups capable of establishing hydrogen interactions chosen from ester, amide, sulfonamide, carbamate, thiocarbamate, urea and urethane groups, thiourea, oxamido, guanidino, biguanidino and their combinations.

These copolymers may be block polymers, block polymers or graft polymers.

According to an advantageous embodiment of the invention, the groups capable of establishing hydrogen interactions are amide groups of formula -C (O) NH- and - HN-C (O) -. In this case, the structuring agent may be a polymer comprising at least one unit of formula (III) or (IV):

or

wherein R, R, R, R, X, Y, m and n are as defined above.

Such a unit can be obtained: either by a condensation reaction between a silicone with α, ω-carboxylic acid ends and one or more diamines, according to the following reaction scheme:

either by reacting two α-unsaturated carboxylic acid molecules with a diamine according to the following reaction scheme: followed by the addition of a siloxane to the ethylenic unsaturations, according to the following scheme:

CH ₂ = CH-X ¹ -CO-NH-Y-NH-CO-X ¹ -CH = CH ₂

in which X ¹ - (CH ₂ ) ₂ - corresponds to the X defined above and Y, R ⁴ , R ⁵ , R ⁶ , R ⁷ and m are as defined above, either by reaction of a silicone with ends oc, ω-NH ₂ and a diacid of formula HOOC-Y-COOH according to the following reaction scheme:

In these polyamides of formula (III) or (IV), m ranges from 1 to 700, in particular from 15 to 500 and in particular from 50 to 200, and is particularly preferably from 1 to 500, preferably from 1 to 100 and better still from 4 to 25, X is preferably a linear or branched alkylene chain having 1 to 30 carbon atoms, in particular 1 to 20 carbon atoms, especially 5 to 15 carbon atoms and more particularly 10 carbon atoms; , and

Y is preferably a linear or branched alkylene chain or which may comprise rings and / or unsaturations, having from 1 to 40 carbon atoms, in particular from 1 to 20 carbon atoms, and more preferably from 2 to 6 carbon atoms , in particular of 6 carbon atoms.

In formulas (III) and (IV), the alkylene group representing X or Y may optionally contain in its alkylene part at least one of the following elements: 1) 1 to 5 amide groups, urea, urethane, or carbamate,

2) a C ₅ or C ₆ cycloalkyl group, and

3) a phenylene group optionally substituted with 1 to 3 identical or different C ₁ -C ₃ alkyl groups.

In the formulas (III) and (IV), the alkylene groups may also be substituted with at least one member selected from the group consisting of: a hydroxy group, a C ₃ -C ₈ cycloalkyl group, one to three alkyl groups, and Ci -C ₄ o, phenyl optionally substituted by one to three alkyl groups, Ci to C ₃ hydroxyalkyl group to C _3, and a aminoalkyl group to C _6. In these formulas (III) and (IV), Y can also represent:

where R ⁸ represents a polyorganosiloxane chain, and T represents a group of formula

wherein a, b and c are independently integers from 1 to 10, and R ¹³ is a hydrogen atom or a group such as those defined for R ⁴ , R ⁵ , R ⁶ and R ⁷ .

In the formulas (III) and (IV), R ⁴ , R ⁵ , R ⁶ and R ⁷ preferably represent, independently, a C 1 to C ₄₀ alkyl group, linear or branched, preferably a group

CH ₃ , C ₂ H ₅ , nC ₃ H ₇ or isopropyl, a polyorganosiloxane chain or a phenyl group optionally substituted with one to three methyl or ethyl groups. As has been seen previously, the polymer may comprise identical or different units of formula (III) or (IV). Thus, the polymer may be a polyamide containing several units of formula (III) or (IV) of different lengths, ie a polyamide corresponding to formula (V):

in which X, Y, n, R ⁴ to R ⁷ have the meanings given above, OI ₁ and m ₂ which are different, are chosen in the range from 1 to 1000, and p is an integer ranging from 2 at 300.

In this formula, the units may be structured to form either a block copolymer, a random copolymer, or an alternating copolymer. In this copolymer, the units may be not only of different lengths but also of different chemical structures, for example having different Ys. In this case, the polymer can satisfy the formula VI:

in which R ⁴ to R ⁷ , X, Y, mi, m ₂ , n and p have the meanings given above and Y ¹ is different from Y but chosen from the groups defined for Y. As previously, the different units may be structured to form either a block copolymer, a random copolymer, or an alternating copolymer.

In this first embodiment of the invention, the structuring agent may also consist of a graft copolymer. Thus, the polyamide with silicone units can be grafted and optionally crosslinked with silicone chains containing amide groups. Such polymers can be synthesized with trifunctional amines.

In this case, the polymer may comprise at least one unit of formula (VII):

wherein X ¹ and X ² which are the same or different, have the meaning given for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I) ), R ¹⁴ to R ²¹ are groups selected from the same group as R ⁴ to R ⁷ , mi and m ₂ are numbers in the range of 1 to 1000, and p is an integer from 2 at 500.

In formula (VII), it is preferred that: p is from 1 to 25, more preferably from 1 to 7,

R ¹⁴ to R ²¹ are methyl groups,

T responds to one of the following formulas:

in which R ²² is a hydrogen atom or a group selected from the groups defined for R ⁴ to R ⁷ , and R ²³ R ²⁴ and R ²⁵ are independently linear or branched alkylene groups, more preferably, the formula in particular with R ²³ , R ²⁴ and R ²⁵ representing -CH ₂ -CH ₂ -, mi and m ₂ are from 15 to 500, and more preferably from 15 to 45, - Xi and X ₂ represent - (CH ₂ ) ₁₀ -, and

Y represents -CH ₂ -.

These silicone-grafted polyamides of formula (VII) may be copolymerized with polyamide-silicones of formula (II) to form block copolymers, alternating copolymers or random copolymers. The weight percentage of grafted silicone units (VII) in the copolymer can range from 0.5 to 30% by weight.

According to the invention, as seen above, the siloxane units may be in the main chain or backbone of the polymer, but they may also be present in grafted or pendant chains. In the main chain, the siloxane units may be in the form of segments as described above. In the pendant or grafted chains, the siloxane units may appear individually or in segments.

According to an alternative embodiment of the invention, it is possible to use a copolymer of silicone polyamide and of hydrocarbon-based polyamide, ie a copolymer comprising units of formula (III) or (IV) and hydrocarbon-based polyamide units. In this case, the polyamide-silicone units may be disposed at the ends of the hydrocarbon polyamide.

Preferably, the preferred compounds are those of formula III, whose INCI name is nylon-61 1 / dimethicone copolymers. According to this embodiment, the groups R4, R5, R6 and R7 represent methyl groups, one of X and Y represents an alkylene group of 6 carbon atoms and the other a group of alkylene groups of 11 carbon atoms.

By way of example, mention may be made of the compounds marketed by Dow

Corning as DC 2-8179 (DP 100) and DC 2-8178 (DP 15). The degree of polymerization

DP of these compounds corresponds to n in formula III.

Advantageously, the composition according to the invention comprises at least one polydimethylsiloxane block polymer of general formula (I) having an index m of approximately

15.

More preferably, the composition according to the invention comprises at least one polymer comprising at least one unit of formula (III) in which m is from 5 to 100, in particular from 10 to 75 and more particularly is of the order of 15; more preferably, R ⁴ , R ⁵ , R ⁶ and R ⁷ independently represent a linear or branched C 1 to C ₄₀ alkyl group, preferably a CH ₃ , C ₂ H ₅ , n C ₃ H ₇ or isopropyl group in the formula By way of example of a silicone polymer which may be used, mention may be made of one of the silicone polyamides obtained according to Examples 1 to 3 of US Pat. No. 5,981,680.

According to an alternative embodiment of the invention, the polymer consists of a homopolymer or copolymer comprising urethane or urea groups. These polymers are described in detail in application WO 2003/106614 published on 24/12/2003.

As before, such a polymer may comprise polyorganosiloxane units containing two or more urethane and / or urea groups, either in the backbone of the polymer, either on side chains or as pendant groups. The polymers comprising at least two urethane and / or urea groups in the backbone may be polymers comprising at least one unit corresponding to the following formula (VIII):

wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , X, Y, m and n have the meanings given above for formula (I), and U represents -O- or -NH-, so that:

corresponds to a urethane or urea group.

In this formula (VIII), Y may be an alkylene, Ci-C ₄ 0 linear or branched, optionally substituted by alkyl Cl to C ₅ or an aryl group, C ₅ to Ci ₀ - Preferably, a group - (CH ₂ ) 6 - Y may also be a C ₅ to C ₁₂ cycloaliphatic or aromatic group which may be substituted by a C 1 to C ₅ alkyl group or a C ₅ to C ₁₀ aryl group; , for example a radical chosen from the methylene-4-4-biscyclohexyl radical, the radical derived from isophorone diisocyanate, the 2,4 and 2,6-tolylenes, the 1,5-naphthylene, the p-phenylene and the 4,4'-biphenylene methane. Generally, it is preferred that Y represents an alkylene radical to C _40, linear or branched, or a cycloalkylene radical C ₄ to C _2.

Y may also represent a polyurethane or polyurea sequence corresponding to the condensation of several diisocyanate molecules with one or more molecules of couplers of the diol or diamine type. In this case, Y comprises several urethane or urea groups in the alkylene chain. It can answer the formula (IX):

wherein B ¹ is a group selected from the groups given above for Y, U is -O- or -NH-, and B ² is selected from:

Linear or branched C 1 to C ₄₀ alkylene groups; C ₅ to C ₁₂ cycloalkylene groups, optionally bearing alkyl substituents, for example one to three methyl or ethyl groups, or alkylene, for example the diol radical; : cyclohexane dimethanol,

• phenylene groups that may optionally be alkyl substituents carriers to C _3, and • groups of formula: in which T is a trivalent hydrocarbon radical which may contain one or more heteroatoms such as oxygen, sulfur and nitrogen and R ⁸ is a polyorganosiloxane chain or a linear or branched C 1 -C ₅₀ alkyl chain. T can represent for example:

with w being an integer from 1 to 10 and R ⁸ being a polyorganosiloxane chain.

When Y is a linear or branched C ₁ -C ₄ alkylene group, the groups - (CH ₂ ) ₂ - and - (CH ₂ ) ₆ - are preferred.

In the formula given above for Y, d may be an integer ranging from 0 to 5, preferably from 0 to 3, more preferably equal to 1 or 2.

Preferably B ² is a linear or branched C ₁ -C 40 alkylene group, in particular -

(CH ₂ ) 2- or - (CH ₂ ) 6-, or the group:

with R ⁸ being a polyorganosiloxane chain.

As before, the polymer constituting the texturizing copolymer may be formed of silicone urethane and / or silicone-urea units of different lengths and / or constitution, and may be in the form of block, random or random block copolymers. The polymers of formula (VIII) containing urea or urethane groups in the chain of the silicone polymer may be obtained by reaction between a silicone with α, ω-NH ₂ or -OH end groups, of formula:

wherein m, R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are as defined for formula (I), and an OCN-Y-NCO diisocyanate wherein Y has the meaning given in formula (I); and optionally a diol or diamine coupler of formula H ₂ NB ² -NH ₂ or HO-B ² -OH, where B ² is as defined in formula (IX). According to the stoichiometric proportions between the two reactants, diisocyanate and coupler, we can have for Y the formula (IX) with d equal to 0 where d is equal to 1 to 5. As in the case of silicone polyamides of formula (IV), (II) or (III), it is possible to use in the invention polyurethanes or silicone polyureas having patterns of different length and structure, in particular length patterns. different by the number of silicone units. In this case, the copolymer can respond, for example, to the formula:

wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , X, Y and U are as defined for formula (VIII) and mi, m ₂ , n and p are as defined for formula (V).

According to the invention, the silicone may also comprise urethane and / or urea groups, no longer in the backbone but in lateral branches. In this case, the polymer may comprise at least one unit of formula:

in which R ⁴ , R ⁶ , R ⁵ , mi and m ₂ have the meanings given above for formula (II), and R ⁵ for formula (I),

U represents O or NH,

R ²⁶ represents a C ₁ -C 40 alkylene group, optionally comprising one or more heteroatoms selected from O and N, or a phenylene group, and

R ²⁷ is selected from linear, branched or cyclic, saturated or unsaturated C 1 -C ₅₀ alkyl groups, and phenyl groups optionally substituted with one to three C ₁ -C ₃ alkyl groups.

The polymers comprising at least one unit of formula (X) contain siloxane units and urea or urethane groups, and they can be used as texturizing copolymer in the compositions of the invention.

The siloxane polymers may have a single urea or urethane group by branching or may have two-group urea or urethane groups, or may contain a mixture of branching with a urea or urethane group and branching with two groups of urea or urethane.

They can be obtained from branched polysiloxanes having one or two amino groups by branching, by reacting these polysiloxanes with monoisocyanates. By way of examples of starting polymers of this type having amino and diamino branches, mention may be made of the polymers corresponding to the following formulas:

In these formulas, the symbol 7 "indicates that the segments may be of different lengths and in random order, and R represents a linear aliphatic group preferably having 1 to 6 carbon atoms and more preferably 1 to 3 carbon atoms.

Such branched polymers may be formed by reacting a siloxane polymer, having at least three amino groups per polymer molecule, with a compound having a single monofunctional group (eg, an acid, an isocyanate or isothiocyanate) to react that group. monofunctional with one of the amino groups and form groups capable of establishing hydrogen interactions. The amino groups may be on side chains extending from the main chain of the siloxane polymer so that groups capable of establishing hydrogen interactions are formed on these side chains, or the amino groups may be at the ends of the chain main so that groups capable of hydrogen interaction will be end groups of the polymer. As the procedure for forming a polymer containing siloxane units and groups capable of establishing hydrogen interactions, there may be mentioned the reaction of a siloxane diamine and a diisocyanate in a silicone solvent so as to directly provide a gel. The reaction can be carried out in a silicone fluid, the resulting product being dissolved in the silicone fluid at elevated temperature, the temperature of the system then being reduced to form the gel.

The preferred polymers for incorporation into the compositions according to the present invention are siloxane-urea copolymers which are linear and which contain urea groups as groups capable of establishing hydrogen interactions in the polymer backbone. As an illustration of a polysiloxane terminated by four urea groups, mention may be made of the polymer of formula:

where Ph is a phenyl group and n is a number from 0 to 300, in particular from 0 to 100, for example 50.

This polymer is obtained by reacting the following amino group-containing polysiloxane:

with phenyl isocyanate.

It is also possible to obtain branched silicone polyurethanes or polyureas using, in place of the OCN-Y-NCO diisocyanate, a triisocyanate of formula:

Thus, a silicone polyurethane or polyurea having branching having an organosiloxane chain with groups capable of establishing hydrogen interactions is obtained. Such a polymer comprises, for example, a unit corresponding to the formula: wherein X ¹ and X ² which are the same or different, have the meaning given for X in formula (I), n is as defined in formula (I), Y and T are as defined in formula (I) ), R ¹⁴ to R ²¹ are groups selected from the same group as R ⁴ to R ⁷ , mi and m ₂ are numbers in the range of 1 to 1000, and p is an integer from 2 at 500.

As in the case of polyamides, it is possible to use in the invention copolymers of polyurethane or polyurea silicone and of polyurethane or hydrocarbon polyurea by carrying out the synthesis reaction of the polymer in the presence of an α, ω-difunctional sequence of non-silicone nature, for example a polyester, a polyether or a polyolefin.

As has been seen previously, the copolymers of the invention may have siloxane units in the main chain of the polymer and groups capable of establishing hydrogen interactions, either in the main chain of the polymer or at the ends thereof. , or on side chains or branches of the main chain. This can correspond to the following five provisions:

wherein the continuous line is the main chain of the siloxane polymer and the squares represent the groups capable of establishing hydrogen interactions. In case (1), groups capable of establishing hydrogen interactions are arranged at the ends of the main chain. In case (2), two groups capable of establishing hydrogen interactions are arranged at each end of the main chain. In case (3), the groups capable of establishing hydrogen interactions are arranged inside the main chain in repetitive patterns. In cases (4) and (5), these are copolymers in which the groups capable of establishing hydrogen interactions are arranged on branches of the main chain of a first series of patterns which are copolymerized with patterns not having groups capable of establishing hydrogen interactions. The polymers and copolymers used in the composition of the invention advantageously have a solid-liquid transition temperature of 45 ° C. to 190 ^° C. They preferably have a solid-liquid transition temperature ranging from 70 ° to 130 ^° C. and better from 80 ° C to 105 ^° C. Organogelators:

The oily structurant can also be chosen from nonpolymeric molecular organic gelling agents, also called organogelators, which are compounds whose molecules are capable of establishing between them physical interactions leading to a self-aggregation of the molecules with formation of a supra-molecular 3D network which is responsible for the gelation of the oil (s) (also called phase liquid fat). The supramolecular network may result from the formation of a network of fibrils

(due to stacks or aggregations of organogelling molecules), immobilizing the molecules of the liquid fatty phase.

The ability to form this network of fibrils, and thus to gel, depends on the nature (or chemical class) of the organogelator, the nature of the substituents carried by its molecules for a given chemical class and the nature of the phase liquid fat.

Physical interactions are diverse but exclude co-crystallization. These physical interactions are in particular interactions of the type self-complementary hydrogen interactions, π interactions between unsaturated rings, dipolar interactions, coordination bonds with organometallic derivatives and their associations. In general, each molecule of an organogelator can establish several types of physical interactions with a neighboring molecule. Also, advantageously, the molecules of the organogelators according to the invention comprise at least one group capable of establishing hydrogen bonds and better at least two groups capable of establishing hydrogen bonds, at least one aromatic ring and better at least two aromatic rings. at least one or more ethylenically unsaturated bonds and / or at least one or more asymmetric carbons. Preferably, the groups capable of making hydrogen bonds are chosen from hydroxyl, carbonyl, amine, carboxylic acid, amide, urea and benzyl groups and their combinations.

The organogelling organism (s) according to the invention are soluble in the liquid fatty phase after heating until a transparent homogeneous liquid phase is obtained. They can be solid or liquid at room temperature and atmospheric pressure.

The molecular organogelling agent (s) that can be used in the composition according to the invention are in particular those described in the document "Specialist Surfactants", edited by D. Robb of 1997, p.209-263, chapter 8 of P. Terech, European applications EP And in application WO-A-02/47031.

Among these organogelators, there may be mentioned amides of carboxylic acids, in particular tri-carboxylic acids such as cyclohexanetricarboxamides (see European Patent Application EP-A-1068854), the diamines having hydrocarbon chains each containing from 1 to 22 carbon atoms, for example from 6 to 18 carbon atoms, said chains being unsubstituted or substituted with at least one substituent chosen from ester, urea and fluoro groups (see application EP-A-1086945) and in particular the resulting diamides of the reaction of diaminocyclohexane, in particular of diaminocyclohexane in trans form, and of an acid chloride such as, for example, N, N'-bis (dodecanoyl) -1,2-diaminocyclohexane, the amides of N-acylamino acids, for example the diamides resulting from the action of an N-acylamino acid with amines comprising from 1 to 22 carbon atoms, for example those described in document WO-93/23008 and in particular the amides of the acid N-acylglutamic acid wherein the acyl group represents a C ₈ to C ₂₂ alkyl chain, such as N-Lauroyl-L-glutamic acid dibutylamide, manufactured or marketed by Ajinomoto under the name GP-1 and their mixtures .

It is also possible to use as organogelators bis-urea type compounds of the following general formula:

in which : - A is a group of formula (II):

R1 is alkyl to C ₄ linear or branched, and ^* stands ^for the group points of attachment of A to each of the two nitrogen atoms of the residue of the compound of general formula (I), and

R and R ', which are identical or different, are chosen from:

i) the radicals of formula (III):

in which :

L is a single bond or a divalent carbon, especially hydrocarbon (alkylene), linear, branched and / or cyclic, saturated or unsaturated radical, comprising 1 to 18 carbon atoms, and which may comprise 1 to 4 heteroatoms chosen from N, O and S;

Ra is: a) a linear, branched and / or cyclic, saturated or unsaturated, hydrocarbon radical (alkyl), comprising 1 to 18 carbon atoms, and which can comprise 1 to 8 heteroatoms chosen from N, O, Si; and S; or else b) a silicone radical of formula:

with n being between 0 and 100, in particular between 1 and 80, or even 2 to 20; and R2 to R6 being, independently of one another, carbon radicals, in particular linear or branched hydrocarbon (alkyl) radicals having 1 to 12, in particular 1 to 6 carbon atoms, and possibly comprising 1 to 4 heteroatoms, in particular O;

- Rb and Rc are, independently of one another, selected from: a) carbon radicals, in particular linear, branched and / or cyclic hydrocarbon radicals, saturated or unsaturated, containing 1 to 18 carbon atoms, and may comprise 1 to 4 heteroatoms selected from N, O, Si and S; b) radicals of formula:

with n being between 0 and 100, in particular between 1 and 80, or even 2 to 20; and R'2 to R'6 being, independently of one another, carbon radicals, in particular linear or branched hydrocarbon (alkyl) radicals having 1 to 12, in particular 1 to 6 carbon atoms, and possibly comprising 1 to 4 heteroatoms, including O. and

ii) linear, branched and / or cyclic, saturated or unsaturated C 1 to C ₃₀ alkyl radicals, optionally comprising 1 to 3 heteroatoms chosen from O, S, F and N; it being understood that at least one of the radicals R and / or R 'is of formula (III).

In particular, the group A can be of formula:

with R1 and the ^* being as defined previously.

In particular, R 1 may be a methyl group, which leads to a group A of formula:

in which the ^* are as defined above.

In particular, the compounds according to the invention may be in the form of a mixture linked to the fact that A may be a mixture of 2,4-tolylene and 2,6-tolylene, especially in proportions (2,4 isomer) / (isomer 2.6) ranging from 95/5 to 80/20. According to the invention, at least one of the radicals R and / or R 'must be of formula (III):

In this formula, L is preferably a linear, branched and / or cyclic, saturated or unsaturated, hydrocarbon-based (alkylene), divalent radical containing 1 to 18 carbon atoms, and which may comprise 1 to 4 heteroatoms chosen from N, O and S. In the radical L, the carbon chain may be interrupted by the heteroatom (s) and / or may comprise a substituent comprising said heteroatom (s). In particular, L may be of - (CH ₂ ) n- structure with n = 1 to 18, in particular 2 to 12, or even 3 to 8. Preferably, L is chosen from methylene, ethylene, propylene and butylene radicals, in particular n-butylene or octylene.

The radical L can also be branched, for example of the type -CH ₂ -CH (CH ₃ ) -, which leads to the radical of formula (III) below:

The radical Ra may be a linear, branched and / or cyclic, saturated or unsaturated, hydrocarbon radical (alkyl), comprising 1 to 18 carbon atoms, and capable of comprising 1 to 8 heteroatoms selected from N, O, Si and S. The carbon chain may be interrupted by the heteroatom (s) and / or may include a substituent comprising said heteroatom (s); the heteroatoms may in particular form one or more -SiO- (or -OSi) - groups.

Thus, the radical Ra may have a structure - (CH ₂ ) n -CH ₃ with n '= 0 to 17, in particular 1 to 12, or even from 1 to 6. In particular, Ra may be methyl, ethyl, propyl or butyl.

It can also be of the structure - (CH ₂ ) XO- (CH ₂ ) ₂ -CH ₃ or - (CH ₂ ) xO- (CH ₂ ) y O- (CH ₂ ) ₂ -CH ₃ , with x = 1 to 10, preferably 2; y = 1 to 10, preferably 2, and z = 0 to 10, preferably 0 or 1.

The radical Ra can also be of structure -SiR ₄ R ₅ R ₆ (where n = 0), in which R 4, R 5 and R 6 are, independently of one another, preferably alkyl radicals having 1 to

12 carbon atoms, especially 1 to 6 carbon atoms; in particular, R4, R5 and / or R6 may be chosen from methyl, ethyl, propyl and butyl.

The radical Ra can also be a silicone radical of formula:

wherein R2 to R6 are, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular R2 to R6 may be selected from methyl, ethyl, propyl, butyl; and in particular a radical:

with n = 1 to 100; and even more particularly a radical:

The radicals Rb and Rc, which may be identical or different, may be carbon, especially hydrocarbon (alkyl), linear, branched and / or cyclic, saturated or unsaturated radicals, comprising 1 to 18 carbon atoms, and may comprise 1 to 8 selected heteroatoms. among N, O, Si and S. In these radicals, the carbon chain may be interrupted by the heteroatom (s) and / or may comprise a substituent comprising said heteroatom (s); the heteroatoms may in particular form one or more -SiO- (or -OSi) - groups.

Thus, they may be of structure - (CH ₂ ) m -CH ₃ with m = 0 to 17, especially 1 to 12, or even 2 to 5; in particular, Rb and / or Rc may be methyl, ethyl, propyl or butyl;

They may also be of the structure -O- (CH ₂ ) n -CH ₃ with m '= 0 to 5, in particular 1 to 4, and in particular methoxy or ethoxy.

They can also be of the structure -O- (CH ₂ ) xO- (CH ₂ ) z -CH ₃ or -O- (CH ₂ ) xO- (CH ₂ ) yO-

(CH ₂ ) Z-CH ₃ , with x = 1 to 10, preferably 2; y = 1 to 10, preferably 2, and z = 0 to 10, preferably 0 or 1.

They can still be of structure: with n being between 0 and 100, in particular between 1 and 80, or even 2 to 20; and R'2 to R'6 being, independently of one another, preferably alkyl radicals having 1 to 12 carbon atoms, especially 1 to 6 carbon atoms; in particular R'2 to R'6 can be selected from methyl, ethyl, propyl, butyl.

When they are of formula, the radicals R and / or R 'are preferably chosen from the following radicals:

and also those of formula with n varying from 0 to 100 and in particular

in which x = 1 to 10, preferably 2; and y = 1 to 10, preferably 2; and L being as defined above.

Preferably, in these formulas, L is a linear or branched C1-C8 alkylene radical, in particular methylene, ethylene, propylene or butylene, and especially n-butylene or octylene, or of formula -CH ₂ -CH (CH ₃ ) -.

In a particular embodiment, R and R ', which are identical or different, are both of formula (III).

In another embodiment, one of the radicals R or R 'represents a linear, branched and / or cyclic, saturated or unsaturated C 1 -C ₃₀ alkyl radical, and optionally comprising 1 to 3 heteroatoms chosen from O, S , F and N. This is particularly advantageous in conferring a universal character on compounds of formula (I), that is to say, allow them to texture both polar or apolar carbonaceous media, linear or cyclic silicone media, mixed oils that is to say carbon partially silicone, and as their mixtures.

The carbon chain may be interrupted by the heteroatom (s) and / or may comprise a substituent comprising said heteroatom (s), especially in the form of a carbonyl group (-CO-), one or more hydroxyl radicals (-OH), and / or or an ester radical -COOR "with R" = linear or branched alkyl radical having 1 to 8 carbon atoms.

Thus, said radical R or R 'can be a group chosen from:

with ^* having the definition given above.

In a preferred embodiment, R or R 'represents a branched alkyl radical, especially monoramified, preferably non-cyclic, saturated or unsaturated, comprising 3 to 16 carbon atoms, especially 4 to 12, or even 4 to 8 carbon atoms, and optionally comprising 1 to 3 heteroatoms chosen from O, S, F and / or N, preferably O and / or N. In particular, R or R 'may be tert-butyl or 2-ethylhexyl radicals or of formula:

When the compound of formula (I) comprises a radical R which is an alkyl radical, and therefore a radical R 'which is of formula (III), the ratio of n _R and n _R > is preferably between 5/95 and 95/5, for example between 10/90 and 90/10, in particular between 40/60 and 85/15, in particular between 50/50 and 80/20, or even between 60/40 and 75/25; with n _R being the number of moles of NH ₂ -R amine and n _R > being the number of moles of NH ₂ -R 'amine used to prepare the compound of formula (I). The compounds according to the invention may be in the form of salts and / or isomers of compounds of formula (I).

In general, the compounds of general formula (I) according to the invention can be prepared as described in application FR2910809.

The silicone bis-urea type compounds described above may be mixed with other non-silicone bis-urea compounds. The non-silicone bis-urea compounds may, according to a first aspect, satisfy the following general formula (II):

in which :

- A is a group of formula:

with R 'being an alkyl radical with linear or branched C ₄ and ^* stands ^for the group points of attachment of A to each of the two nitrogen atoms of the residue of the compound of general formula (II), and

- R is a C ₆ to C ₅ alkyl radical, mono-branched, non-cyclic, saturated or unsaturated and whose hydrocarbon chain is optionally interrupted by 1 to 3 heteroatoms chosen from

O, S and N, or one of its salts or isomers. According to a preferred embodiment of the invention, the group represented by A is a group of formula:

with R 'and the ^* being as defined previously.

In particular, R 'can be a methyl group, and the group A is then more particularly a group of formula:

with the ^* being as defined previously.

According to a first embodiment of the invention, R may be chosen from mono-branched radicals of general formula C _n H _{2n + I} , n being an integer ranging from 6 to 15, in particular from 7 to 9, or even equal to 8.

Thus, the two R groups of the compound of formula (II) may respectively represent a grouping: with ^* symbolizing the point of attachment of each of the groups R to each of the nitrogen atoms of the remainder of the compound of general formula (II).

According to a second embodiment of the invention, R may be chosen from mono-branched radicals of general formula C _m- pH2m + i-2pX _P! P being equal to 1, 2 or 3, preferably 1, m being an integer ranging from 6 to 15, preferably from 10 to 14, in particular from 10 to 12, even equal to 1 1 and X representing the atoms sulfur and / or oxygen, in particular oxygen atoms.

More particularly, R may be a radical of the formula C H _nV _2NV X- (C ^ H _2P XX-C _x H _{2x + 1} wherein X and X 'are independently from each other an oxygen atom or sulfur, preferably oxygen, r is 0 or 1, m ', p' and x are integers such that their sum varies from 6 to 15, in particular from 10 to 12, or is equal to 1 1 and it being understood that at least one of the carbon chains C _n V H _2n V, C _p H _2p , or C _x H _{2x +} I is branched.

Preferably, the chain C _x H _{2x + 1} is branched, preferably r is 0, preferably m 'is an integer varying from 1 to 10, in particular from 2 to 6, in particular equal to 3, and or preferably x is an integer ranging from 4 to 16, in particular from 6 to 12, in particular equal to 8. Thus, the two R groups of the compound of formula (I) may respectively be a grouping:

with ^* symbolizing the point of attachment of each of the groups R to each of the nitrogen atoms of the remainder of the compound of general formula (I).

Such compounds may be present in the compositions according to the invention in mixtures with isomers, especially isomers of position on the group A, especially in proportions of 95/5 or 80/20.

As is apparent from the examples below, the presence of one or other of its radicals in the molecule of general formula (II) proves particularly advantageous for conferring a universal character, within the meaning of the invention, on the corresponding non-silicone bis-urea derivatives.

As a representative and non-limiting example of the compounds that are particularly suitable for the invention, mention may be made more particularly of the following compounds, used pure or as a mixture:

and their salts.

According to another aspect of the invention, the non-silicone bis-urea derivatives (III) below

in which :

A is a group of formula:

with R ₃ being a hydrogen atom or a linear or branched C ₁ -C ₄ alkyl radical, n and m being, independently of one another, equal to 0 or 1, and * symbolizing the point of attachment of the grouping To the two nitrogen atoms of the remainder of the compound of general formula (III),

R 1 is a branched, non-cyclic, saturated or unsaturated C ₃ to C ₅ carbon radical and optionally containing from 1 to 3 heteroatoms selected from O, S, F and N and / or a carbonyl, and combinations thereof,

R ₂ βst different from R 1 and is chosen from linear or branched or cyclic saturated or unsaturated C ₁ -C ₂₄ alkyl radicals, optionally containing from 1 to 3 heteroatoms chosen from O, S, F and N, and optionally substituted by :

1, 2 or 3 hydroxy radicals, an ester radical (-COOR ₄ ), with R ₄ being a linear or branched alkyl radical having from 1 to 8, especially 1 to 6, or even 2 to 4 carbon atoms; a saturated, unsaturated or aromatic cyclic radical having 5 to 12 carbon atoms, in particular a phenyl radical optionally substituted with one or more identical or different radicals chosen from C ₁ -C ₄ alkyl, trifluoromethyl radicals, or a morpholine derivative, and or one or more linear or branched alkyl radicals in dC ₄ , or one of its salts or isomers.

In particular, n and m are equal, and more particularly equal to zero, and R ₃ is a radical R ' ₃ , as defined below. Thus, preferably, A represents a grouping

With R ₃ 'being a linear or branched C ₁ -C ₄ alkyl radical and ^* symbolizing the point of attachment of the group A to the two nitrogen atoms of the remainder of the compound of general formula (III). According to a variant of the invention, the compound of general formula (III) comprises as A, at least one group chosen from:

with R ₃ 'and ^* being as previously defined.

In particular, R ₃ 'can be a methyl group, and in this case the group A represents a grouping

or

^* being as defined previously.

In particular, the compounds are such that A is a mixture of 2,4-tolylene and 2,6-tolylene, in particular in proportions (2,4-isomer) / (2,6-isomer) ranging from 95/5 to 80/20. .

According to one embodiment of the invention, the compound of general formula (III) comprises, as R, a radical C ₆ -C ₅ branched.

According to one embodiment of the invention, the compound of general formula (III) comprises, as R-1, a group chosen from:

with ^* symbolizing the point of attachment of the group R ₁ to the nitrogen of the remainder of the compound of general formula (III).

As is apparent from the examples below, the presence of one and / or the other of its two radicals in the molecule of general formula (III) proves to be particularly advantageous in conferring a universal character on the meaning of the invention. to the corresponding asymmetric bis-urea derivatives.

As regards R ₂ which is different from Ri, it may advantageously be chosen from the following groups:

with ^* symbolizing the point of attachment of the group R ₂ to nitrogen of the remainder of the compound of general formula (III).

In general, the compounds described can be prepared as described in application FR2910809.

Fatty phase gelling silicone elastomers

The term "elastomer" is understood to mean a flexible, deformable solid material having viscoelastic properties and in particular the consistency of a sponge. This elastomer is formed of high molecular weight polymer chains whose mobility is limited by a uniform network of crosslinking points.

The organopolysiloxane elastomers used in the composition according to the invention are preferably partially or completely crosslinked. They are in the form of particles. In particular, the organopolysiloxane elastomer particles have a size ranging from 0.1 to 500 μm, preferably from 3 to 200 μm and better still from 3 to 50 μm. These particles may be any shape and for example be spherical, flat or amorphous.

When they are included in an oily phase, these elastomer organopolysiloxanes are transformed, depending on the level of oily phase used, into a product of spongy appearance when they are used in the presence of low levels in the oily phase, or in a homogeneous gel. presence of higher amounts of oily phase. The gelling of the oily phase by these elastomers may be total or partial.

Thus, the elastomers of the invention may be transported in the form of an anhydrous gel consisting of an elastomeric organopolysiloxane and an oily phase. The oily phase used in the manufacture of the anhydrous organopolysiloxane elastomer gel contains one or more liquid oils at ambient temperatures (25 ° C.) chosen from hydrocarbon-based oils and / or silicone oils. Advantageously, the oily phase is a silicone liquid phase, containing one or more oils chosen from linear or cyclic chain or linear cyclic polydimethylsiloxanes optionally comprising an alkyl or pendant aryl chain or at the end of the chain, the alkyl chain having 1 at 6 carbon atoms.

According to one embodiment, the elastomeric organopolysiloxanes used according to the invention can be obtained by addition and crosslinking reaction, in the presence of a catalyst, preferably a platinum-type catalyst, of at least:

(i) an organopolysiloxane having two vinyl groups in the α-ω position of the silicone chain per molecule; and

- (ii) an organopolysiloxane having at least two hydrogen atoms bonded to one silicon atom per molecule.

The first organopolysiloxane (i) is chosen from polydimethylsiloxanes; it is preferably an α-ω-dimethylvinyl polydimethylsiloxane.

The organopolysiloxane is preferably in a gel obtained according to the following steps:

- (a) mixing the first and second organopolysiloxanes (i) and (ii);

(b) adding an oily phase to the mixture of step (a); (c) polymerizing the first and second organopolysiloxanes (i) and (ii) in the oily phase in the presence of a catalyst, preferably a platinum catalyst.

According to one embodiment, the crosslinked organopolysiloxane can be obtained by a polymeric addition reaction of an organohydrogenpolysiloxane of formula (I) with an organopolysiloxane of formula (II) and / or an unsaturated hydrocarbon chain of formula

According to one variant, the crosslinked organopolysiloxane is obtained by a polymeric reaction of an organohydrogenpolysiloxane of formula (I) with an organopolysiloxane of formula (II). Organohydrogenopolysiloxane of formula (I)

The organohydrogenpolysiloxane of formula (I) comprises at least one structural unit selected from the group consisting of a SiO ₂ unit, a HSiOi unit _5, a RSiO unit _5, an RHSiO unit, R ₂ SiO unit, a unit ₃ R SiO ₀ , ₅ and a unit R ₂ HSiO ₀ , ₅ , the group R being in these units a monovalent hydrocarbon chain containing 1 to 16 carbon atoms, which may or may not be substituted, but being distinct from an unsaturated aliphatic group, and having on average at least 1.5 hydrogen atoms bonded to a silicon atom. The group R in the organohydrogenpolysiloxane of formula (I) may be an alkyl group having 1 to 16, preferably 10 to 16 carbon atoms. This group R may for example be a methyl group, an ethyl group, a propyl group, a lauryl group, a myristyl group and a palmityl group.

The group R in the organohydrogenpolysiloxane of formula (I) may also be an aryl group such as a phenyl or tolyl group.

The group R always in the organohydrogenpolysiloxane of formula (I) may also be a monovalent hydrocarbon-based chain comprising a cycloalkyl group such as cyclohexyl or a hydrocarbon-based chain substituted with one, two or more groups chosen from a halogen atom such as chlorine, bromine, fluorine and a cyano group, for example an α-trifluoropropyl or chloromethyl group.

In particular, it is preferred that the group R represents at least 30 mol% of methyl group and 5 to 50 mol%, preferably 10 to 40 mol% of hydrocarbon chain containing 10 to 16 carbon atoms.

The hydrocarbon chain can then advantageously comprise at least one lauryl group, or even the majority of the R groups may be lauryl groups.

The organohydrogenpolysiloxane of formula (I) may be linear, branched or cyclic. The organohydrogenpolysiloxane of formula (I) preferably contains from 2 to 50 and even more preferably from 2 to 10 hydrogen atoms bonded to a silicon atom (Si-H). The content of hydrogen atom bonded to a silicon atom in this compound of formula (I) typically varies from 0.5 to 50 mol%, and even more preferably from 1 to 20 mol% relative to the total sum. hydrogen atoms and all organic groups bonded to a silicon atom.

Organopolysiloxane of formula (II)

The organopolysiloxane of formula (II) comprises at least one structural unit selected from the group consisting of one SiO ₂ unit, one (CH ₂ = CH) SiO ₅ unit, one RSiO ₅ unit and one R (CH _{2) unit.} = CH) SiO, a unit R ₂ SiO, a unit R ₃ SiO ₀ , ₅ and a unit R ₂ (CH ₂ = CH) SiO ₀ , ₅ , the group R being as defined in formula (I) and having on average at least 1.5 vinyl groups bonded to a silicon atom.

This compound preferably contains from 2 to 50 vinyl groups bonded to a silicon atom.

The average number of vinyl groups bonded to a silicon atom preferably ranges from 2 to 10, and even more preferably from 2 to 5.

Preferably, at least 30 mol% of the R groups are methyl groups and 5 to 50 mol%, preferably 10 to 40 mol% of the R groups are a hydrocarbon chain having 10 to 16 carbon atoms.

The organopolysiloxane of formula (II) can be linear, branched or cyclic. The vinyl group content in the compound of formula (II) preferably varies between 0.5 and 50 mol%, even more preferably from 1 to 20 mol% relative to all the organic groups bonded to a silicon atom.

Unsaturated hydrocarbon chain of optional formula (III) The unsaturated hydrocarbon chain of formula (III) has the following formula: wherein m is an integer ranging from 2 to 6 and x is an integer of at least 1. x is preferably an integer ranging from 1 to 20.

By way of example of this compound of formula (III), mention may be made of pentadiene, hexadiene, heptadiene, octadiene, pentadecadiene, heptadecadiene and pentatriacontadiene. Polymeric addition reactions are described in detail in US 2004/0234477.

Among the crosslinked organopolysiloxanes, crosslinked polyalkyl dimethylsiloxanes are preferred. By polyalkyl dimethylsiloxane is meant a linear organopolysiloxane of formula (IV) having monovalent or divalent linked grafts of formula (V)

in which :

Ra is an alkyl group having from 10 to 16 carbon atoms, and may be preferably a lauryl group, ya is an integer from 1 to 100; za is an integer from 1 to 100, yb is an integer from 1 to 100, zb is an integer from 1 to 100. By "divalently bound" is meant bound to two distinct organopolysiloxanes of formula (IV) . In other words, it is a bridge between two linear chains as defined by formula (IV).

As non-emulsifying elastomers that can be used according to the invention, dimethicone / vinyldimethicone copolymers (INCI name: Dimethicone / Vinyldimethicone crosspolymer) are preferably used, and vinyldimethicone / alkyl dimethicone copolymers, such as vinyldimethicone / lauryl dimethicone copolymers (INCI name: Vinyl). Dimethicone / Lauryl Dimethicone Crosspolymer). As non-emulsifying elastomers that can be used according to the invention, mention may be made of:

those of INCI name Dimethicone / Vinyldimethicone Crosspolymer (and) C12-14 Pareth-12: such as those sold under the name "DC 9509" by Dow Corning,

those of INCI name Dimethicone / Vinyldimethicone Crosspolymer: such as those sold under the name "DC9505", or "DC 9506" by the company Dow Corning, those of INCI name Cyclomethicone (and) Dimethicone / Vinyldimethicone Crosspolymer: like those sold under KSG- 15® by Shin-Etsu, Methyl Trimethicone (and) Dimethicone / Vinyldimethicone Crosspolymer: like those sold by Shin-Etsu under KSG-1610®,

those of INCI name Dimethicone (and) Dimethicone / Vinyldimethicone Crosspolymer: as those sold under KSG-16® by Shin-Etsu, Isododecane (and) Dimethicone / Vinyldimethicone Crosspolymer: such as those sold under USG-106® by Shin-Etsu, those of INCI name: Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer: KSG-41® (in a mineral oil), KSG-42® (in isododecane), KSG-43® (in triethylhexanoine) and KSG-44® (in in squalane), sold by Shin-Etsu. As non-emulsifying elastomer, mention may also be made of spherical non-emulsifying silicone elastomers in the form of an elastomeric crosslinked organopolysiloxane powder coated with silicone resin, in particular of silsesquioxane resin, as described, for example, in patent US5538793. Such elastomers are sold under the names "KSP-100", "KSP-101", "KSP-102", "KSP-103", KSP-104 "," KSP-105 "by Shin Etsu.

Other elastomeric crosslinked organopolysiloxanes in the form of spherical powders may be hybrid silicone powders functionalized with fluoroalkyl groups, especially sold under the name "KSP-200" by the company Shin Etsu; hybrid silicone powders functionalized with phenyl groups, especially sold under the name "KSP-300" by Shin Etsu.

Silicone elastomers with an MQ group may also be used in the compositions according to the invention, such as those sold by Wacker under the names Belsil RG100, Belsil RPG33 and preferably RG80. These particular elastomers, when they are in combination with the resins according to the invention, may make it possible to improve the non-transfer properties of the compositions comprising them.

Cholesteric liquid crystals: Liquid crystalline agents are compounds that generate a mesomorphic state, that is to say a state for which the melting of the crystals makes it possible to obtain liquids having optical properties comparable to those of certain crystals. These compounds are more precisely defined in the chapter Liquid crystals in the Ullmann encyclopedia. These liquid crystal agents are in particular described in patents or patent applications EP 545 409, WO 941 09086, EP 709 445, GB 2 282 1 45, GB 2 276 883, WO 951 32247, WO 951 32248, EP 686. 674, EP 71 1780.

These liquid crystal agents can react in response to vibration by a change in viscosity and / or a color change. More specifically, the compounds generating a mesomorphic state are comets with cholesteric function, the structure of which is the following:

R is an alkyl, alkylcarbonyl group comprising from 1 to 30 carbon atoms optionally substituted with cyclic, aromatic, halogenated, branched or unbranched groups.

Nonlimitatively, mention may be made of a liquid crystal agent that meets this definition: cholesterol erucyl carbonate, choleterol methyl carbonate, cholesterol oleyl carbonate, para-nonyl phneyl carbonate cholesterol, cholesterol phenyl carbonate, cholesterol acetate, cholesterol benzoate, cholesterol butyrate, cholesterol isobutyrate, cholesterol chorol loride, cholesterol ch loroacetate, cholesterol cin namate, cholesterol crotanoate, cholesterol decanoate, cholesterol erucate, cholesterol heptanoate, cholesterol hexanoate, cholesterol myristate, cholesterol nonaoate, cholesterol octanoate, cholesterol oleate, cholesterolpropionate, cholesterol valerate, dicholesteryl carbonate.

The composition according to the invention may comprise an aqueous continuous phase or an oily continuous phase.

By aqueous continuous phase composition is meant that the composition has a conductivity, measured at 25 ^° C., greater than or equal to 23 S / cm (microSiemens / cm), the conductivity being measured, for example using a conductivity meter. MPC227 from Mettler Toledo and a lnlab730 conductivity cell. The measuring cell is immersed in the composition, so as to eliminate air bubbles that may form between the 2 electrodes of the cell. The reading of the conductivity is made as soon as the value of the conductivity meter is stabilized. An average is performed on at least 3 successive measurements.

By oily continuous phase composition is meant that the composition has a conductivity, measured at 25 ^° C., of less than 23 μS / cm (microSiemens / cm), the conductivity being measured for example using an MPC227 conductivity meter. Mettler Toledo and a conductivity measuring cell lnlab730. The measuring cell is immersed in the composition, so as to eliminate air bubbles that may form between the 2 electrodes of the cell. The reading of the conductivity is made as soon as the value of the conductivity meter is stabilized. An average is performed on at least 3 successive measurements.

The compositions may contain from 1 to 60% fatty phase rheological agent. Preferably, the composition contains from 2% to 50% by weight, more preferably from 5% to 40% fatty phase rheological agent.

In the case where the composition comprises a rheological agent of fatty phase, it comprises an oily continuous phase. waxes

The composition according to the invention may comprise at least one wax.

The compositions according to the invention may thus comprise at least one wax, and the mixture 1) described above.

For the purposes of the present invention, the term "wax" means a lipophilic compound, solid at room temperature (25 ^° C.), with a reversible solid / liquid state change, having a melting point of greater than or equal to 30 ^° C. at 120 ^° C.

The melting point of the wax may be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company

Mettler.

The waxes may be hydrocarbon-based, fluorinated and / or silicone-based and may be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting temperature greater than 25 ^° C. and better still greater than 45 ^° C. The wax or the mixture of waxes is present in a content at least equal to 7% by weight. Preferably, it is present in a content ranging from 10 to 40% by weight relative to the total weight of the composition, more preferably from 15 to 35% and more preferably from 16 to 30% by weight.

In particular, it is possible to use hydrocarbon-based waxes such as beeswax, lanolin wax, and Chinese insect waxes; rice wax, Carnauba wax, Ouricurry wax, Alfa wax, cork fiber wax, sugar cane wax, Japanese wax and sumac wax; montan wax, microcrystalline waxes, paraffins; polyethylene waxes, waxes obtained by Fisher-Tropsch synthesis and waxy copolymers and their esters. Mention may also be made of waxes obtained by catalytic hydrogenation of animal or vegetable oils having linear or branched C8-C32 fatty chains. Among these, there may be mentioned hydrogenated jojoba oil, hydrogenated sunflower oil, hydrogenated castor oil, hydrogenated coconut oil and hydrogenated lanolin oil, di-tetrastearate ( trimethylol-1, 1, 1 propane) sold under the name "HEST 2T-4S" by the company HETERENE, di- (trimethylol-1, 1, 1 propane) tetraprenate sold under the name HEST 2T-4B by the company HETERENE. We can also mention fluorinated waxes. It is also possible to use the wax obtained by hydrogenation of esterified olive oil with the stearyl alcohol sold under the name "PHYTOWAX Olive 18 L 57" or even the waxes obtained by hydrogenation of castor oil esterified with alcohol. cetyl sold under the name "PHYTOWAX ricin 16L64 and 22L73", by the company SOPHIM. Such waxes are described in application FR-A-2792190.

According to one particular embodiment, the compositions in accordance with the invention may comprise at least one so-called sticky wax, that is to say having a tackiness greater than or equal to 0.7 N.s and a hardness less than or equal to 3.5 MPa. The use of a sticky wax may in particular make it possible to obtain a cosmetic composition which is easily applied to the eyelashes, having good grip on the eyelashes and which leads to the formation of a smooth, homogeneous and thickening makeup . The tacky wax used may in particular have a tack ranging from 0.7 N to 30 N, in particular greater than or equal to 1 N, in particular ranging from 1 N to 20 N, in particular greater than or equal to 2 N. s, in particular ranging from 2 N. s to 10 N. s, and in particular ranging from 2 Ns to δ Ns

The stickiness of the wax is determined by measuring the evolution of the force (compressive force or stretching force) as a function of time, at 20 ^° C. using the texturometer sold under the name "TA-TX2i" ® "by the company RHEO, equipped with a mobile cone-shaped acrylic polymer forming an angle of 45 °. The measurement protocol is as follows:

The wax is melted at a temperature equal to the melting point of the wax + 10 ^° C. The melted wax is cast in a container 25 mm in diameter and 20 mm deep. The wax is recrystallized at ambient temperature (25 ^° C.) for 24 hours in such a way that the surface of the wax is flat and smooth, and then the wax is kept for at least 1 hour at 20 ^° C. before carrying out the measurement of the wax. tights.

The mobile of the texturometer is moved at a speed of 0.5 mm / s, then penetrates into the wax to a depth of penetration of 2 mm. When the mobile penetrated the wax to the depth of 2 mm, the mobile is held stationary for 1 second (corresponding to the relaxation time) and then removed at a speed of 0.5 mm / s. During the relaxation time, the force (compression force) decreases sharply until it becomes zero and then, when the mobile is removed, the force (stretching force) becomes negative and then increases again to the value 0. The pantyhose corresponds to the integral of the force vs. time curve for the part of the curve corresponding to the negative values of the force (stretching force). The value of the stickiness is expressed in N. s. The tacky wax that can be used generally has a hardness of less than or equal to 3.5 MPa, in particular ranging from 0.01 MPa to 3.5 MPa, in particular ranging from 0.05 MPa to 3 MPa, or even from 0 to 1 MPa at 2.5 MPa. The hardness is measured according to the protocol described above. As sticky wax, a C20-C40 alkyl (hydroxystearyloxy) stearate (the alkyl group comprising 20 to 40 carbon atoms), alone or in a mixture, in particular a 12- (12'-hydroxystearyloxy) stearate, may be used. C20-C40 alkyl of formula (II): wherein m is an integer from 18 to 38, or a mixture of compounds of formula (II). Such a wax is especially sold under the names "Kester Wax K 82 P®" and "Kester Wax K 80 P®" by the company Koster Keunen. The waxes mentioned above generally have a starting melting point of less than 45 ^° C.

It is also possible to use the microcrystalline wax sold under the reference SP18 by the company Strahl and PITSCH, which has a hardness of approximately 0.46 MPa and a tack value of approximately 1 N.sup..s. The wax (es) may be present in the form of an aqueous microdispersion of wax. By aqueous microdispersion of wax is meant an aqueous dispersion of wax particles in which the size of said wax particles is less than or equal to about 1 μm.

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

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

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

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

Hydrophilic gelling agents:

The composition according to the invention may comprise at least one hydrophilic gelling agent, also called hydrophilic thickening thereafter.

These thickeners can be used alone or in combination. These thickeners may be chosen in particular from gums and cellulosic polymers.

By hydrophilic thickener is meant a thickening agent which is soluble or dispersible in water.

As hydrophilic thickeners, mention may in particular be made of water-soluble or water-dispersible thickening polymers. These may especially be chosen from: polyvinylpyrrolidone, polyvinyl alcohol, modified or unmodified carboxyvinyl polymers, such as the products sold under the names Carbopol (CTFA name: carbomer) by the company Goodrich; - homo- or copolymers of acrylic or methacrylic acid or their salts and esters and in particular the products sold under the names Versicol E or Versicol K ^® ^® or Salcare SC95 by the company Allied Colloid, Ultrahold 8 ^® by Ciba -GEIGY, polyacrylates and polymethacrylates such as the products sold under the names Lubrajel and Norgel by the company GUARDIAN or under the name Hispagel by the company HISPANO CHIMICA, polyacrylic acids of SYNTHALEN K type; polyacrylamides; of acrylic acid and of acrylamide sold in the form of their sodium salt under the names Reten ^® by the company Hercules, the sodium polymethacrylate sold under the name Darvan 7 ^® by the company

VANDERBILT, the sodium salts of polyhydroxycarboxylic acids sold under the name HYDAGEN F ^® by Henkel; polymers and copolymers of 2-acrylamido-2-methylpropanesulphonic acid, optionally cross-linked and / or neutralized, such as poly (2-acrylamido-2-methylpropanesulphonic acid) sold by Clariant under the name "Hostacerin AMPS" (CTFA name ammonium polyacryldimethyltauramide); crosslinked anionic copolymers of acrylamide and of AMPS, in the form of an W / O emulsion, such as those marketed under the name SEPIGEL 305

(C.T.F.A. name: Polyacrylamide / C13-14 Isoparaffin / Laureth-7) and under the name SIMULGEL 600 (C.T.F.A. name: Acrylamide / Sodium acryloyldimethyltaurate copolymer /

Isohexadecane / Polysorbate 80) by the company SEPPIC; polyacrylic acid / alkyl acrylate copolymers of PEMULEN type; polysaccharide biopolymers such as xanthan gum, guar gum, gum arabic, locust bean gum, acacia gum, scleroglucans, chitin and chitosan derivatives, carrageenans, gellans, alginates, celluloses such as microcrystalline cellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroethylcellulose and hydroxypropylcellulose; hydrophilic pyrogenic silicas obtained by high temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. Hydrophilic silicas have a large number of silanol groups on their surface. Such hydrophilic silicas are, for example, sold under the names "AEROSIL 130®", "AEROSIL 200®", "AEROSIL 255®", "AEROSIL 300®", "AEROSIL 380®" by the company Degussa, "CAB-O- SIL HS-5® "'

"CAB-O-SIL EH-5®" "CAB-O-SIL LM-130®" "CAB-O-SIL MS-55®" "CAB-O-SIL M-5®" by the company Pooch. They preferably have a particle size that can be nanometric to micrometric, for example ranging from about 5 to 200 nm; hydrophilic clays; associative polymers such as PEG-150 / STEARYL ALCOHOL / SMDI COPOLYMER sold under the name Aculyn 46 by Rohm & Haas, or the STEARETH-100 / PEG-136 / HDI COPOLYMER sold under the name Rheolate FX 1100 by Elementis); and their mixtures.

The hydrophilic thickener may be chosen from associative polymers. For the purposes of the present invention, the term "associative polymer" is intended to mean any amphiphilic polymer comprising in its structure at least one fatty chain and at least one hydrophilic portion The associative polymers according to the present invention may be anionic, cationic, nonionic or amphoteric.

Among the associative anionic polymers, mention may be made of those comprising at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly from those whose hydrophilic unit consists of an ethylenically unsaturated anionic monomer, more particularly with a vinyl carboxylic acid and very particularly with an acrylic acid, a methacrylic acid or their mixtures, and whose fatty-chain allyl ether unit corresponds to the following monomer of formula (I):

CH ₂ = C (R ') CH ₂ OB _n R (I) in which R' denotes H or CH ₃ , B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals comprising 8 to 30 carbon atoms, preferably 10 to 24, and more particularly 12 to 18 carbon atoms. Anionic amphiphilic polymers of this type are described and prepared, according to an emulsion polymerization method, in patent EP-0,216,479. Associative anionic polymers that may also be mentioned are anionic polymers comprising at least one hydrophilic unit of acidic type. olefinic unsaturated carboxylic acid, and at least one hydrophobic unit exclusively of the (C ₁₀ -C 30) alkyl ester of unsaturated carboxylic acid. By way of example, mention may be made of the anionic polymers described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949.

As cationic associative polymers, mention may be made of quaternized cellulose derivatives and polyacrylates with amine side groups. The nonionic associative polymers may be chosen from: - celluloses modified with groups comprising at least one fatty chain, for example hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl groups, especially C ₈ - C ₂₂ , arylalkyl, alkylaryl, such as NATROSOL PLUS GRADE 330 CS (C ₆ alkyl) sold by AQUALON, - celluloses modified with polyalkylene glycol ether alkyl phenol groups, guars such as hydroxypropyl guar modified by groups comprising at least one fatty chain such as an alkyl chain, copolymers of vinylpyrrolidone and hydrophobic fatty-chain monomers; copolymers of methacrylates or of alkyl acrylates in dC ₆ and of amphiphilic monomers comprising at least one fatty chain, copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, copolymer polyethylene glycol methacrylate / lauryl methacrylate, associative polyurethanes, - mixtures thereof.

Preferably, the associative polymer is chosen from associative polyurethanes. The associative polyurethanes are nonionic block copolymers comprising in the chain both hydrophilic sequences of a most often polyoxyethylenated nature and hydrophobic sequences which may be aliphatic chains alone and / or cycloaliphatic and / or aromatic chains.

In particular, these polymers comprise at least two hydrocarbon-based lipophilic chains having from C ₆ to C ₃₀ carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains may be pendant chains or chains at the end of the hydrophilic sequence. In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block. Associative polyurethanes can be sequenced as triblock or multiblock. The hydrophobic sequences may therefore be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These polymers may also be graft or star. Preferably, the associative polyurethanes are triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain comprising from 50 to 1,000 oxyethylenated groups. In general, the associative polyurethanes comprise a urethane bond between the hydrophilic sequences, hence the origin of the name. By way of example, associative polymers that can be used in the invention include the polymer Ci ₆ -OE ₁₂₀ -Ci ₆ from the company Servo Delden (under the name SER AD FX1 100, urethane functional molecule and average molecular weight by weight of 1300), EO being an oxyethylenated unit. As an associative polymer, it is also possible to use also the urea-functional Rheolate 205 sold by Rheox or the Rheolate 208 or 204 or the Rheolate FX 1100 by Elementis. These associative polyurethanes are sold in pure form. The product DW 1206B from RHOM & HAAS with a C ₂₀ alkyl chain and a urethane bond, sold at 20% solids content in water, may also be used. It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example, such polymers include SER AD FX1010, SER AD FX1035 and SER AD 1070 from SERVO DELDEN, Rheolate 255, Rheolate 278 and Rheolate 244 sold by RHEOX. It is also possible to use Aculyn 46, DW 1206F and DW 1206J, as well as Acrysol RM 184 or Acrysol 44 from Rohm & Haas, or even Borchigel LW 44 from Borchers.

Charges:

The composition according to the invention may comprise at least one filler.

The filler (s) may be present in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 30% by weight.

By fillers, it is necessary to include particles of any form, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or the texture of the composition.

The fillers can be mineral or organic of any shape, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) powders (Orgasol® from Atochem), polymethyl methacrylate powders, acrylic polymer powders, poly-β-alanine powders and polyethylene, tetrafluoroethylene polymer powders (Teflon®), lauroyl-lysine powders, starch powders, cellulose powders, boron nitride, hollow microspheres made of organic polymers, in particular the hollow polymeric microspheres of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), acrylic acid copolymers (Polytrap® from Dow Corning) and silicone resin microspheres (Toshiba Tospearls®, for example), elastomeric polyorganosiloxanes, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or glass microcapsules ceramic, clay, quartz, natural diamond powder, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc stearate, magnesium or lithium, zinc laurate, magnesium myristate.

By mineral fillers, mention may notably be made of talc, mica, silica, kaolin, boron nitride, precipitated calcium carbonate, magnesium carbonate and magnesium carbonate, hydroxyapatite and silica microspheres. hollow (Silica Beads® from Maprecos), or microcapsules of glass or ceramics, clay, quartz, natural diamond powder or their mixture.

As silica powder, mention may be made of:

- The porous silica microspheres sold under the name SILICA BEADS SB-700 by the company MYOSHI; "SUNSPHERE® H51", "SUNSPHERE® H33" by the company ASAHI GLASS; the polydimethylsiloxane-coated amorphous silica microspheres sold under the name "SA Sunsphere® H 33", "SA Sunsphere® H53" by the company Asahi Glass.

Preferably, the mineral filler is silica, talc or their mixture. Of the spherical fillers, silicas, such as hollow silica microspheres, in particular SB700® from Miyoshi Kasei, are preferred.

According to a preferred embodiment, the composition according to the invention further comprises at least one other filler. Said at least one other filler may be mineral or organic. It can thus be a mixture of mineral and organic fillers.

According to an alternative, the composition according to the invention may contain a mineral filler and another mineral filler, said mineral filler being as defined above, and optionally at least one organic filler, as defined below. According to another alternative, the composition according to the invention may contain a mineral filler and an organic filler.

Organic fillers that may especially be mentioned include polyamide powders (Nylon® or Orgasol® from Arkema), acrylic polymer powders, in particular polymethyl methacrylate, poly methyl methacrylate / ethylene glycol dimethacrylate, polymethacrylate powders, and the like. allyl / ethylene glycol dimethacrylate, ethylene glycol dimethacrylate / lauryl methacrylate copolymer, cellulose, poly-β-alanine and polyethylene powders, tetrafluoroethylene (Teflon®) polymer powders, lauroyl -lysine, starch, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel Industry), copolymers of acrylic acid (Polytrap® from Dow Corning) and resin microbeads silicone (Toshiba Tospearls®, for example), elastomeric polyorganosiloxane particles, especially obtained by polymerization of organopolysiloxane having at least ins two hydrogen atoms each bonded to a silicon atom and an organopolysiloxane comprising at least two ethylenically unsaturated groups (especially two vinyl groups) in the presence of platinum catalyst, or metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example zinc, magnesium or lithium stearate, zinc laurate, magnesium myristate.

Ionic surfactants

The composition according to the invention may comprise at least one ionic surfactant. The compositions according to the invention may thus comprise at least one ionic surfactant, and the mixture 1) described above.

The surfactant may be lipophilic and / or hydrophilic, used alone or in coupling. The surfactant may be chosen from anionic, cationic and amphoteric surfactants. The surfactant may be present in the composition according to the invention in a content ranging from 0.1% to 10% by weight, relative to the total weight of the composition, and preferably ranging from 0.5% to 8% by weight. and preferably ranging from 0.5% to 7% by weight.

When the ionic surfactant is an anionic surfactant, it is chosen from: carboxylates, such as sodium 2- (2-hydroxyalkyloxy) acetate;

taurates and N-acyl N-methyltaurates;

alkylsulfoacetates;

the polypeptides;

anionic derivatives of alkyl polyglycoside (acyl-D-galactoside uronate); salts of C16-C30 fatty acids, in particular those derived from amines, such as triethanolamine stearate and / or 2-amino-2-methylpropane diol-1,3-stearate;

salts of polyoxyethylenated fatty acids, in particular those derived from amines or alkaline salts, and mixtures thereof;

phosphoric esters and their salts, such as "DEA oleth-10 phosphate" (Crodafos N 1ON from the company CRODA) or monocotyl monopotassium phosphate (Amphisol K from Givaudan); sulfosuccinates such as "Disodium PEG-5 citrate lauryl sulfosuccinate" and "Disodium ricinoleamido MEA sulfosuccinate";

alkyl sulphates; isethionates and N-acylisethionates;

- acyl glutamates such as "Disodium hydrogenated tallow glutamate" (Amisoft HS-21 R ^® sold by the company Ajinomoto) and sodium stearoyl glutamate (Amisoft HS-1 1 PF ^® sold by the company Ajinomoto), and mixtures thereof;

- soy derivatives such as potassium soyate;

citrates, such as Glyceryl stearate citrate (Axol C 62 Pellets from Degussa); proline derivatives, such as Sodium palmitoyl proline (Sepicalm VG of

Seppic), or Sodium Palmitoyl Sarcosinate Mixture, Palmitoyl Glutamate Magnesium, Palmitic Acid and Palmitoyl Proline (Sepifeel One Seppic);

lactylates, such as Sodium stearoyl lactylate (Akoline SL from Karlshamns AB); sarcosinates, such as sodi um palmitoyl sarcosinate (N ikkol sarcosinate PN) or the mixture of Stearoyl sarcosine and Myristoyl sarcosine 75/25 (Crodasin SM from Croda); sulfonates, such as Sodium C14-17 alkyl seculphonate (Hostapur SAS 60 from Clariant); glycinates, such as sodium cocoyl glycinate (Amilite GCS-12 from Ajinomoto).

The compositions in accordance with the invention may also contain one or more amphoteric surfactants such as N-acyl amino acids such as N-alkylaminoacetates and disodium cocoamphodiacetate and amine oxides such as stearamine oxide and betaines. , N-alkylamidobetaines and their derivatives, sultaines, alkyl polyaminocarboxylates, alkylamphoacetates, or silicone surfactants such as dimethicone copolyols phosphates such as that sold under the name PECOSIL PS 100 ^® by the company Phoenix Chemical and their mixtures. Preferably, the compositions according to the invention also comprise an amphiphilic silicone elastomer comprising hydrophilic groups, polyoxyalkylene or hydrophilic groups, in particular polyoxyethylene and / or polyoxypropylenes, or hydrophilic polyglycerol groups, sequences or grafts, and which can additionally possess lateral alkyl groups, in particular lateral lauryyl groups, in particular a polyglycerolated silicone elastomer. By way of example, an elastomeric crosslinked organopolysiloxane obtainable by crosslinking addition reaction of diorganopolysiloxane containing at least one silicon-bonded hydrogen and polyglycerolated compounds having ethylenically unsaturated groups, in particular in the presence of platinum catalyst, is used.

As polyglycerolated silicone elastomers, those sold under the names "KSG-710", "KSG-810", "KSG-820", "KSG-830", "KSG-840" by the company Shin Etsu can be used. fibers

The composition may comprise fibers.

By "fiber" is meant an object of length L and diameter D such that L is greater than D, where D is the diameter of the circle in which the section of the fiber is inscribed. In particular, the L / D ratio (or form factor) is chosen in the range from 3.5 to 2500, preferably from 5 to 500, and more preferably from 5 to 150.

The fibers that can be used in the composition of the invention may be fibers of synthetic or natural, mineral or organic origin. They can be short or long, unitary or organized, for example braided, hollow or full. Their shape can be any and in particular of circular or polygonal section (square, hexagonal or octagonal) depending on the specific application envisaged. In particular, their ends are blunt and / or polished to avoid injury.

In particular, the fibers have a length ranging from 1 μm to 10 mm, preferably from 0.1 mm to 5 mm and better still from 0.3 mm to 3 mm. Their cross section may be in a circle with a diameter ranging from 2 nm to 500 μm, preferably ranging from 100 nm to 100 μm and better still from 1 μm to 50 μm. The weight or titer of the fibers is often given in denier or decitex and represents the weight in gram for 9 km of yarn. Preferably, the fibers according to the invention have a title chosen in the range from 0.01 to 10 to denier, preferably from 0.1 to 2 denier and better still from 0.3 to 0.7 denier.

Such fibers are described in particular in Applications FR-A-2844710 and EP-A-1201221, the contents of which are incorporated by reference.

The fibers may be present in the composition in a content ranging from 0.1% to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.1% to 20% by weight, and preferably ranging from 0.1% to 10% by weight.

Other Ingredients and / or Additives The ingredients described below may be used alone in combination with the resins of the invention or as additives in addition to the other aforementioned ingredients in combination with said resins according to the invention.

Silicone elastomers

The compositions according to the invention may further comprise an amphiphilic silicone elastomer, preferably chosen from polyoxyalkylenated and polyglycerolated silicone elastomers. Polyoxyalkylene silicone elastomers include those described in US Pat.

As polyoxyalkylenated silicone elastomers, it is possible to use: those of INCI name PEG-10 Dimethicone / Vinyl dimethicone crosspolymer: such as those sold under the names "KSG-21", "KSG-20", by Shin Etsu; INCY name products Lauryl PEG-15 Dimethicone / Vinyldimethicone

Crosspolymer: as those marketed under the names "KSG-30" and "KSG-31",

KSG-32 "(in isododecane)," KSG-33 "(in trioctanoine)," KSG-210 "," KSG-310 "

(in mineral oil), "KSG-320" (in isododecane), "KSG-330", "KSG-340" by Shin Etsu. As polyglycerolated silicone elastomers, those of INCI name Dimethicone (and) Dimethicone / Polyglycerin-3 crosspolymer can be used: such as those marketed under the names "KSG-710" by Shin Etsu; those INCI name Lauryl Dimethicone / Polyglycerin-3 crosspolymer: such as those sold under the names "KSG-840" (in squalene) by the company Shin Etsu. These particular elastomers, when they are in combination with the resins according to the invention, may make it possible to improve the non-transfer and comfort properties (flexibility) of the compositions comprising them.

Oils

The composition according to the invention may comprise at least one oil.

The oil may be chosen from hydrocarbon oils, silicone oils and fluorinated oils.

The oil may be chosen from volatile oils, non-volatile oils, and mixtures thereof.

The term "hydrocarbon-based oil" means an oil formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and not containing a silicon or fluorine atom; it may contain ester, ether, amine, amide groups.

By silicone oil is meant an oil containing at least one silicon atom, and in particular containing Si-O groups.

By fluorinated oil is meant an oil containing at least one fluorine atom.

The composition according to the invention may comprise at least one volatile oil. By "volatile oil" is meant an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic oil which is liquid at ambient temperature, in particular having a non-zero vapor pressure, at ambient temperature and atmospheric pressure, in particular having a vapor pressure ranging from 0.13 Pa to 40 000 Pa (10 300 mm Hg), and preferably ranging from 1.3 Pa to 13 000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mm Hg). mm Hg).

In addition, the volatile oil generally has a boiling point, measured at atmospheric pressure, ranging from 150 ^° C. to 260 ^° C., and preferably ranging from 170 ^° C. to 250 ^° C.

The composition according to the invention may comprise a hydrocarbon-based volatile oil chosen in particular from hydrocarbon-based oils having a flash point ranging from 40 ^° C. to 102 ^° C., preferably ranging from 40 ^° C. to 55 ^° C., and preferably ranging from 40 ^° C. to 40 ^° C. C. at 50 ^° C. As volatile hydrocarbon-based oil, mention may be made of volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof, and in particular C8-C16 branched alkanes, such as isoalkanes (also known as isoparaffins), C8-C16, isododecane, isodecane, isohexadecane and for example the oils sold under the trade names of Isopars or permetyls, branched C8-C16 esters such as isohexyl neopentanoate, and their mixtures. Preferably, the volatile hydrocarbon oil is chosen from volatile hydrocarbon oils having from 8 to 16 carbon atoms and mixtures thereof, in particular from isododecane, isodecane and isohexadecane, and is especially isododecane. For good color retention properties while maintaining a matte and comfortable deposit for dyed applications, volatile hydrocarbon solvents of 8 to 16 carbon atoms, especially 9 to 13 carbon atoms, are preferred. As volatile hydrocarbon solvent C8 to C16, there may be mentioned linear or branched alkanes, in particular branched, such as iso-alkanes (also called isoparaffins) C8-C16, isododecane, isodecane, isohexadecane, and for example the oils sold under the trade names Isopars or permetyls, and mixtures thereof. Preferably, the volatile hydrocarbon solvent having from 8 to 16 carbon atoms is chosen from isododecane, isodecane, isohexadecane and their mixture. According to a particular embodiment, the volatile solvent is isododecane.

According to another particular embodiment, the volatile hydrocarbon solvent is a volatile linear alkane having a flash point in the range of from 70 to 120 ^° C., and more particularly from 80 to 100 ^° C., and in particular from approximately 89 ^° C. A volatile linear alkane suitable for the invention is liquid at ambient temperature (approximately 25 ^° C.).

According to one embodiment, an alkane that is suitable for the invention may be a volatile linear alkane comprising from 8 to 16 carbon atoms, in particular from 10 to 15 carbon atoms, and more particularly from 11 to 13 carbon atoms. A volatile linear alkane suitable for the invention may advantageously be of plant origin.

Such an alkane can be obtained, directly or in several stages, from a vegetable raw material such as an oil, a butter, a wax, etc.

As an example of an alkane that is suitable for the invention, mention may be made of the alkanes described in the patent application of Cognis WO 2007/068371. These alkanes are obtained from fatty alcohols, themselves obtained from coconut oil or palm oil.

By way of example of a linear alkane suitable for the invention, mention may be made of n-nonane (C9), n-decane (C10), n-undecane (C1 1), n-dodecane (C12) , n-tridecane (C13), n-tetradecane (C14), n-pentadecane (C15), n-hexadecane (C16) and n-heptadecane (C17), and mixtures thereof, and in particular the mixture n-undecane (C11) and n-tridecane (C13) sold under the reference CETIOL UT by Cognis. According to a particular embodiment, a volatile linear alkane suitable for the invention may be chosen from n-nonane, n-undecane, n-dodecane, n-tridecane, n-heptadecane, and mixtures thereof. More particularly, a volatile linear alkane suitable for the invention can be used in the form of a n-undecane / n-tridecane mixture.

Preferably, in such a mixture, the weight ratio n-undecane: n-tridecane may be 50:50 to 90:10, preferably ranging from 60:40 to 80:20, preferably ranging from 65:35 to 75: 25. In particular, a composition according to the invention may comprise a n-undecane: n-tridecane mixture in a weight ratio of 70: 30. Such a mixture is marketed under the name CETIOL UT by the company COGNIS.

For skin makeup products, especially foundations and lipsticks, it is advantageous to use linear hydrocarbon volatile oils having from 8 to 16 carbon atoms.

As volatile silicone oil, mention may be made of linear or cyclic silicones having from 2 to

7 atoms of silicon, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil usable in the invention may be mentioned especially octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and mixtures thereof.

The volatile oil may be present in the composition according to the invention in a content ranging from 0.1% to 90% by weight, relative to the total weight of the composition, preferably ranging from 1% to 70% by weight. and preferably ranging from 5% to 50% by weight. The composition according to the invention may comprise at least one non-volatile oil.

By "non-volatile oil" is meant an oil remaining on the keratin materials at ambient temperature and atmospheric pressure for at least several hours and in particular having a vapor pressure of less than 10 ^-3 mmHg (0.13 Pa). also define a non-volatile oil as having an evaporation rate such that under the conditions defined above, the amount evaporated after 30 minutes is less than 0.07 mg / cm ² .

As the non-volatile hydrocarbon oil, paraffin oil (or petroleum jelly), squalane, hydrogenated polyisobutylene (Parleam oil), perhydrosqualene, mink, turtle, soybean oil, coconut oil and the like can be used. sweet almond, calophyllum, palm, grape seed, sesame, maize, arara, rapeseed, sunflower, cotton, apricot, castor oil, avocado, jojoba, olive or cereal sprouts; esters of lanolic acid, oleic acid, lauric acid, stearic acid; fatty esters, especially C12-C36, such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, palmitate 2-ethyl-hexyl, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, myristate or 2-octyl-dodecyl lactate, di (2-ethyl hexyl) succinate, malate diisostearyl, glycerol triisostearate or diglycerine; behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid; higher fatty alcohols, especially C16-C22, such as cetanol, oleic alcohol, linoleic or linolenic alcohol, isostearyl alcohol or octyl dodecanol; and their mixtures.

In particular, to obtain a makeup mattifying complexion, while maintaining a comfortable use, both during application and after makeup, use non-volatile hydrocarbon oils C6-C22 may be chosen from:

the carbonates of formula (I) below: R 1 -OC (= O) -O-R '1, with R 1 and R' 1, which are identical or different, represent a C 4 to C 12 alkyl chain, and preferentially from C 5 to C C10, linear or branched, saturated or unsaturated (preferably saturated), optionally having at least one ring, saturated or unsaturated, preferably saturated; these oils of formula (I) may be dicaprylyl carbonate, sold under the name Cetiol CC® by the company Cognis, di (ethyl-2-hexyl) carbonate, sold under the name TEGOSOFT DEC® by the company Goldschmidt, di- isobutyryl carbonate; di-neopentyl carbonate; dipentyl carbonate; di neoheptyl carbonate; di-heptyl carbonate; di-isononyl carbonate; or di-nonyl carbonate; the monoesters of formula (II): R2-OC (= O) -R'2, with R2 and R'2, which are identical or different, represent a C4 to C12 alkyl chain, and preferentially a C5 to C10 linear chain; or branched, saturated or unsaturated (preferably saturated), optionally having at least one ring, saturated or unsaturated, preferably saturated; these oils of formula (II) may be ethyl 2-hexyl isobutyrate, ethyl 2-hexyl butyrate, caprylyl butyrate, isononyl isobutyrate, ethyl 2 hexyl hexanoate, isononyl hexanoate, neopentyl hexanoate, caprylyl heptanoate, octyl octanoate, sold under the name DRAGOXAT EH® by SYMRISE, isononyl isononanoate, the di-esters of formula (III) below: R3-OC (= O) -R'3-C (= O) -OR "3, with R3 and R" 3, which are identical or different, represent an alkyl chain in C4 to C12, and preferably C5 to C10, linear or branched, saturated or unsaturated (preferably saturated), optionally having at least one ring, saturated or unsaturated, preferably saturated, and R'3 represents an alkylene chain, saturated or unsaturated

C1 to C4, preferably C2 to C4, for example an alkylene chain derived from succinate (in this case R'3 is a saturated C2 alkylene chain), maleate (in this case R'3 is a C2 alkylene chain; unsaturated), glutarate (in this case R'3 is a saturated C3 alkylene chain), or adipate (in this case R'3 is a saturated C4 alkylene chain); in particular, R 3 and R "3 are chosen from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, ethyl 2-hexyl, octyl, nonyl and isononyl, preferentially dicaprylyl maleate, especially marketed by the company ALZO; di (2-ethylhexyl) succinate, the ethers of the following formula (IV): R4-O-R4 ', with R4 and R4', which may be identical or different, represent a C4-C12 alkyl chain, and preferentially C5 chain; at

C10, linear or branched, saturated or unsaturated (preferably saturated), optionally having at least one ring, saturated or unsaturated, preferably saturated; in particular, R4 and R4 'are chosen from isobutyl, pentyl, neopentyl, hexyl, heptyl, neoheptyl, ethyl 2-hexyl, octyl, nonyl, isononyl; among the compounds of formula (IV), there may be mentioned preferentially dicaprylyl ether, marketed under the name of Cetiol OE® by the company COGNIS;

the alkyl tri-esters of formula (V): R5-OC (O) -CH2-CH [-OC (O) -R'5] -CH2-O-C (O) -R "5, with R5, R'5 and R "5, which are identical or different, represent a C4-C10, preferably C5-C8, linear or branched, saturated or unsaturated (preferably saturated) alkyl chain, in particular R5, R'5 and R "5 are identical, preferably

R5, R'5 and R "5 (in particular identical) are alkyl radicals of the following fatty acids: caprylic acid, 2-ethylhexyl, neopentanoic or neoheptanoic acid, there may be mentioned preferentially, as compound of formula (V), the caprylic capric triglyceride, sold in particular under the name MYRITOL 318® by the company COGNIS, and mixtures thereof.

The C 6 -C 22 hydrocarbon-based nonvolatile oil advantageously used in said makeup and / or care compositions intended to matify the complexion is dicaprylyl carbonate, especially sold under the name CETIOL CC by the company COGNIS.

Advantageously, when the composition is intended for makeup and / or care of the lips and comprises a non-volatile oil, this oil is chosen from phenyl silicone oils. Such an oil is also called phenyl silicone. By phenyl silicone is meant an organopolysiloxane substituted with at least one phenyl group.

The phenyl silicone is preferably non-volatile. By "non-volatile" is meant an oil whose vapor pressure at ambient temperature and atmospheric pressure is non-zero and less than 0.13 Pa.

Preferably, the weight-average molecular weight of the phenyl silicone oil is between

500 and 10,000 g / mol.

The silicone oil may be chosen from phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes and 2-phenylethyl trimethylsiloxysilicates.

The silicone oil can meet the formula: wherein the R groups independently represent a methyl or a phenyl. Preferably in this formula, the silicone oil comprises at least three phenyl groups, for example at least four, at least five or at least six.

According to another embodiment, the silicone oil corresponds to the formula

wherein the R groups independently represent a methyl or a phenyl. Preferably in this formula, said organopolysiloxane comprises at least three phenyl groups, for example at least four or at least five. Mixtures of the phenyl organopolysiloxanes described above can be used.

For example, mixtures of organopolysiloxane triphenyl, tetra- or penta-phenyl. According to another embodiment, the silicone oil corresponds to the formula

in which Me is methyl, Ph is phenyl. Such phenyl silicone is especially manufactured by Dow Corning under the reference Dow Corning 555 Cosmetic Fluid (INCI name: trimethyl pentaphenyl trisiloxane). The reference Dow Corning 554 Cosmetic Fluid can also be used.

According to another embodiment, the silicone oil corresponds to the formula

wherein Me is methyl, y is 1 to 1000, and X is -CH 2 -CH (CH 3) (Ph).

According to another embodiment, the silicone oil corresponds to the formula

where -OR 'is -O-SiMe3, y is 1 to 1000 and z is 1 to 1000. The phenyl silicone oil may be chosen from the phenyl silicones of formula (VI) below:

in which

- R1 to R10, independently of each other, are hydrocarbon radicals, saturated or unsaturated, linear, cyclic or branched, C1-C30,

- m, n, p and q are, independently of one another, integers between 0 and 900, provided that the sum 'm + n + q' is not 0.

Preferably, the sum 'm + n + q' is between 1 and 100. Preferably, the sum 'm + n + p + q' is between 1 and 900, more preferably between 1 and 800. Preferably, q is 0.

The phenyl silicone oil may be chosen from the phenyl silicones of formula (VII) below:

in which :

- R1 to R6, independently of each other, are linear or cyclic hydrocarbon radicals, saturated or unsaturated, C1-C30,

- m, n and p are, independently of one another, integers between 0 and 100, provided that the sum 'n + m' is between 1 and 100.

Preferably, R1 to R6, independently of each other, represent a saturated hydrocarbon radical, linear or branched, C1-C30, especially C1-C12, and in particular a methyl, ethyl, propyl or butyl radical.

In particular, R1 to R6 may be identical, and may furthermore be a methyl radical. Preferably, one can have m = 1 or 2 or 3, and / or n = 0 and / or p = 0 or 1, in formula (VII). It is possible to use a phenyl silicone oil of formula (VI) having a viscosity at 25 ° C. of between 5 and 1500 mm ² / s (ie 5 to 1500 cSt), preferably having a viscosity of between 5 and 1000 mm ² / s (ie 5 to 1000 cSt).

As phenylated phenylated oil of formula (VII), it is possible especially to use phenyltrimethicones such as DC556 from Dow Corning (22.5 cSt), Silbione 70663V30 from Rhône Poulenc (28 cSt), or diphenyldimethicones such as oils Belsil, including Belsil PDM1000 (100OcSt), Belsil PDM 200 (200 cSt) and Belsil PDM 20 (2OcSt) from Wacker. Values in parentheses represent viscosities at 25 ° C. The non-volatile silicone oil may be chosen from silicones of formula:

in which :

R 1, R ₂ , R 5 and R ₆ are, together or separately, an alkyl radical having 1 to 6 carbon atoms,

R 3 and R ₄ are, together or separately, an alkyl radical having from 1 to 6 carbon atoms, or an aryl radical, X is an alkyl radical having from 1 to 6 carbon atoms, a hydroxyl radical or a vinyl radical, n and p being chosen so as to impart to the oil a molecular weight of less than 200 000 g / mol, preferably less than 150 000 g / mol and more preferably less than 100 000 g / mol.

The non-volatile oil may be present in a content ranging from 0.1% to 70% by weight, relative to the total weight of the non-volatile liquid fatty phase, preferably ranging from 0.5% to 60% by weight. and preferably ranging from 1% to 50% by weight. For skin makeup products, especially foundations and lipsticks, advantageously use volatile or nonvolatile linear silicone oils. The combination of the resins according to the invention and a linear silicone oil can in particular make it possible to improve non-transfer. For skin makeup products, especially lipsticks, phenyl silicone oils will advantageously be used. The combination of the resins according to the invention and a phenyl silicone oil can in particular make it possible to improve the brightness, the comfort and to reduce the sensation of the adhesive. Nonionic surfactants

The composition according to the invention may comprise at least one nonionic surfactant.

In particular, it is possible to use an emulsifier having at 25 ^° C. an HLB (hydrophilic-lipophilic balance) balance in the Griffin sense, specific for the composition that it is desired to obtain.

The HLB value according to GRIFFIN is defined in J. Soc. Cosm. Chem. 1954 (volume 5), pages

249-256.

Reference can be made to "Encyclopedia of Chemical Technology, KIRK-OTHMER", Vol. 22, p. 333-432, ^3rd edition, 1979, Wiley, for the definition and properties functions (emulsifier) of surfactants, in particular p. 347-377 of this reference, for nonionic surfactants.

The nonionic surfactants preferably used in the composition according to the invention are chosen from: a) nonionic surfactants with a HLB greater than or equal to 8 at 25 ^° C., used alone or as a mixture; we can mention in particular:

esters and ethers of osteos such as the mixture of cetylstearyl glucoside and of cetyl and stearyl alcohols, such as Montanov 68 from Seppic; oxyethylenated and / or oxypropylenated ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylene groups) of glycerol;

oxyethylenated and / or oxypropylenated ethers (which can contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular of C8-C24 and preferably of C12-C18 alcohols) such as oxyethylenated ether; oxyethylenated cetearyl alcohol (CTFA name "Ceteareth-30"), the oxyethylenated ether of oxyethylenated stearyl alcohol (CTFA name "Steareth-20"), and the oxyethylenated ether of the mixture of fatty alcohol C12-C15 comprising 7 oxyethylene groups (CTFA name "C12-15 Pareth- 7") sold under the name NEODOL 25-7 by Shell Chemicals ^®,

fatty acid esters (in particular C 8 -C 24, and preferably C 16 -C 22) and polyethylene glycol (which may comprise from 1 to 150 ethylene glycol units), such as PEG-50 stearate and monostearate PEG-40 marketed under the name Myrj ^® 52P by ICI Uniqema;

fatty acid esters (in particular of C 8 -C 24, and preferably C 16 -C 22) and oxyethylenated and / or oxypropylenated glycerol ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylene groups), as monostearate PEG-200 glyceryl sold under the name Simulsol 220 TM ^® by Seppic; polyethoxylated glyceryl stearate with 30 ethylene oxide groups, such as the product TAGAT S ^® sold by the company GOLDSCHMIDT, polyethoxylated glyceryl oleate with 30 ethylene oxide groups, such as the product TAGAT O ^® sold by the company GOLDSCHMIDT company, glycerol cocoate polyethoxylated with 30 ethylene oxide groups such as the product VARIONIC Ll 13 ^® sold by the company SHEREX, glyceryl isostearate polyethoxylated with 30 ethylene oxide groups as the product TAGAT L ^® sold by the company GOLDSCHMIDT and polyethoxylated glyceryl laurate with 30 ethylene oxide groups, such as the product TAGAT I ^® from GOLDSCHMIDT, - fatty acid esters (in particular C8-C24 acid, and preferably in

C16-C22) and oxyethylenated and / or oxypropylenated sorbitol ethers (which may contain from 1 to 150 oxyethylenated and / or oxypropylene groups), such as polysorbate 20 sold under the name Tween ^20® by the company CRODA, polysorbate 60 sold under the name Tween ^60® by the company CRODA, - dimethicone copolyol, such as that sold under the name Q2-

5220 ^® by the company Dow Corning,

- dimethicone copolyol benzoate (SLB FINSOLV 101 ^® and 201 ^® FINTEX of the company)

copolymers of propylene oxide and of ethylene oxide, also called EO / PO polycondensates,

- and their mixtures.

The EO / PO polycondensates are more particularly copolymers consisting of polyethylene glycol and polypropylene glycol blocks, such as, for example, polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polycondensates. These triblock polycondensates have, for example, the following chemical structure:

H- (O-CH ₂ -CH ₂ ) _a - (O-CH (CH ₃ ) -CH ₂ ) _b - (O-CH ₂ -CH ₂ ) _a -OH, in which a is from 2 to 120, and b is from 1 to 100.

The polycondensate OE / OP preferably has a weight average molecular weight ranging from 1000 to 15000, and better from 2000 to 13000. Advantageously, said polycondensate OE / OP has a cloud temperature, at 10 g / 1 in distilled water, greater than or equal to 20 ⁰ C, preferably greater than or equal to 60 ⁰ C. The cloud temperature is measured according to the ISO 1065 standard. polycondensate OE / OP used according to the invention, mention may be made of polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polycondensates sold under the trade names SYNPERONIC ^® such as SYNPERONIC PE / L44 ^® and SYNPERONIC PE / F127 ^® by the company ICI. b) nonionic surfactants of HLB less than 8 at 25 ⁰ C, optionally combined with one or more nonionic surfactants of HLB greater than 8 at 25 ⁰ C, as mentioned above such that:

- the saccharide esters and ethers such as sucrose stearate, sucrose cocoate, sorbitan stearate and mixtures thereof as Arlatone 2121 ^® sold by ICI;

oxyethylenated and / or oxypropylenated ethers (which can contain from 1 to 150 oxyethylenated and / or oxypropylenated groups) of fatty alcohols (in particular of C8-C24 and preferably of C12-C18 alcohols) such as oxyethylenated ether; stearyl alcohol with 2 oxyethylenated groups (CTFA name "Steareth-2");

esters of fatty acids (in particular of C8-C24 and preferably C16-C22 acids) and of polyol, in particular glycerol or sorbitol, such as glyceryl stearate, glyceryl stearate, such as the product sold under the name Tegin M ^® by the company Goldschmidt, glyceryl laurate, such as the product sold under the name Imwitor 312 ^® by the company Hüls, polyglyceryl-2 stearate, sorbitan tristearate, glyceryl ricinoleate; lecithins, such as soy lecithins (such as Emulmetik 100 J from Cargill, or Biophilic H from Lucas Meyer);

- the mixture of cyclomethicone / dimethicone copolyol sold under the name Q2-3225C ^® by Dow Corning.

The nonionic surfactant may also be chosen from a C8-C22 alkyl dimethicone copolyol, that is to say an oxypropylenated and / or oxyethylenated poly (C 8 -C 22) dimethyl methyl siloxane alkyl.

The C8-C22 alkyl dimethicone copolyol is advantageously a compound of formula (I) below:

in which :

PE represents (-C 2 H 4 O) x- (C 3 H 6 O) y R, R being chosen from a hydrogen atom and an alkyl radical of 1 to 4 carbon atoms, x ranging from 0 to 100 and y ranging from 0 to 80; and y not being simultaneously 0

- m ranging from 1 to 40 - n ranging from 10 to 200 - o ranging from 1 to 100

p ranging from 7 to 21

q ranging from 0 to 4 and preferably: R = H m = 1 to 10 n = 10 to 100 o = 1 to 30 P = 15 q = 3

As C8-C22 alkyl dimethicone copolyol, mention may be made of cetyl dimethicone copolyol such as the product marketed under the name Abil EM-90 by the company Goldschmidt.

According to a particular mode for formulating stable emulsions, having a low viscosity allowing easy application, while giving the makeup product a lasting effect of the makeup once applied, it will be advantageous to use at least one silicone nonionic surfactant, optionally associated with at least one hydrocarbon surfactant and optionally at least one wax:

As nonionic silicone surfactant, mention may be made, for example, of: a) polydialkyl silicones with polyoxyalkylene (or POE) and / or polyoxypropylene (or PPO) hydrophilic and / or terminal hydrophilic groups, Moreover, these silicone surfactants comprise preferably linear or branched C1-C20 alkyl side groups, preferably linear alkyl groups, such as lauryl or cetyl These surfactants may also carry organosiloxane side groups, in particular, in this first category, may mention:

polydimethylsiloxanes with POE side groups, such as in particular KF-601 1, KF-6012, KF-6013, KF-6015, KF-6016 and KF-6017 from Shin Etsu. ;

polydimethylsiloxanes with POE side groups and alkyl side groups, such as cetyl PEG-PPG 10/1 dimethicone, sold under the name ABIL EM90 by the company Evonik GOLDSCHMIDT;

the branched polydimethylsiloxanes with POE side groups, such as in particular PEG-9 polydimethyl siloxyethyl dimethicone, sold under the name KF-6028 by the company Shin Etsu;

branched polydimethyl siloxanes with alkyl side groups, such as, in particular, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, sold under the name KF-6038 by the company Shin Etsu. b) Polydialkyl silicones with polyglycerolated or glycerolated side groups. These silicone surfactants also preferably comprise linear or branched C1-C20 alkyl side groups, and also preferably linear alkyl groups such as lauryl or cetyl. Likewise, these silicone and glycerolated surfactants may, in addition, carry organosiloxane side groups. In particular, in this category, we can mention:

polydimethylsiloxanes with polyglycerolated side groups, such as polyglyceryl-3-disiloxane dimethicone, sold under the name KF-6100 by the company Shin Etsu;

polygamyl siloxanes branched and with polyglycerolated side groups, such as polyglyceryl-3 polydimethylsiloxyethyl dimethicone, sold under the name KF-6104 by the company Shin Etsu; branched polydimethyl siloxanes with polyglycerol side groups and alkyl side groups, such as lauryl polyglyceryl-3 polydimethyl siloxyethyl dimethicone, sold under the name KF-6105 by the company Shin Etsu. Of the silicone nonionic surfactants, Cetyl PEG / PPG-10/1 dimethicone, marketed under the name ABIL EM90 by the company EVONIK GOLDSCHMIDT, is preferred.

The nonionic silicone surfactant is advantageously in combination with at least one nonionic organic surfactant.

Nonionic organic surfactants that may be mentioned include polyol fatty acid esters such as sorbitol or glycerol mono-, di-, tri- or sesquiolates or stearates, and glycerol or polyethylene glycol laurates; fatty acid esters of polyethylene glycol (monostearate or polyethylene glycol monolaurate); fatty acid esters (stearate, oleate) of polyoxyethylenated sorbitol; polyoxyethylenated alkyl (lauryl, cetyl, stearyl, octyl) ethers.

Among the nonionic organic surfactants, the following are preferred: polyglycerolated fatty acid esters comprising at least 3 glycerol ether units, such as polyglyceryl 3; polyoxyalkylenated fatty acid esters (polyoxyethylenated and / or polyoxypropylenated), preferably having at least 3 oxyethylene groups; ethers of fatty alcohols and polyglycerols with at least 3 units of glyceryl ether; ethers of fatty alcohols and of polyoxyalkylene (POE and / or POE / PPO) with at least

3 POE groups.

Of the nonionic organic surfactants, polyglyceryl-4 isostearate sold under the name ISOLAN GI34® by the company Evonik GOLDSCHMIDT is preferred.

In combination with the nonionic silicone surfactant and the nonionic organic surfactant, it is advantageous to use at least one wax.

Among the waxes, the mixture of ethylene glycol stearate acetyl / glyceryl tri-stearate is preferred, especially sold under the name UNITVVIX by the company UNITED GARDIAN.

Coloring matters

The composition according to the invention may comprise at least one dyestuff.

The coloring material may be chosen from pulverulent dyestuffs (in particular pigments and pearlescent agents) and water-soluble or liposoluble dyestuffs. By pigments, it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.

By nacres, it is necessary to understand particles of any iridescent form, in particular produced by certain molluscs in their shell or else synthesized.

The pigments may be white or colored, mineral and / or organic. Mention may be made, among inorganic pigments, of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc and iron (black, yellow or red). or chromium, manganese violet, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum.

Mention may also be made of effect pigments such as particles comprising an organic or inorganic, natural or synthetic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, said substrate being covered or not with metallic substances such as aluminum, gold, silver, platinum, copper, bronze, or metal oxides such as titanium dioxide, iron oxide, chromium oxide and their mixtures.

The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated with, inter alia, blue. ferric oxide or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride. It is also possible to use interferential pigments, in particular liquid crystal or multilayer pigments.

The term alkyl mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms.

Hydrophobic-treated pigments are described in particular in application EP-A-1086683.

The pulverulent dyestuffs as described above may be totally or partially surface-treated with a hydrophobic agent, in particular a compound of a silicone nature, a compound of a fluorinated nature, a compound of fluorosilicone nature, a fatty acid or amino acid, or one of their mixtures.

By silicone compound is meant a compound comprising at least one silicon atom. By fluorinated compound is meant a compound comprising at least one fluorine atom. By fluoro-silicone compound is meant a compound comprising at least one fluorine atom and at least one silicon atom.

By way of example, the hydrophobic treatment agent may be chosen from silicones such as meticones, dimethicones, perfluoroalkylsilanes, perfluoroalkyl silazanes, triethoxy caprylylsilane and triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone; fatty acids such as stearic acid; metallic soaps such as aluminum dimyristate, aluminum salt of hydrogenated tallow glutamate; perfluoroalkyl phosphates, hexafluoropropylene polyoxides, polyorganosiloxanes comprising perfluoroalkyl perfluoropolyether groups, silicone-grafted acrylic polymers (described in particular in application JP-A-05-339125, the contents of which are incorporated by reference); amino acids; N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate, and mixtures thereof.

The surface-treated pulverulent dyestuffs may be prepared according to chemical, electronic, mechano-chemical or mechanical surface treatment techniques well known to those skilled in the art. Commercial products can also be used.

The surfactant can be absorbed or adsorbed onto the pulverulent dyestuffs by solvent evaporation, chemical reaction and creation of a covalent bond. According to one variant, the surface treatment consists of a coating of the pulverulent dyestuffs. The coating may represent from 1 to 300% by weight of the untreated pulverulent dyestuffs, for example from 5 to 200%, in particular from 10 to 100% by weight, of the weight of untreated pulverulent dyestuffs. The coating may represent from 0.1 to 10% by weight, and in particular from 1 to 5% by weight of the total weight of the coated powdery coloring material.

The coating may be carried out for example by adsorption of a liquid surface agent on the surface of the pulverulent dyestuffs by simple mixing with pulverulent dyestuffs and said surfactant, optionally while hot, prior to the incorporation of the particles into the other ingredients of the makeup or care composition.

The coating can be carried out for example by chemical reaction of a surfactant with the surface of the pulverulent dyestuffs and creation of a covalent bond between the surfactant and the pulverulent dyestuffs. This method is described in particular in US Pat. No. 4,578,266.

The chemical surface treatment may consist of diluting the surfactant in a volatile solvent, dispersing the pulverulent dyestuffs in this mixture, then slowly evaporating the volatile solvent, so that the surfactant settles at the surface of pulverulent dyestuffs.

Fluoride surfactant

The solid particles may be surface-treated totally or partially with a fluorinated compound.

The fluorinated surfactants may be selected from perfluoroalkyl phosphates, perfluoropolyethers, polytetrafluoroethylene (PTFE) and perfluoroalkanes.

Perfluoropolyethers are described in particular in the patent application EP-A-486135 and sold under the trade names Fomblin by the company Montefluis.

Perfluoroalkyl phosphates are in particular described in application JP H05-86984. The perfluoroalkyl phosphate-diethanol amines marketed by Asahi Glass under the reference AsahiGuard AG530 may be used.

The perfluoroalkanes may be linear or cyclic perfluoroalkanes. Among the linear perfluoroalkanes, there may be mentioned the series of linear alkanes, such as perfluorooctane, perfluorononane or perfluorodecane. Among the cyclic perfluoroalkanes, there may be mentioned perfluorocycloalkanes, perfluoro (alkylcycloalkanes), perfluoropolycycloalkanes, aromatic perfluorinated hydrocarbons (perfluoroarenes). Among the perfluoroalkanes, mention may also be made of perfluorinated hydrocarbon compounds containing at least one heteroatom.

Among the perfluorocycloalkanes and perfluoro (alkylcycloalkanes), there may be mentioned perfluorodecalin sold under the name "FLUTEC PP5 GMP" by the company Rhodia, perfluoro (methyldecalin), perfluoro (C3-C5 alkyl-cyclohexanes) such as perfluoro (butylcyclohexane).

Among the perfluoropolycycloalkanes, there may be mentioned derivatives of bicyclo [3.3.1] nonane such as perfluorotrimethylbicyclo [3.3.1] nonane, derivatives of adamantane, such as perfluorodimethyladamantane, and perfluorinated derivatives of hydrogenated phenanthrene, such as tetracosafluoro-tetradecahydrophenanthrene.

Among the perfluoroarenes, there may be mentioned perfluorinated derivatives of naphthalene such as perfluoronaphthalene and peiluoromethyl-1-naphthalene. By way of example of commercial references of pigments treated with a fluorinated compound, mention may be made of:

Yellow iron oxide / perfluoroalkyl phosphate, sold in particular under the reference PF 5 Yellow 601 by the company Daito Kasei,

- Red iron oxide / perfluoroalkyl phosphate, sold in particular under the reference PF 5 Red R 516L by the company Daito Kasei,

Black iron oxide / perfluoroalkyl phosphate, sold in particular under the reference PF 5 Black BL 100 by the company Daito Kasei, titanium dioxide / perfluoroalkyl phosphate, sold in particular under the reference PF 5 TiO 2 CR 50 by the company Daito Kasei,

Yellow iron oxide / perfluoropolymethylisopropylether, sold in particular under the reference Iron oxide yellow BF-25-3 by the company Toshiki,

DC Red 7 / perfluoropolymethylisopropylether, sold in particular under the reference D & C Red 7 FHC by the company Cardre Inc.,

- DC Red 6 / PTFE, sold in particular under the reference T 9506 by the company Warner - Jenkinson,

Fatty Acid or Amino Acid Treatment Agent The hydrophobic treatment agent may be selected from fatty acids, such as stearic acid; metallic soaps, such as aluminum dimyristate, aluminum salt of hydrogenated tallow glutamate; amino acids; N-acyl amino acids or their salts; lecithin, isopropyl trisostearyl titanate (or also called ITT), and mixtures thereof.

The N-acylamino acids may comprise an acyl group having from 8 to 22 carbon atoms, for example a 2-ethylhexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl or cocoyl group. The salts of these compounds may be the aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. The amino acid can be for example lysine, glutamic acid, alanine. The fatty acids are in the present invention in particular hydrocarbon chain acids having 1 to 30 carbon atoms, preferably having 5 to 18 carbon atoms. The hydrocarbon chain can be saturated, monounsaturated or polyunsaturated.

By way of example of pigments coated with fatty acids, mention may be made of those sold under the trade reference NAI-TAO-77891, NAI-C33-8073-10, NAI-C33-8075, NAI-C47-051-10, NAI - C33-115, NAI - C33-134, NAI - C33-8001-10, NAI - C33-7001-10, NAI - C33-9001-10 of the MIYOSHI KASEI Company.

The water-soluble dyes are, for example, beet juice, methylene blue.

Liposoluble, synthetic or natural dyes are, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan Red carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto, curcumin.

The dyestuffs, in particular the pigments treated with a hydrophobic agent, may be present in the composition in a content ranging from 0.1% to 50% by weight, relative to the total weight of the composition, preferably ranging from 5% to 30% by weight, and preferably ranging from 1% to 20% by weight.

The composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, anti-inflammatory agents, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, or mixtures thereof. Of course, a person skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the corresponding composition according to the invention are not, or not substantially, impaired by the envisaged addition.

According to a preferred embodiment, the composition according to the invention is a lipstick.

According to a preferred embodiment, the composition according to the invention is in liquid form at 25 ° C.

According to another embodiment, the composition is in solid form at 25 ° C. In the case of a lipstick, it can act as a lipstick stick or a lipstick poured cup for example. According to another aspect, the invention also relates to a process for the makeup and / or cosmetic care of keratin materials comprising a step of applying a composition according to the invention to said materials.

According to another aspect, the invention also relates to a cosmetic assembly comprising: i) a container delimiting at least one compartment, said container being closed by a closure element; and ii) a composition disposed within said compartment, the composition being in accordance with the invention.

The container can be in any suitable form. It may especially be in the form of a bottle, a tube, a pot, a case, a box, a bag or a case.

The closure element may be in the form of a removable cap, a lid, a lid, a tearable strip, or a capsule, in particular of the type comprising a body fixed to the container and an articulated cap. on the body. It can also be in the form of an element ensuring the selective closure of the container, including a pump, a valve, or a valve. The container may be associated with an applicator, particularly in the form of a brush comprising an arrangement of bristles held by a twisted wire. Such a twisted brush is described in particular in US Pat. No. 4,887,622. It may also be in the form of a comb comprising a plurality of application elements, obtained in particular from molding. Such combs are described for example in patent FR 2 796 529. The applicator may be in the form of a brush, as described for example in patent FR 2 722 380. The applicator may be in the form of a block of foam or elastomer, felt, or spatula. The applicator may be free (puff or sponge) or integral with a rod carried by the closure member, as described for example in US Patent 5,492,426. The applicator may be integral with the container, as described for example the patent FR 2 761 959.

The product can be contained directly in the container, or indirectly. By way of example, the product may be placed on an impregnated support, in particular in the form of a wipe or a tampon, and arranged (individually or in several) in a box or in a bag. Such a support incorporating the product is described for example in the application WO 01/03538.

The closure member may be coupled to the container by screwing. Alternatively, the coupling between the closure element and the container is other than by screwing, in particular via a bayonet mechanism, by snapping, clamping, welding, gluing, or by magnetic attraction. By "latching" is meant in particular any system involving the crossing of a bead or a bead of material by elastic deformation of a portion, in particular of the closure element, then by return to the position not elastically constrained of said portion after crossing the bead or cord.

The container may be at least partly made of thermoplastic material. Examples of thermoplastic materials include polypropylene or polyethylene. Alternatively, the container is made of non-thermoplastic material, in particular glass or metal (or alloy).

The container may have rigid walls or deformable walls, in particular in the form of a tube or a tube flask. The container may include means for causing or facilitating the dispensing of the composition. By way of example, the container may have deformable walls so as to cause the composition to exit in response to an overpressure inside the container, which excess pressure 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 stick, the latter can be driven by a piston mechanism. Still in the case of a stick, in particular makeup product (lipstick, foundation, etc.), the container may comprise a mechanism, including rack, or with a threaded rod, or with a helical ramp, and able to move a stick towards said opening. Such a mechanism is described, for example, in patent FR 2 806 273 or in patent FR 2 775 566. Such a mechanism for a liquid product is described in patent FR 2 727 609.

The container may consist of a housing with a bottom defining at least one housing containing the composition, and a cover, in particular articulated on the bottom, and adapted to cover at least part of said bottom. Such a housing is described for example in the application WO 03/018423 or in the patent FR 2 791 042.

The container may be equipped with a wiper arranged in the vicinity of the opening of the container. Such a wiper makes it possible to wipe the applicator and possibly the rod which it can be secured. Such a wiper is described, for example, in patent FR 2 792 618.

The composition may be at atmospheric pressure inside the container (at room temperature) or pressurized, in particular by means of a propellant (aerosol). In the latter case, the container is equipped with a valve (of the type used for aerosols). The present invention also relates to a process for making up the lips, comprising applying to said lips a composition according to the invention.

Outfit measurement protocol:

The resistance index of the deposit obtained with the composition according to the invention is determined according to the measurement protocol described below.

A support (rectangle 40 mm X 70 mm) made of acrylic coating is prepared

(Hypoallergenic acrylic adhesive on polyethylene film sold under the name BLENDERME ref FH5000-55113 by the company 3M Health) stuck on a layer of adhesive polyethylene foam on the opposite side to that on which is fixed the adhesive plaster (layer of foam sold under the denomination RE40X70EP3 of the company JOINT TECHNIQUE

LYONNAIS IND).

The color L ^* 0a ^* 0b ^* 0 of the support is measured using a MINOLTA CR 300 colorimeter, on the acrylic coating side. The support thus prepared is preheated on a heating plate maintained at a temperature of 40 ^° C. so that the surface of the support is maintained at a temperature of 33 ° C. ± 1 ^° C.

While leaving the support on the hot plate, the composition is applied to the entire non-adhesive surface of the support (i.e., on the surface of the acrylic coating) by spreading it with a brush to obtain a deposit of the composition of about 15 microns and then allowed to dry for 10 minutes.

After drying, the color L ^* a ^* b ^* of the film thus obtained is measured.

The color difference ΔE1 is then determined between the color of the film with respect to the color of the bare substrate by the following relation.

The support is then adhered by its adhesive side (adhesive side of the foam layer) on an anvil with a diameter of 20 mm and provided with a screw thread. A test piece of the support / deposit assembly is then cut using a punch with a diameter of 18 mm. The anvil is then screwed onto a press (MANUAL STATIF IMADA SV-2 from SOMECO) equipped with a dynamometer (IMADA DPS-20 from SOMECO). On a 80 g / m2 white photocopy paper, draw a strip 33 mm wide and 29.7 cm long, draw a first line 2 cm from the edge of the sheet, then a second line at 5 cm the edge of the sheet, the first and second lines thus delimiting a box on the strip; then we have a first mark and a second mark located in the band at 8 cm and 16 cm markings respectively. 20 μl of water are placed on the first mark and on the second mark 10 μl of refined sunflower oil (sold by the company LESIEUR). The white paper is placed on the base of the press and the specimen placed on the square of the paper strip is pressed at a pressure of approximately 300 g / cm 2 exerted for 30 seconds. Then the press is raised and the test piece is placed again just after the second line (hence beside the box), a pressure of approximately 300 g / cm 2 is again made and is moved rectilinearly on contact. made the paper with a speed of 1 cm / s, over the entire length of the strip so that the specimen passes through the water and oil deposits.

After removal of the specimen, a portion of the deposit was transferred to the paper. We then measure the color L ^* ', a ^* ', b of the deposit remained on the specimen.

The color difference ΔE2 is then determined between the color of the deposit remaining on the specimen with respect to the color of the bare support by the following relation.

The strength index of the composition, expressed in percentage, is equal to the ratio: 100 X ΔE2 / ΔE1

The measurement is carried out on 6 supports in succession and the resistance value corresponds to the average of the 6 measurements obtained with the 6 supports.

In the application, the contents, unless expressly stated otherwise, are expressed by weight relative to the total weight of the composition. The following examples are intended to illustrate the compositions and methods of this invention, but are in no way limiting the scope of the invention. All parts and percentages in the examples are by weight and all measurements were obtained at about 23 ⁰ C, unless otherwise indicated. EXAMPLE NO. 1: Obtaining the Mixture of MQ and Propyl Resins According to the Invention Materials

Resin MQ = an MQ resin of formula M _o , ₄ 3Qo, 57 and M _n = 3230 dissolved in xylene at 70.8% by weight solids. The MQ resin was manufactured according to the techniques described by Daudt in US Patent 2,676,182.

Propyl T-resin = a propyl resin silsesquioxane at 74.8% by weight in toluene. Silsesquioxane propyl resin was obtained by hydrolysis of propyl trichlorosilane.

Different solutions of MQ resin and propyl T resin are mixed in a tricolor equipped with a stirrer. Aliquots of each mixture are placed in an aluminum cup 2 inches in diameter, and heated under vacuum at a temperature of 110 ^° C. for one hour, followed by 1 h 25 at 140 ^° C. Visual qualitative observations on the clarity and the hardness of the mixtures obtained are made (see Table 1 below):

Table 1

The results obtained show the unexpected miscibility of the propylene MQ and T resins, based on the clarity of the solvent-free mixture and the increasing hardness as the amount of MQ resin increases.

According to an alternative named 1-g, the mixture described in Example 22 of application WO2005 / 075567 is used in which the weight ratio between the MQ resin and the propyl T resin is 85/15.

According to an alternative named 1-h, using the resin mixture described in Example 13 of the application WO2007 / 145765 in which the weight ratio between the MQ resin and the propyl T resin is 60/40.

Example 2: Liquid Lipstick

The following liquid lipstick formulas have been prepared.

Procedure: a. The fillers and pigments possibly present are milled in part of the oily phase. b. The remainder of the fat-soluble ingredients are then mixed at a temperature of the order of 100 ^° C. The ground material is then added to the oily phase. vs. The RAYNERI mixture is stirred for 45 minutes and the siloxane resin is added at room temperature. d. The formula is poured into isododecane-tight water bottles. Comparative composition 3 contains substantially the same dry matter content of the film-forming polymer as the compositions according to the invention 1 and 2 (siloxane resin + vinyl polymer with a carbosiloxane dendrimer-derived unit).

For the composition 1 according to the invention containing a vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer and a MQ-propyl siloxane resin, a holding value of 27.28 ± 3.17 is measured.

For the composition 2 according to the invention containing a vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer and a MQ-propyl siloxane resin, a holding value of 24.75 ± 2.24 is measured.

For the comparative composition 3 containing no siloxane resin, a resistance value of 18.32 ± 0.56 is measured.

A better resistance is thus obtained with the compositions according to the invention.

EXAMPLE 3 Preparation of a Poly (Isobornyl Acrylate / Isobornyl Methacrylate / Isobutyl Acrylate / Acrylic Acid) Polymer

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

Then added to 90 ⁰ C and 1 hour, 105 g of isobornyl methacrylate (manufactured by

Arkema), 105 g of isobornyl acrylate (manufactured by Arkema) and 1, 8 g of 2.5- Bis (2- ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox ^® 141, Akzo Nobel).

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

75 g of isobutyl acrylate (manufactured by Fluka), 15 g of acrylic acid and 1.2 g of 2.5-bis (2-ethylhexanoylperoxy) are then introduced into the above mixture, still at 90 ^° C. and over 30 minutes. ) -2,5-dimethyl hexane.

The mixture is maintained for 3 hours at 90 ^° C. and then the mixture is cooled.

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

A polymer is obtained comprising a first poly (isobornyl acrylate / isobornyl methacrylate) rigid block having a Tg of 110 ^° C., a second poly (isobutyl acrylate / acrylic acid) flexible sequence having a Tg of -9 ° C. C and an intermediate block which is a random isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate / acrylic acid polymer.

Example # 4: Liquid Lipid Reds

The following compositions 3 and 4 are prepared

Operating mode:

The fillers and pigments possibly present are milled in part of the oily phase.

The remainder of the fat-soluble ingredients are then mixed at a temperature of the order of 100 ^° C. The ground material is then added to the oily phase.

The RAYNERI mixture is stirred for 45 minutes and the siloxane resin is added at room temperature. h. The formula is poured into isododecane-tight water bottles.

The composition 3 according to the invention contains 15% of polymer (weight in the dry extract) prepared according to Example 2 and 3.5% (weight in dry extract) of siloxane resin prepared according to Example 1-C), that is to say a total of 18.5% of film-forming polymer. Comparative composition 4 contains 18.5% of polymer (weight in dry extract) prepared according to Example 2.

The comparative composition 4 is very viscous and sticky and is very thick during application. It is uncomfortable on the lips because the formed film is very thick and sticky.

The composition 3 according to the invention is much more pleasant (slippery) to the application and it forms a deposit much finer and comfortable.

The preceding example is reproduced by replacing in the composition the resin MQ: T 60: 40 weight for weight with the resin MQ: T as prepared in Example 1-f (which corresponds to a resin MQ: T (51: 49)) also solubilized in 60% of isododecane. A result similar to that obtained with the resin MQ: T (60:40) is obtained.

Claims

claims

1. - Composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units: in which

• a and b have values strictly greater than 0; • and the ratio a / b is between 0.5 and 1, 5, b) a propyl silsesquioxane resin comprising at least 80 mole% of units (R "SiC> _3/2) wherein R" independently represents a alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 80 mol% of the R "groups are propyl groups, the weight ratio of the ) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, the resins a) and b) not being bonded to one another by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one film-forming polymer chosen from the group comprising: a block ethylenic copolymer (also called ethylene-sequence polymer), containing at least a first sequence having a glass transition temperature (Tg) greater than or equal to at 40 ^° C. and being derived in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least one second block having a glass transition temperature less than or equal to 20 ⁰ C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a lower glass transition temperature or equal to 20 ° C, said first sequence and said second sequence being interconnected by a random intermediate segment comprising at least one of said first monomers constituting the first sequence and at least one of said second constituent monomers of the second sequence, and said block copolymer having a polydispersity index I greater than 2, - a vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer, a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase.

2. - Composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units: in which R 'independently represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 95 mol% of the R' groups are alkyl groups,

• a and b have values strictly greater than 0;

And the ratio a / b is between 0.5 and 1.5, and b) a film-forming propyl silsesquioxane resin comprising at least 80 mol% of units (R "SiO _3/2 ) in which R" represents independently an alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol% of the R "groups are propyl groups, the weight ratio of the resins a) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, the resins a) and b) not being bonded to one another by covalent bonds and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one film-forming polymer chosen from the group comprising: an ethylenic block copolymer, containing at least a first sequence having a glass transition temperature (Tg) of greater than or equal to 40 ^° C. and resulting entirely or in part of one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least one second sequence having a lower glass transition temperature or equal to 20 ⁰ C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ^° C., said first sequence and said second sequence being connected to each other by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second constituent monomers of the second block, and said block copolymer having a higher polydispersity index I e 2, a vinyl polymer comprising at least one unit derived from dendr carbosiloxane, - a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase.

3. - Composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units: in which

• a and b have values strictly greater than 0; • and the ratio a / b is between 0.5 and 1, 5, and b) a propyl silsesquioxane resin comprising at least 80 mole% of units (R "SiO _3/2) wherein R" independently represents a alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol% of the R "groups are propyl groups, the weight ratio of the ) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, the resins a) and b) not being bonded to one another by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one film-forming polymer chosen from the group comprising: a block ethylene copolymer, containing at least a first block having a glass transition temperature (Tg) greater than or equal to 40 ^° C. and originating wholly or in part of one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least one second sequence having a glass transition temperature of less than or equal to 40 ^° C. 20 ⁰ C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature of less than or equal to 20 ° C, said first sequence and said second sequence being interconnected by a random intermediate segment comprising at least one of said first monomers constituting the first block and at least one of said second monomers constituting the second block, and said block copolymer having a polydispersity index I greater than 2, a vinyl polymer comprising at least one unit derived from carbosyl dendrimer loxane, a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase.

the siloxane and propyl silsesquioxane resins being formulated in the composition via a mixture obtainable by the following process: • Mixing a solution of siloxane resin with a solution of propyl silsesquioxane resin, and then • Heating, under the conditions following specific conditions: heating homogeneously for at least 1 hour, preferably between 1 hour and 5 hours, at a single temperature or at temperature ranges between 90 ° C and 250 ° C; provided that this heating is done without the presence of a chemical condensation catalyst between the two resins.

4. - Composition according to claim 3, characterized in that the mixture of resins a) and b) is obtainable by the method comprising, after or even during the mixing step, an additional step of partial distillation or total aromatic solvents, replacing them with a cosmetically acceptable volatile solvent.

5. - Composition comprising, in a physiologically acceptable medium: a) a siloxane resin comprising at least 80 mol% of units: in which

• a and b have values strictly greater than 0; • and the ratio a / b is between 0.5 and 1, 5, and b) a propyl silsesquioxane resin comprising at least 80 mole% of units (R "SiO _{_3/2)} wherein R" independently represents a alkyl group having 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group, with the proviso that at least 40 mol% of the R "groups are propyl groups, the weight ratio of the ) and b) being between 1/99 and 99/1, in particular between 85/15 and 15/85, the resins a) and b) not being bonded to one another by covalent bonds, and the number of units M of the final mixture being strictly less than the number of units (T + Q), and c) at least one film-forming polymer chosen from the group comprising: a block ethylenic copolymer (also called ethylene-sequence polymer), containing at least a first sequence having a higher glass transition temperature (Tg) or equal to 40 ^° C. and resulting in whole or in part from one or more first monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature greater than or equal to 40 ^° C., and at least a second block having a glass transition temperature less than or equal to 20 ° C and being derived in whole or in part from one or more second monomers, which are such that the homopolymer prepared from these monomers has a glass transition temperature less than or equal to 20 ⁰ C, said first sequence and said second sequence being interconnected by a random intermediate segment comprising at least one of said first monomers constituting the first sequence and at least one of said second constituent monomers of the second sequence, and said block copolymer having a polydispersity index I greater than 2, a vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer, a dispersion of particles of homopolymer or radical copolymer, acrylic or vinyl dispersed in said liquid fatty phase.

the siloxane and propyl silsesquioxane resins being formulated in the composition via a mixture obtainable according to the following process:

• Mixing a solution of siloxane resin with a solution of propyl silsesquioxane resin, then

Heating, under the following specific conditions: heating homogeneously in an extruder for at least 10 minutes, preferably between 10 minutes and 2 hours, at a single temperature or at a temperature range between 90 ° C and 250 ° C; provided that this heating is done without the presence of a chemical condensation catalyst between the two resins.

6. - Composition according to claim 5, characterized in that the mixture of resins a) and b) is obtainable according to the process comprising, after or even during the mixing step, an additional step of partial distillation or total of the aromatic solvents, leaving the mixture directly in the solid state.

7. - Composition according to one of claims 1 to 6 characterized in that the resin a) comprises residual silanols-SiOH groups, in an amount of between 2 and 10% by weight of the resin MQ, preferably between 2 and 5% by weight of the resin MQ.

8. - Composition according to one of claims 1 to 7 characterized in that the resin b) comprises residual silanol groups -SiOH in an amount of between 2 and 10% by weight of the resin b), and / or alkoxy groups. amount less than or equal to 20% by weight of the resin b).

9. - Composition according to one of claims 1 to 8 characterized in that the radical R of the resin a) independently represents: - an alkyl group having 1 to 8 atoms selected from methyl, ethyl, propyl, butyl, pentyl groups hexyl and octyl;

an aryl group chosen from phenyl, naphthyl, benzyl, tolyl, xylyl, xenyl, methylphenyl, 2-phenylethyl, 2-phenyl-2-methylethyl, chlorophenyl, bromophenyl and fluorophenyl groups; a carbinol group chosen from groups of formula R ¹ OH in which R ¹ represents a divalent hydrocarbon radical containing at least 3 carbon atoms or a divalent hydrocarbonoxy radical containing at least 3 carbon atoms, and the groups of formula R OH in which R ² represents an arylene radical - (CH ₂ ) χC ₆ H ₄ -, x having a value of between 0 and 10, -CH ₂ CH (CH ₃ ) (CH ₂ ) _X C ₆ H ₄ -, x having a value between 0 and 10,

- (CH ₂ ) _x C ₆ H ₄ (CH ₂ ) χ-, x having a value of between 1 and 10;

an amino group chosen from the groups of formula -R ³ NH ₂ or -R ³ NHR ⁴ NH ₂ , R ³ representing a divalent hydrocarbon radical having at least 2 carbon atoms and R ⁴ representing a divalent hydrocarbon radical having at least 2 carbon atoms.

10. - Composition according to claim 9, characterized in that the group R ¹ is chosen from:

the alkylene radicals - (CH ₂ ) _X -, the value of x being between 3 and 10, -CH ₂ CH (CH ₃ ) -, -CH ₂ CH (CH ₃ ) CH ₂ -,

-CH ₂ CH ₂ CH (CH ₂ CH ₃ ) CH ₂ CH ₂ CH ₂ - and

-OCH (CH ₃ ) (CH ₂ ) _X -, the value of x being between 1 and 10.

1 1. - Composition according to claim 9 or 10, characterized in that the groups R ³ and R ⁴ are chosen from ethylene, propylene, -CH ₂ CHCH ₃ -, butylene, -CH ₂ CH (CH ₃ ) CH groups. ₂ -, pentamethylene, hexamethylene, 3-ethyl hexamethylene, octamethylene and decamethylene.

12. - Composition according to one of claims 9 to 11, characterized in that the amino groups are chosen from:

-CH ₂ CH ₂ CH ₂ NH ₂ , -CH ₂ (CH ₃ ) CHCH ₂ (H) NCH ₃ , -CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ NHCH ₃ ,

- (CH ₂ CH ₂ NH) ₃ H and -CH ₂ CH ₂ NHCH ₂ CH ₂ NHC ₄ H ₉ .

13. - Composition according to one of claims 1 to 9, characterized in that the radical R 'is a methyl group.

14. - Composition according to one of the preceding claims, characterized in that the resin b) is such that at least 90 mol% of the groups R "are propyl groups.

15. - Composition according to one of the preceding claims, characterized in that ethylene polymer film-forming sequence comprises an intermediate sequence comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block and in that has a polydispersity index greater than 2, and in that the second block is obtained from acrylic acid and isobutyl acrylate and in that the first block is obtained from isobornyl acrylate and isobornyl methacrylate.

16. - Composition according to one of claims 1 to 14, characterized in that said vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer the vinyl polymer having at least one carbosiloxane dendritic structure is selected from polymers such as the dendritic structure is represented by formula (I):

in which Z is a divalent organic group, "p" is 0 or 1, R ¹ is an aryl or alkyl group of 1 to 10 carbon atoms and X 'is a silylalkyl group represented by the formula (II):

in which R ¹ is the same as above, R ² is an alkylene group of 1 to 10 carbon atoms, R ³ is an alkyl group of 1 to 10 carbon atoms, and X ^{1 + 1} is a group selected from the group comprising hydrogen atoms, aryl groups and alkyl groups having up to 10 carbon atoms, and silylalkyl groups X 'where the exponent "i" is an integer of 1 to 10 indicating the generation of the grouping silylalkyl starting in each carbosiloxane dendritic structure with a value of 1 for the group X 'in formula (I) and the index "a'" is an integer of θ to 3.

17. -Composition according to one of claims 1 to 14, characterized in that said dispersion of homopolymer or copolymer particles is such that the particles of the dispersion polymer are chosen from acrylic polymers or copolymers, and in that they are insoluble in water-soluble alcohols.

18. Composition according to one of the preceding claims, characterized in that the film-forming polymer is present in a content of 0.1 to 60% by weight of dry matter of film-forming polymer, preferably 0.5 to 50% by weight. and more preferably from 1 to 40% by weight.

19. - Composition according to one of the preceding claims, characterized in that it further comprises at least one additional ingredient selected preferably from pasty compounds of non-animal origin, rheological thickening agents or gelling agents of fatty phase with except for dimethicone crosspolymers, waxes with the exception of candelilla wax, ozokerite and silicone waxes, hydrophilic gelling agents, fillers, ionic surfactants with the exception of lauryl ether sulfate, fibers, and their mixtures.

20. - Process for the makeup and / or cosmetic care of keratin materials, in particular the lips, comprising a step of applying a composition according to one of the preceding claims to said materials.