WO2018122014A1

WO2018122014A1 - Superhydrophobic cosmetic composition in aerosol form

Info

Publication number: WO2018122014A1
Application number: PCT/EP2017/083177
Authority: WO
Inventors: Laura JAYAWARDENE; Anaïs GAUTHIER; Nathalie Jager-Lezer; Laure DAUBERSIES; Vincent THIRIOUX
Original assignee: L'oreal
Priority date: 2016-12-29
Filing date: 2017-12-15
Publication date: 2018-07-05
Also published as: FR3061428A1

Abstract

The present invention relates to a cosmetic composition in aerosol form comprising, in a physiologically acceptable medium: (a) at least superhydrophobic particles; (b) at least one volatile solvent; (c) at least one propellant. The present invention also relates to a cosmetic composition intended to prepare said cosmetic composition, aerosol devices comprising said compositions, a cosmetic process for making up and/or caring for keratin materials and also the use, in a cosmetic composition in aerosol form, of at least superhydrophobic particles and of at least one film-forming polymer in order to obtain a dry film with good stability and/or which is water-resistant and/or sweat-resistant and/or resistant to friction.

Description

"Superhydrophobic cosmetic composition in aerosol form"

The present invention mainly relates to a cosmetic composition in aerosol form for forming on the surface of a keratinous material a hydrophobic deposit including resistance to water, perspiration and friction.

In general, it is necessary to guarantee the various types of cosmetic deposits on the surface of a keratinous material a certain resistance to friction whatever they are (skin against skin and / or fabrics such as clothing against skin) as well as some resistance to water, perspiration.

Thus, it is important that a foundation applied to the skin of the face has sufficient resistance to sweat, tear fluid or any friction. It is the same for a lipstick confronted with the regular contact of saliva, or even a liquid or an object such as a glass, a tissue, a cloth napkin, etc.

This requirement is also required in the field of cosmetic care, particularly with regard to sun products which must be resistant on the one hand to sweat and water, in particular salt water and on the other hand to all type of friction so as not to affect the effectiveness of the sun protection factor.

Finally, in the field of antiperspirant / deodorant products, the perception of "dry" on the skin, especially at the axillary level, and the resistance to friction are, for obvious reasons, particularly required.

It should be noted that the concern to enhance the hydrophobicity of certain substrates with respect to water has also been encountered in other technical fields. Thus, in the field of materials dedicated to construction for example, it has already been proposed to apply to the surface of these materials, a coating capable of forming therein a deposit in relief that is to say consisting of a succession of elevations and depressions thereby significantly reducing the contact area between water and its surface and thus to ensure better impermeability to the substrate.

In fact, this solution aims to artificially reproduce a naturally occurring surface architecture, especially in plants and in particular on the lotus leaf. Indeed, this sheet is composed on the surface of hydrophobic fatty materials, which are organized in a random succession of elevations and depressions. The contact of the water droplets is generally limited to the surface of the peaks of the elevations.

The reproduction of such a relief effect, still described as a lotus effect, has in particular already been considered in US 6,660,363, for the development of self-cleaning coatings with improved hydrophobicity.

In the cosmetic field, formulations have already been developed, reproducing such a phenomenon durably, as described in US 5,500,216 and WO2009 / 082565.

However, currently available products are not completely satisfactory.

The object of the present invention is therefore precisely to propose new cosmetic formulations which make it possible to give improved satisfaction in these terms.

Surprisingly, the inventors have discovered that the implementation of specific combinations of superhydrophobic particles as described below, with at least one volatile solvent and optionally at least one film-forming polymer in cosmetic compositions in the form of an aerosol to give the deposits of these compositions on the surface of keratin materials a significant "lotus effect" and also advantageous properties in terms of cosmetics, namely good adhesion, good resistance to water, perspiration and friction, perception a "dry" deposit on keratin materials with very fine droplets of water that slide to the surface. The size of the halos on the clothes decreases considerably especially during intense physical efforts.

For the purposes of the present invention, the term "keratin materials" is understood to mean the skin of the face and / or of the body and / or the contour of the eyes, the lips, the armpits (also called axillary cavities).

The present invention describes a cosmetic composition in aerosol form (also called final composition in the present invention) comprising in a physiologically acceptable medium:

(a) at least superhydrophobic particles;

(b) at least one film-forming polymer;

(c) at least one volatile solvent; (d) at least one propellant.

The present invention also discloses a cosmetic composition (also referred to as a liquid phase or juice in the present invention) for preparing a cosmetic composition (also referred to as the final composition in the present invention) as defined in the present invention, comprising in a physiological environment acceptable:

(a) at least superhydrophobic particles;

(b) at least one film-forming polymer; and

(c) at least one volatile solvent chosen from:

volatile hydrocarbon oils such as those chosen from:

hydrocarbon-based oils containing from 8 to 16 carbon atoms, especially Cs-C16 isoalkanes of petroleum origin (also called isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and isohexadecane, and branched C 8 -C 18 esters such as isohexyl or isodecyl neopentanoate,

- petroleum distillates,

volatile linear alkanes, in particular C8-C16 linear alkanes, such as an undecane / tridecane mixture;

C2-4 monoalcohols such as ethanol, isopropanol and propanol;

volatile linear silicone oils, in particular those having a viscosity less than or equal to 8 centistokes (8 × 10 ^-6 m ² / s), and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, such as heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane sold especially under the name DC®-200 Fluid 1 by Dow Corning, decamethyltetrasiloxane sold especially under the name DC --200 Fluid 1.5 by Dow Corning, dodecamethyl pentasiloxane, hexamethyl disiloxane, hexamethyl siloxane;

volatile alkyltrisiloxane linear oils of general formula (Ia):

wherein R represents an alkyl group having 2 to 4 carbon atoms and one or more hydrogen atoms of which may be substituted by a fluorine or chlorine atom; and

- their mixtures,

characterized in that the composition (liquid phase or juice) comprises a volatile solvent content of between 55% and 95% by weight, preferably between 60% and 93% by weight, more preferably between 70% and 91% by weight. weight, and more preferably between 80 and 90%> by weight relative to the total weight of the liquid phase, that is to say when the propellants are not considered.

Thus, according to a first aspect, the present invention relates to a cosmetic composition in aerosol form (also called final composition in the present invention) comprising in a physiologically acceptable medium:

(a) at least one of the superhydrophobic particles selected from:

superhydrophobic silica airgel particles having a specific surface per unit mass (SM) ranging from 500 to 1500 m ² / g;

superhydrophobic acrylic acid copolymer powders; and

- their mixtures;

(b) at least one volatile solvent;

(c) at least one propellant.

In a preferred embodiment, a cosmetic composition (final composition) in aerosol form according to the invention further comprises at least one film-forming polymer as defined in the present invention.

According to another of its aspects, the present invention relates to a cosmetic composition (also called liquid phase or juice in the present invention) for preparing a cosmetic composition (also named final composition in the present invention) as defined herein. invention, comprising in a physiologically acceptable medium: (a) at least one of the superhydrophobic particles selected from:

superhydrophobic silica airgel particles having a surface per unit mass (SM) ranging from 500 to 1500 m ² / g;

superhydrophobic acrylic acid copolymer powders; and

- their mixtures; and

(b) at least one volatile solvent chosen from:

volatile hydrocarbon oils such as those chosen from:

hydrocarbon-based oils containing from 8 to 16 carbon atoms, especially C 6 -C 16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and isohexadecane, and branched C 8 -C 18 esters such as isohexyl or isodecyl neopentanoate,

- petroleum distillates,

C2-4 monoalcohols such as ethanol, isopropanol and propanol;

volatile alkyltrisiloxane linear oils of general formula (Ia):

(the) wherein R represents an alkyl group having 2 to 4 carbon atoms and one or more hydrogen atoms of which may be substituted by a fluorine or chlorine atom; and

- their mixtures,

In a preferred embodiment, a cosmetic composition (liquid phase or juice) intended to prepare a cosmetic composition (final composition) as defined in the present invention further comprises at least one film-forming polymer as defined in the present invention.

By "final composition" is meant the combination of the liquid phase and the propellant (s).

In the present invention, the agent (s) propellant (s) can be indifferently called propellant.

For the purposes of the present invention, the term "liquid phase" or "juice" means the base of the composition without the agent or the propellants (s).

In a final composition according to the invention, the weight ratio between the liquid phase and the propellant gas varies in a ratio of 5/95 to 50/50, preferably 10/90 to 40/60, more preferably 15/85. at 30/70 or better is 15/85 or 20/80.

According to another of its aspects, the present invention relates to an aerosol device constituted by:

(A) a container comprising a composition (final composition) according to the invention; and

(B) at least one means for dispensing said composition.

(A) a container comprising a composition (liquid phase or juice) as defined according to the invention; (B) at least one propellant and at least one means for dispensing said composition.

According to another of its aspects, the present invention relates to a cosmetic process for making up and / or caring for keratinous substances, in particular the skin of the face and / or of the body, characterized in that materials are applied to the surface. keratin, in particular the skin of the face and / or the body, a composition (final composition) as defined in the present invention or a composition (liquid phase or juice) as defined in the present invention carried by at least one propellant .

According to another of its aspects, the present invention relates to the use in an aerosol cosmetic composition of at least superhydrophobic particles as defined in the present invention and of at least one film-forming polymer as defined in the present invention to obtain a dry film, of good behavior and / or resistant to water and / or resistant to perspiration and / or resistant to friction.

In addition, the present invention describes the use in an aerosol cosmetic composition of at least superhydrophobic particles as defined in the present invention to provide a dry effect, good performance and / or resistance to water and / or resistance to perspiration and / or resistance to friction after application of this composition to the surface of keratin materials.

The superhydrophobic particles as defined in the present invention can thus be used in a cosmetic composition in aerosol form according to the invention for anti-deodorant and / or antiperspirant purposes.

LOTUS EFFECT

The lotus effect is the name given to a physical phenomenon of interactions between water droplets and a hydrophobic surface studied especially by Barthlott and Neinhuis in the 1970s and described in particular in US 6,660,363.

It is known that a drop of water deposited on a hydrophobic smooth surface forms a contact angle slightly greater than 90 °. However, it has been observed that this angle increases strongly in the presence of microaspérités, up to 180 °. Such an increase caused by this so-called "superhydrophobic" state is characteristic of the lotus effect. It should be noted that the lotus effect is not observable for all the hydrophobic charges (particles) but it is only for charges qualified as superhydrophobic. SUPERHYDROPHOBIC PARTICLES

A composition according to the invention comprises, in addition to a physiologically acceptable medium, at least superhydrophobic particles which can be chosen from:

superhydrophobic silica airgel particles;

superhydrophobic acrylic acid copolymer powders; and

- their mixtures,

preferably from superhydrophobic silica airgel particles and superhydrophobic acrylic acid copolymer powders, and even more preferably from superhydrophobic silica airgel particles.

More particularly, a composition according to the invention comprises, in addition to a physiologically acceptable medium, at least superhydrophobic particles chosen from:

superhydrophobic silica airgel particles having a specific surface per unit mass (SM) ranging from 500 to 1500 m ² / g; superhydrophobic acrylic acid copolymer powders; and

- their mixtures.

SUPERHYDROPHOBIC SILICA AEROGELS

Silica aerogels are porous materials obtained by replacing (by drying) the liquid component of a silica gel with air.

They are generally synthesized by sol-gel process in a liquid medium and then usually dried by extraction of a supercritical fluid, the most commonly used being the supercritical CO ₂ . This type of drying avoids the contraction of the pores and the material. The sol-gel process and the various dryings are described in detail in Brinker CJ, and Scherer GW, Sol-Gel Science: New York: Academy Press, 1990.

The superhydrophobic silica airgel particles used in the present invention have a surface area per unit mass (SM) of from 500 to 1500 m ² / g, preferably from 600 to 1200 m ² / g and better still from 600 to 800 m ² / g, and a size expressed in volume mean diameter (D [0.5]) ranging from 1 to 1500 μιη , better from 1 to 1000 μιη, preferably from 1 to 100 μιη, in particular from 1 to 30 μιη, more preferably from 5 to 25 μιη, better still from 5 to 20 μιη and better still from 5 to 15 μιη.

According to one embodiment, the superhydrophobic silica airgel particles used in the present invention have a size expressed in volume mean diameter (D [0.5]) ranging from 1 to 30 μιη, preferably from 5 to 25 μιη. better from 5 to 20 μιη and even better from 5 to 15 μιη.

The specific surface area per unit mass can be determined by the nitrogen absorption method called the BET method (BRUNAUER - EMMET - TELLER) described in "The Journal of the American Chemical Society", vol. 60, page 309, February 1938 and corresponding to the international standard ISO 5794/1 (Appendix D). The BET surface area corresponds to the total specific surface area of the particles under consideration.

The silica airgel particle sizes can be measured by static light scattering using a MasterSizer 2000 commercial particle size analyzer from Malvern. The data is processed on the basis of Mie scattering theory. This theory, which is accurate for isotropic particles, makes it possible to determine, in the case of non-spherical particles, an "effective" diameter of particles. This theory is particularly described in the work of Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

According to an advantageous embodiment, the superhydrophobic silica aerogel particles used in the present invention have a specific surface per unit mass (SM) ranging from 600 to 800 m ² / g and a size expressed as the mean diameter by volume ( D [0.5]) ranging from 5 to 20 μιη and even better from 5 to 15 μιη.

The silica airgel particles used in the present invention may advantageously have a packed density p ranging from 0.04 g / cm ³ to 0.10 g / cm ³ , preferably from 0.05 g / cm ³ to 0.08 g / cm ³ .

In the context of the present invention, this density can be evaluated according to the following protocol, referred to as packed density:

40 g of powder are poured into a graduated cylinder; then the specimen is placed on the STAV 2003 device from STAMPF VOLUMETER; the specimen is then subjected to a series of 2500 settlements (this operation is repeated until the difference in volume between 2 consecutive tests is less than 2%); then the final volume Vf of compacted powder is measured directly on the test piece. The packed density is determined by the ratio m / V f, in this case 40 / V f (Vf being expressed in cm ³ and m in g) -

According to one embodiment, the superhydrophobic silica airgel particles used in the present invention have a specific surface area per unit volume (Sv) ranging from 5 to 60 m ² / cm ³ , preferably from 10 to 50 m ² / cm ³ and better from 15 to 40 m ² / cm ³ .

The specific surface per unit volume is given by the relation: Sv = SM X p where p is the packed density expressed in g / cm ³ and SM is the specific surface per unit mass expressed in m ² / g, as defined upper.

Preferably, the superhydrophobic silica aerogel particles according to the invention have an oil absorption capacity measured with WET POINT ranging from 5 to 18 ml / g, preferably from 6 to 15 ml / g and better still from 8 to 18 ml / g. at 12 ml / g.

The absorption capacity measured at WET POINT, and denoted Wp, corresponds to the amount of oil that must be added to 100 g of particles to obtain a homogeneous paste.

It is measured according to the so-called WET POINT method or powder oil uptake determination method described in standard NF T 30-022. It corresponds to the quantity of oil adsorbed on the available surface of the powder and / or absorbed by the powder by measuring the WET POINT, described below:

An amount m = 2 g of powder is placed on a glass plate and then the oil (isononyl isononanoate) is added dropwise. After addition of 4 to 5 drops of oil in the powder, mixing is carried out with a spatula and oil is added until the formation of oil and powder conglomerates. From this moment, the oil is added one drop at a time and then triturated with the spatula. The addition of oil is stopped when a firm and smooth paste is obtained. This paste should be spread on the glass plate without cracks or lumps. The volume Vs (expressed in ml) of oil used is then noted.

The oil intake corresponds to the ratio Vs / m.

The aerogels used according to the present invention are superhydrophobic silica aerogels, preferably silylated silica (INCI name: silica silylate). By superhydrophobic silica is meant any silica whose surface is treated with silylating agents, for example by halogenated silanes such as alkylchlorosilanes, siloxanes, in particular dimethylsiloxanes such as hexamethyldisiloxane, or silazanes, so as to functionalizing the OH groups with Si-Rn silyl groups, for example trimethylsilyl groups.

With respect to the preparation of superhydrophobic silica airgel particles surface-modified by silylation, reference can be made to US Pat. No. 7,470,725.

In particular, silylated silica airgel particles will be used, in particular superhydrophobic silica airgel particles surface-modified with trimethylsilyl groups (trimethylsiloxylated silica).

Examples of superhydrophobic silica aerogels that can be used in the invention include, for example, the airgel marketed under the name VM-2260 (INCI name Silica silylate), by Dow Corning, whose particles have an average size. of about 1000 microns and a specific surface area per unit mass of 600 to 800 m ² / g.

The aerogels marketed by Cabot under the references AEROGEL TLD 201, AEROGEL OGD 201, AEROGEL TLD 203, ENOVA® AEROGEL MT 1100 and ENOVA AEROGEL MT 1200 may also be mentioned.

Mention may also be made of aerogels marketed by JIOS Aerogel Limited under the names JIOS AEROVA® AEROGEL POWDER 5 MICRONS (INCI name: silica (and) water), JIOS AEROVA® AEROGEL POWDER 20 MICRONS (INCI name: silica (and) water ).

The airgel marketed under the name VM-2270 (INCI name: Silica silylate), by the company Dow Corning, whose particles have an average size ranging from 5 to 15 microns and a specific surface per unit mass ranging from from 600 to 800 m ² / g.

The superhydrophobic silica airgel particles that are suitable for the invention make it possible to obtain a superhydrophobic deposition which is moreover advantageously non-whitening because of the small aggregation of the particles with each other, as is confirmed in particular by Scanning Electron Microscopy (SEM). ). SUPERHYDROPHOBIC ACRYLIC ACID COPOLYMER POWDERS

The superhydrophobic acrylic acid copolymer powders that are suitable for the invention are chosen from ethylene glycol dimethacrylate / lauryl methacrylate copolymer powders, such as those sold under the name POLYTRAP® 6603 ADSORBER by the company Dow Corning.

A composition according to the invention may comprise at least superhydrophobic particles as defined above in a content of between 0.2% and 10% by weight, preferably between 0.5% and 5% by weight, and even more preferentially between 1% and 3% by weight relative to the total weight of the final composition, that is to say when the propellants are considered.

In particular, for a weight ratio between the liquid phase and the propellant gas of 15/85, a composition according to the invention may comprise at least superhydrophobic particles as defined above in a content of between 0.15% and 1.50. % by weight, preferably between 0.30% and 1.35% by weight, and even more preferably between 0.60% and 1.20% by weight relative to the total weight of the final composition, that is to say ie when the propellants are considered.

A composition according to the invention may comprise at least superhydrophobic particles as defined above in a content of between 1% and 10% by weight, preferably between 2% and 9% by weight, and even more preferentially between 4% and 8%. % by weight relative to the total weight of the liquid phase, that is to say when the propellants are not considered.

FILMOGENE POLYMER

A composition according to the invention may furthermore advantageously comprise at least one film-forming polymer.

"Film-forming polymer" means any polymer:

- (1) capable of forming alone or in the presence of an auxiliary filming agent, a continuous and adherent film on a support, in particular on keratin materials, in particular the skin; and

(2) which makes it possible to maintain the adhesion of the superhydrophobic particles to the support, in particular to the keratin materials, in particular to the skin. A film-forming polymer suitable for the present invention is water resistant.

For the purposes of the present invention, the term "water-resistant" is understood to mean a film-forming polymer which has two possible behaviors, namely either this polymer is a point of glue between the particles of superhydrophobic particles, or it is covered with superhydrophobic particles.

Advantageously, a film-forming polymer that is suitable for the invention makes it possible to maintain the adhesion of the superhydrophobic particles as defined above to keratinous substances, in particular to the skin.

In addition, the presence of a film-forming polymer in the composition according to the invention makes it possible to improve the resistance to abrasion or to the various abrasions to which keratin materials, in particular the skin, are generally exposed.

Of course, those skilled in the art will choose the polymers according to their compatibility with the superhydrophobic particles used in a composition according to the invention.

Preferably, the film-forming polymers that can be used according to the invention can be chosen from:

(i) non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

(ii) aqueous latices;

(iii) film-forming pseudoblocks;

(iv) vinyl polymers grafted with a carbosiloxane dendrimer; and

(v) their mixtures.

(i) Copolymers of acrylic acid and N-tert-butylacrylamide

Among the copolymers of acrylic acid and N-tert-butylacrylamide, which may be present in a composition according to the invention, it is preferable to use non-neutralized acrylic acid / ethyl acrylate / N-tert-butylacrylamide copolymers (in which acrylic acid is in free form) as ULTRAHOLD® products

STRONG and ULTRAHOLD® 8 (INCI name: Acrylates / t-Butylacrylamide Copolymer) in unneutralized form from BASF. By "copolymer of (meth) acrylic acid and unneutralised N-tert-butylacrylamide" is meant any copolymer of (meth) acrylic acid and N-tert-butylacrylamide whose (meth) acrylic acid function is free and is not neutralized by an organic or mineral base.

These copolymers are generally available in the form of powders.

(ii) Aqueous latex

Among the aqueous latexes suitable for the invention, which may be present in a composition according to the invention, mention may be made of acrylate copolymers and their derivatives. They may be chosen from those which have a glass transition temperature (Tg) ranging from 15 ° C. to 100 ° C., for example from 30 ° C. to 70 ° C. By way of illustration, mention may in particular be made of an ammonium copolymer acrylate, an acrylate copolymer, and / or their derivatives, such as those sold under the name DERMACRYL® 79 by the company AkzoNobel; and SYNTRAN® 5760 CG by Interpolymer Corporation.

These latices are generally available in the form of powders or dispersion in water.

(iii) Fumogenic pseudoblocks

Among the thermoplastic pseudoblocks that are suitable for use in the invention, which may be present in a composition according to the invention, mention may be made of a film-forming ethylenic polymer, a dispersion of polymeric particles and their mixtures.

(iii) Ethylenic Ethyl Polymer

Preferably, the film-forming ethylenic polymer according to the invention is a polymer with a linear or grafted structure. In contrast, a non-linear or non-grafted polymer is, for example, a star-shaped or cross-linked polymer.

The ethylene block polymer according to the invention is preferably prepared exclusively from mono-functional monomers. This means that the sequenced ethylenic polymer does not contain multifunctional monomers which make it possible to break the linearity of a polymer in order to obtain a polymer, in particular a crosslinked polymer, as a function of the level of multifunctional monomer. Preferably, the ethylenic polymer according to the invention is a non-elastomeric polymer, that is to say a polymer which, when it is subjected to a stress aimed at stretching it (for example by 30% relative to its length initial), does not return to a length substantially identical to its initial length when the stress ceases.

More specifically, a non-elastomeric polymer denotes a polymer having an instantaneous recovery Ri <50% and a delayed recovery R ₂ h <70%> after undergoing an elongation of 30%>. Preferably, R 1 is <30% and R ₂ h is <50%.

The non-elastomeric nature of the polymer can be determined according to the following protocol: A polymer film is prepared by pouring a solution of the polymer into a teflon matrix and then dried for 7 days in a controlled atmosphere at 23 ± 5 ° C. and 50 ± 10% relative humidity. A film approximately 100 .mu.m in thickness is obtained in which are cut rectangular specimens (for example, with a "punch") of a width of 15 mm and a length of 80 mm. These specimens in the form of specimens are subjected to a tensile stress with the aid of 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 (10) of the specimen.

The instantaneous recovery Ri is determined as follows:

the specimen is stretched by 30% (smax), that is to say approximately 0.3 times its initial length (10);

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

The instantaneous recovery Ri (in%) is determined by the following formula: Ri = ((smax - si) / smax) x 100

To determine the delayed recovery, the residual elongation of the specimen is measured in percentage (s2h), two hours after return to zero stress. The delayed recovery R ₂ h (in%) is given by the formula below:

R2h = ((smax - s2h) / smax) x 100 The ethylenic polymer according to the present invention is a sequenced polymer, comprising a first block having a Tg greater than or equal to 85 ° C and a second block having a Tg of less than or equal to 20 ° C.

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

Preferably, the ethylenic polymer comprises two distinct sequences (diblock) or preferably three distinct sequences (triblocks).

Preferably, said first and second sequences are incompatible with each other. By "sequences incompatible with each other", it is meant that the mixture formed of the polymer corresponding to the first block and the polymer corresponding to the second block, is not miscible in the majority polymerization solvent by weight of the polymer. sequenced, at ambient temperature (25 ° C.) and atmospheric pressure (105 Pa), for a content of the polymer mixture greater than or equal to 5% by weight, relative to the total weight of the mixture (polymers and 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 that

ii) each of the polymers corresponding to the first and second blocks has an average molecular weight (in weight or in number) equal to that of the block polymer ± 15%.

In the case of a mixture of polymerization solvents, assuming two or more solvents present, 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 glass transition temperatures (Tg) indicated are, unless indicated otherwise, theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 4th ed. (Brandrup, Immergut, Grulke), 1999, John Wiley, according to the following relationship, known as Fox's Law:

ωί being the mass fraction of the monomer i in the sequence in question and Tgi being the glass transition temperature of the monomer i rhomopolymer (expressed in Kelvin).

The polymer according to the invention therefore comprises a block having a Tg greater than or equal to 85 ° C, for example between 85 ° C and 175 ° C, preferably between 90 ° C and 150 ° C, in particular between 100 ° C and 130 ° C.

The polymer according to the invention also comprises a block having a Tg less than or equal to 20 ° C, for example between -100 and 20 ° C, preferably between -80 and 15 ° C, in particular between -60 and 10 ° vs.

Preferably, the sequence of Tg greater than or equal to 85 ° C represents 50 to

90% by weight, preferably 60 to 80% by weight, of the weight of the final polymer.

Preferably, the Tg sequence of less than or equal to 20 ° C represents 5 to 50% by weight, preferably 10 to 40% by weight, of the weight of the final polymer.

Preferably, said first and second sequences are interconnected by an intermediate segment comprising at least one constituent monomer of said first block and at least one constituent monomer of said second block.

The intermediate segment is preferably a sequence, or block, comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer; it can allow to "compatibilize" these sequences. Said intermediate segment or block is preferably a random copolymer.

Preferably, said intermediate segment or 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%), better at 95% and even better at 100%.

Preferably, said sequenced ethylenic polymer has a polydispersity index Ip greater than 2, especially between 2 and 9, preferably between 2.3 and 8, better still between 2.4 and 7. The polydispersity index Ip is equal to the ratio of the weight average mass Mw to the number average mass Mn.

The weight average molar masses (Mw) and number (Mn) are determined by gel permeation liquid chromatography (solvent THF, calibration curve established with linear polystyrene standards, refractometric detector and UV). The weight average mass (Mw) of the sequenced ethylenic polymer is preferably between 35,000 and 300,000, more preferably between 45,000 and 150,000 g / mol.

The number average mass (Mn) of the sequenced ethylenic polymer is preferably from 10,000 to 70,000, more preferably from 12,000 to 50,000 g / mol.

Each block, or block, of the polymer according to the invention is derived from one type of monomer or from several different types of monomer. This means that each sequence can be a homopolymer or a copolymer, which can be random, alternating or otherwise; preferably statistical. The chemical nature and / or the amount of the monomers constituting each of the sequences can of course be chosen by those skilled in the art, on the basis of his general knowledge, to obtain sequences having the required Tg.

The sequence having a Tg greater than or equal to 85 ° C, or first sequence, can therefore be a homopolymer or a copolymer. It preferably comprises at least one monomer of Tg greater than or equal to 85 ° C.

In the case where this sequence is a homopolymer, it may be derived from a monomer such that the homopolymer prepared from this monomer has a Tg greater than or equal to 85 ° C.

In the case where this sequence is a copolymer, it may be derived from one or more monomers, the nature and concentration of which are chosen so that the Tg of the resulting copolymer is greater than or equal to 85 ° C. The copolymer may for example comprise monomers which are such that the homopolymers prepared from these monomers have Tg greater than or equal to 85 ° C., for example a Tg ranging from 85 to 175 ° C., alone or as a mixture with monomers. which are such that the homopolymers prepared from these monomers have Tg's lower than 85 ° C, preferably selected from monomers having a Tg ranging from -100 ° C to 85 ° C.

Similarly, the sequence having a Tg less than or equal to 20 ° C, or second sequence, may be a homopolymer or a copolymer. It preferably comprises at least one monomer of Tg less than or equal to 20 ° C.

In the case where this sequence is a homopolymer, it may be derived from a monomer such that the homopolymer prepared from this monomer has a Tg less than or equal to 20 ° C. In the case where this sequence is a copolymer, it may be derived from one or more monomers, the nature and concentration of which are chosen such that the Tg of the resulting copolymer is less than or equal to 20 ° C. It may for example comprise monomers including a rhomopolymer corresponding to a Tg less than or equal to 20 ° C, for example a Tg ranging from -100 ° C to 20 ° C, alone or in mixture with monomers including rhomopolymer corresponding to a higher Tg at 20 ° C, preferably selected from monomers having a Tg of between 20 and 175 ° C.

The monomers whose rhomopolymer has a glass transition temperature (Tg) greater than or equal to 85 ° C. (also called monomers with a Tg greater than or equal to 85 ° C.) may be chosen from the following monomers, alone or as a mixture:

methacrylates of formula CH2 = C (CH3) -COORi in which R1 represents a methyl or tert-butyl group; or a C ₆ -C ₁₂ cycloalkyl group such as isobornyl;

acrylates of formula CH 2 CHCH-COOR ₂ in which R ₂ represents a C ₆ to C ₁₂ cycloalkyl group such as isobornyl, or a tert-butyl group;

(meth) acrylamides of formula CH ₂ = C (CH ₃ ) -CC ⁾ NR ₇ R 8 or

in which R ₇ and Rs, which are identical or different, represent a hydrogen atom, a methyl group or isopropyl group; or R ₇ is H and Rs is a branched C ₃ to C ₅ group such as isopropyl, sec-butyl, tert-butyl, 1-methylbutyl; mention may be made of Nt-butylacrylamide, N-isopropylacrylamide and N, N-dimethylacrylamide;

styrene and its derivatives, such as chlorostyrene.

In particular, mention may be made of methyl methacrylate, tert-butyl (meth) acrylate, isobornyl (meth) acrylate and mixtures thereof.

The monomers whose rhomopolymer has a Tg of less than or equal to 20 ° C. can be chosen from the following monomers, alone or as a mixture:

the acrylates of formula CH ₂ = CHCOOR ₃ , with R ₃ representing a linear or branched C 1 to C ₁₂ alkyl group, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or a plurality of heteroatoms selected from O, N, S, said alkyl group being furthermore optionally substituted with one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I and F); the methacrylates of formula CH 2 = C (CH 3) -COOR ₄ , with R ₄ representing a linear or branched C ₆ to C ₁₂ alkyl group, in which one or more heteroatoms chosen from O are optionally intercalated; , N and S, said alkyl group being further optionally substituted with one or more substituents selected from hydroxyl groups and halogen atoms (Cl, Br, I, F);

vinyl esters of formula R 5 -CO-O-CF CH 2 where R 5 represents a linear or branched C ₄ -C 12 alkyl group;

C ₄ -C 12 alkyl vinyl ethers, such as butylvinylether and laurylvinylether;

- C4-C12 N-alkyl acrylamides, such as N-octylacrylamide.

Among the monomers having a Tg of less than or equal to 20 ° C., mention may also be made of the monomers of formula (I) below, alone or as a mixture:

H ₂ C = C ⁽¹⁾

(Z) - (R ₂ ) - (CH ₂ CH ₂ 0) -R 3

in which :

Ri is a hydrogen atom or a methyl radical;

Z is a divalent group selected from -COO-, -CONH-, -CONCH3-, -OCO-, -O-, -SO2- -CO-O-CO- or -CO-CH2-CO-;

- x is 0 or 1;

R2 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, of 1 to 30 carbon atoms, which can comprise 1 to 18 heteroatoms chosen from O, N, S, F, Si and P;

m is 0 or 1;

n is an integer between 3 and 300 inclusive;

- R3 is a hydrogen atom or a carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, of 1 to 30 carbon atoms, which may comprise 1 to 20 heteroatoms selected from O, N, S, F, Si and P.

Preferably, x = 1 and Z represents COO or CONH, preferentially COO.

In the radical R2, the heteroatom (s), when they are present, can be inserted in the chain of said radical R2, or said radical R2 can be substituted by one or more groups including them such as hydroxy, amino (NH ₂ , NH or NR'R "with R 'and R "identical or different representing a linear or branched C1-C22 alkyl, in particular methyl or ethyl), -CF ₃ , -CN, -SO ₃ H or -COOH.

In particular, R ₂ may comprise a group -O-, -N (R) -, -CO- and their combination, and in particular -O-CO-O-, -CO-O-, -N (R) CO- ; -O-CO-NR-, -NR-CO-NR-, where R is H or linear or branched C1-C4 alkyl, optionally comprising 1 to 12 heteroatoms selected from O, N, S, F, Cl, Br , Si and P.

In particular R2 can be:

an alkylene radical having 1 to 20 carbon atoms, such as methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, tert-butylene, pentylene, isopentylene, n-hexylene, isohexylene, heptylene, isoheptylene, n-octylene, iso-octylene, nonylene, isononylene, decylene, isodecylene, n-dodecylene, isododecylene, tridecylene, n-tetradecylene, hexadecylene, n-octadecylene, docosanylene, arachinylene;

- a cycloalkylene radical having 5 to 10 carbon atoms, substituted or unsubstituted, such as cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylne, cyclononylene, cyclodécylène;

a phenylene radical -CeH4- (ortho, meta or para) optionally substituted with a C1-C12 alkyl radical optionally comprising 1 to 18 heteroatoms chosen from O, N, S, F, Si and P;

a benzene radical -C6H4-CH2- optionally substituted with a C1-C12 alkyl radical;

optionally comprising 1 to 18 heteroatoms selected from O, N, S, F, Si and

P;

a radical of formula -CH2-O-CO-O-, CH2-CH2-O-CO-O-, -CH2-CO-O-, -CH2-CH2-CO-O-, -CH2-O-CO -NH-, -CH2-CH2-O-CO-NH-; -CH ₂ -NH-CO-NH-, -CH ₂ -CH ₂ -NH-CO-NH-; -CH ₂ -CHOH-, -CH ₂ -CH ₂ -CHOH-, -CH ₂ -CH ₂ -CH (NH ₂ ) -, -CH ₂ -CH (NH ₂ ) -, -CH ₂ -CH ₂ -CH (NHR) -, -CH ₂ -CH (NHR) -, -CH ₂ -CH ₂ -CH (NRR ") -, -CH ₂ -CH (NRR ") -, -CH2-CH2-CH2-NR-, -CH2-CH2-CH2-O-; -CH2-CH2-CHR-O- with R ^* and R "representing a linear or branched C1-C22 alkyl optionally comprising 1 to 12 heteroatoms selected from O, N, S, F, Si and P;

- or a mixture of these radicals.

Preferably R2 can be: an alkylene radical having 1 to 20 carbon atoms, especially methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene;

a phenylene radical -CeH4- (ortho, meta or para) optionally substituted with a C1-C12 alkyl radical optionally comprising 1 to 18 heteroatoms chosen from O, N, S, F, Si and P; or

a benzylene radical -C6H4-CH2- optionally substituted with a C1-C12 alkyl radical optionally comprising 1 to 18 heteroatoms chosen from O, N, S, F, Si and P.

Preferably, n is between 5 and 200 inclusive, and even more preferably between 6 and 120 inclusive, or even between 7 and 50 inclusive.

Preferably, R3 is a hydrogen atom; a phenyl radical optionally substituted by a C1-C12 alkyl radical optionally comprising 1 to 20 heteroatoms chosen from O, N, S, F, Si and P; a C1-C30 alkyl radical, in particular C1-C22 or even C2-C16, optionally comprising 1 to 18 heteroatoms chosen from O, N, S, F, Si and P; a C 3 -C 12, especially C 4 -C 8 or even C 5 -C 6 cycloalkyl radical, optionally comprising 1 to 18 heteroatoms chosen from O, N, S, F, Si and P.

Among the R 3 radicals, mention may be made of methyl, ethyl, propyl, benzyl, ethylhexyl, lauryl, stearyl and behenyl chains.

and also fluorinated alkyl chains such as, for example heptadecafluorooctyl ethyl sulfonyl amino CF3 (CF2) 7-S02-N (C 2 H ₅₎ -CH 2 CH _2; or -CH2-CH2-CN, succinimido, maleimido, mesityl, tosyl, triethoxysilane or phthalimide chains.

Preferably, the monomers of formula (I) are such that:

- x = 1 and Z represents COO,

- m = 0,

n = 6 to 120 inclusive,

R3 is chosen from a hydrogen atom; a phenyl radical optionally substituted with a C1-C12 alkyl radical; a C1-C30 alkyl radical, in particular C1-C22 or even C2-C16.

Preferably, the monomers of formula (I) have a molecular weight of between 300 and 5000 g / mol.

Among the monomers of formula (I) that are particularly preferred, mention may be made of: poly (ethylene glycol) (meth) acrylate in which R 1 is H or methyl; Z is COO, x = 1, m = 0 and R ₃ = H;

methyl (poly) ethylene glycol (meth) acrylate, also known as methoxy-poly (ethylene glycol) methoxy acrylate, wherein R 1 is H or methyl, Z is COO, x = 1, m = 0 and R ₃ = methyl;

the alkyl (poly) ethylene glycol (meth) acrylate in which R ₁ is H or methyl, Z is COO, x = 1, m = 0 and R ₃ = alkyl.

phenyl-poly (ethylene glycol) (meth) acrylates, also known as poly (ethylene glycol) phenyl ether (meth) acrylate, in which R 1 is H or methyl, Z is COO, x = 1, m = 0 and R ₃ = phenyl.

Examples of commercial monomers are:

CD 350 (methoxy-poly (ethylene glycol 350) methacrylate and CD 550 (methoxy-poly (ethylene glycol 550) methacrylate, supplied by Sartomer Chemicals;

M90G (methoxy-poly (ethylene glycol) methacrylate (9 repeating units)) and M230G (methoxy-polyethylene glycol methacrylate (23 repeating units)) available from Shin-Nakamura Chemicals;

- Methoxy-poly (ethylene glycol) methacrylates of average molecular weight 300, 475 or 1100, available from Sigma-Aldrich;

the methoxypoly (ethylene glycol) acrylate of average molecular weight 426 available from Sigma-Aldrich;

the methoxy-poly (ethylene glycol) methacrylates available from LAPORTE under the trade names: MPEG 350, MPEG 550, S 10W, S20W or from Cognis under the name BISOMER.

poly (ethylene glycol) monomethyl ether, mono (succinimidyl succinate) ester of average molecular weight 1900 or 5000, from Polysciences;

- Behenyl poly (ethylene glycol PEG-25) methacrylate, available from Rhodia under the name SIPOMER BEM;

poly (ethylene glycol) phenyl ether acrylates of average molecular weights 236, 280 or 324 available from Aldrich;

methoxy polyethylene glycol 5000 2- (vinyl sulfonyl) ethyl ether commercially available from Fluka;

polyethylene glycol ethyl ether methacrylate available from Aldrich; polyethylene glycol methacrylates 8000, 4000, 2000 from Monomer & Polymer Dajac laboratories.

- Methoxy-poly (ethylene glycol) methacrylate 2000 Norsocryl 402 Arkema;

- Methoxy-poly (ethylene glycol) 5000 Norsocryl 405 methacrylate from Arkema;

the poly (ethylene glycol) methyl ether acrylate Aldrich, Mn = 454 g / mol, DP =

8-9.

In particular, among the monomers of Tg less than 20 ° C., mention may be made of alkyl acrylates, the alkyl chain of which contains from 1 to 10 carbon atoms, with the exception of the tert-butyl group, such as methyl acrylate. isobutyl acrylate, ethyl-2-hexyl acrylate; as well as the (meth) acrylates of poly (ethylene glycol) and the (meth) acrylates of alkyl-poly (ethylene glycol), more particularly the methacrylates of methyl-poly (ethylene glycol); and their mixtures.

The polymer according to the invention may also comprise additional monomers, which may be chosen from, alone or as a mixture:

ethylenically unsaturated monomers comprising at least one carboxylic or sulfonic acid function, such as, for example, acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and salts thereof,

ethylenically unsaturated monomers comprising at least one hydroxyl group such as 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate,

ethylenically unsaturated monomers comprising at least one tertiary amine function such as 2-vinylpyridine, 4-vinylpyridine, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropylmethacrylamide and the salts thereof.

The sequence of Tg greater than or equal to 85 ° C preferably comprises at least one acrylate monomer of formula CH ₂ = CH-COOR and at least one methacrylate monomer of formula CH ₂ = C (CH 3) -COOR in which R, identical or different, represents a cycloalkyl group, C ₄ -C _12, preferably a cycloalkyl Cs to C _12; preferably R is identical in the monomers; preferably, these monomers are acrylate and isobornyl methacrylate.

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 first block can be obtained exclusively from acrylate and isobornyl methacrylate, which are preferably in an acrylate / methacrylate mass ratio of between 30:70 and 70:30, preferably between 40:60 and 60:40. , in particular of the order of 50:50.

The sequence of Tg less than or equal to 20 ° C preferably comprises at least one monomer chosen from, alone or as a mixture:

acrylates of formula CH ₂ = CHCOOR ₃ in which R ₃ represents a linear or branched C ₁ -C ₁₂ unsubstituted alkyl group, with the exception of the tert-butyl group, in which is (are) optionally intercalated (s) one or more heteroatoms selected from O, N, S; in particular isobutyl acrylate,

methacrylates of formula CH ₂ = C (CH ₃ ) -COOR ₄ , in which R ₄ represents a linear or branched C 6 to C 12 unsubstituted alkyl group, in which one or more of them is optionally intercalated; heteroatoms selected from O, N and S.

- (meth) acrylic acid;

the monomers of formula (I), preferably with x = 1 and Z = COO. Preferentially, the sequence of Tg less than or equal to 20 ° C comprises acrylic acid and / or methacrylic acid.

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

a part of the polymerization solvent can be introduced into a suitable reactor, the mixture is heated until the temperature which is suitable for the polymerization is reached (typically between 60 and 120 ° C.),

once this temperature is reached, the constituent monomers of the first block may be added in the presence of a part of the polymerization initiator, after a time T corresponding to a maximum conversion level of preferably 90%, it is possible to introduce the constituent monomers of the second sequence and the other part of the initiator,

the mixture can be allowed to react for a time T '(especially ranging from 3 to 6 hours) at the end of which the mixture is brought back to ambient temperature (25 ° C.), so as to obtain the polymer in solution in the polymerization solvent .

By polymerization solvent is meant a solvent, or a mixture of solvents, especially chosen from ethyl acetate, butyl acetate, C ₁ -C ₆ alcohols such as isopropanol, ethanol and aliphatic alkanes. such as isododecane and mixtures thereof. Preferably, the polymerization solvent is a mixture of butyl acetate and isopropanol or isododecane.

The polymerization initiator may be chosen from organic peroxides comprising from 8 to 30 carbon atoms. There may be mentioned, for example, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane sold under the reference Trigonox®141 by Akzo Nobel.

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

When present, the segment, or intermediate sequence, which connects the first sequence and the second block of the sequenced polymer may result from the polymerization of at least one monomer of the first block, remaining available after the polymerization at a rate of conversion of at most 90% to form the first block, and at least one monomer of the second block, added to the reaction mixture. The formation of the second sequence is initiated when the monomers of the first sequence 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 monomers of the first available sequence, resulting from a conversion rate of these first monomers lower or equal to 90%, during the introduction of the monomers of the second sequence during the synthesis of the polymer.

Among the block ethylenic polymers of the invention, a polymer chosen from:

a polymer of polyisobornyl acrylate / isobornyl methacrylate / isobutyl acrylate / acrylic acid,

a random isobornyl acrylate / isobornyl methacrylate / PEG methacrylate / acrylic acid polymer and more particularly poly (isobornyl acrylate / isobornyl methacrylate / isobutyl acrylate / acrylic acid) polymer.

According to a particularly preferred embodiment, a flexible ethylenic polymer that is suitable for the invention is an acrylic acid / isobutyl acrylate / isobornyl acrylate copolymer sold especially under the name MEXOMERE® PAS by the company Chimex, described in application FR2995. 785. Such an acrylic acid / isobutyl acrylate / isobornyl acrylate copolymer is conventionally available in solution in isododecane.

(iii) -2 Dispersion of polymeric particles

The dispersion of polymeric particles according to the invention is a dispersion of at least one polymer stabilized with a stabilizing agent in a non-aqueous medium containing at least one hydrocarbon-based oil B, the polymer of the particles being a polymer of (meth) acrylate C1-C4 alkyl and optionally a silicone macromonomer (I) as defined below; the stabilizing agent being a polymer comprising from 50 to 100% by weight of C 8 -C 22 alkyl acrylate, from 0 to 50% by weight of (C 1 -C 4) alkyl (meth) acrylate and optionally a silicone macromonomer (I) as defined below, relative to the total weight of the stabilizer; the stabilizer and / or the polymer of the particles may comprise at least the silicone macromonomer (I), and:

(i) when the stabilizer comprises the silicone macromonomer (I), the macromonomer is present in the stabilizer in a content of less than or equal to 5.5% by weight, relative to the total weight of the stabilizer + polymer set of the particles; the polymer of the particles optionally comprising said silicone macromonomer (I) in a content less than or equal to 28% by weight, relative to the total weight of the stabilizer + polymer group of the particles;

(ii) when the polymer of the particles comprises the silicone macromonomer (I) and the stabilizer does not comprise silicone macromonomer (I), the macromonomer is present in a content of less than or equal to 18% by weight, relative to the total weight of the stabilizer + polymer of the particles.

The presence of the silicone macromonomer (I) in the stabilizer and / or the polymer of the particles makes it possible to obtain a stable polymer dispersion, in particular after storage for 7 days at ambient temperature (25 ° C.).

The dispersions according to the invention therefore consist of particles, generally spherical, of at least one polymer in a non-aqueous medium. The polymer of the particles is a polymer of alkyl (meth) acrylate

The monomers of (C1-C4) alkyl (meth) acrylate may be chosen from methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate and (meth) acrylate. isopropyl, n-butyl (meth) acrylate, t-butyl (meth) acrylate.

Advantageously, a C1-C4 alkyl acrylate monomer is used. Preferably, the polymer of the particles is a polymer of methyl acrylate and / or ethyl acrylate.

The polymer of the particles and / or the stabilizing agent may comprise a mono-terminal macromethyloyloxy or monomethacryloyloxy polydimethylsiloxane macromonomer of formula (I) (hereinafter referred to as a silicone macromonomer), as follows:

in which :

- R-8 denotes a hydrogen atom or a methyl group; preferably methyl;

- R denotes a divalent hydrocarbon group, linear or branched, preferably linear, having 1 to 10 carbon atoms, preferably having 2 to 4 carbon atoms, and optionally containing one or two -O- ether bonds; preferably an ethylene, propylene or butylene group;

- Rio denotes a linear or branched alkyl group having 1 to 10 carbon atoms, especially 2 to 8 carbon atoms; preferably methyl, ethyl, propyl, butyl or pentyl;

n denotes an integer ranging from 1 to 300, preferably ranging from 3 to 200, and preferably ranging from 5 to 100.

In particular, monomethacryloyloxypropyl polydimethylsiloxanes such as those sold under the names MCR-M07, MCR-M17, MCR-M1 1, MCR-M22 by Gelest Inc or X-22-2475, X-22-2426, X-22 may be used in particular. - 174DX by Shin Etsu. The polymer of the particles may furthermore comprise an ethylenically unsaturated acid monomer or of their anhydride, chosen in particular from ethylenically unsaturated acidic monomers comprising at least one carboxylic, phosphoric or sulphonic acid function, such as crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamidopropanesulfonic acid, acrylamidoglyceric acid, and their salts.

Preferably, the ethylenically unsaturated acidic monomer is chosen from (meth) acrylic acid, maleic acid and maleic anhydride. The salts may be chosen from alkali metal salts, for example sodium and potassium; alkaline earth metal salts, for example calcium, magnesium, strontium, metal salts, for example zinc, aluminum, manganese, copper; ammonium salts of formula NH ₄ +; quaternary ammonium salts; organic amine salts, such as for example the salts of methylamine, dimethylamine, trimethylamine, triethylamine, ethylamine, 2-hydroxyethylamine, bis (2-hydroxyethyl) amine, tri- hydroxyethylamine; lysine salts, arginine.

The polymer of the particles may thus comprise, or consist essentially of, from 62 to 100% by weight of (C ₁ -C ₄ ) alkyl (meth) acrylate.

and from 0 to 38% by weight of the mono silicone mother macro (I)

and from 0 to 20% by weight of ethylenically unsaturated acidic monomer, based on the total weight of the polymer. According to a first embodiment of the invention, the polymer consists essentially of a polymer of one or more alkyl (meth) acrylate monomers.

According to a second embodiment of the invention, the polymer essentially consists of a copolymer of (meth) acrylate C1-C4 and (meth) acrylic acid or maleic anhydride.

According to a third embodiment, the polymer consists essentially of a copolymer of (meth) acrylate C1-C4 and silicone macromonomer (I).

According to a fourth embodiment of the invention, the polymer consists essentially of a copolymer of (meth) acrylate C1-C4, (meth) acrylic acid or maleic anhydride and silicone macromonomer (I). The polymer of the particles may be chosen from:

homopolymers of methyl acrylate

methyl acrylate / silicone macromonomer copolymers (I) homopolymers of ethyl acrylate

ethyl acrylate / silicone macromonomer copolymers (I)

methyl acrylate / ethyl acrylate copolymers

methyl acrylate / ethyl acrylate / silicone macromonomer copolymers (I)

methyl acrylate / ethyl acrylate / acrylic acid copolymers methyl acrylate / ethyl acrylate / acrylic acid / silicone macromonomer copolymers (I)

methyl acrylate / ethyl acrylate / maleic anhydride copolymers methyl acrylate / ethyl acrylate / maleic anhydride / silicone macromonomer copolymers (I)

methyl acrylate / acrylic acid copolymers

methyl acrylate / acrylic acid / mono silicone mono polymer copolymers

(I)

ethyl acrylate / acrylic acid copolymers

ethyl acrylate / acrylic acid / silicone macromonomer copolymers (I) methyl acrylate / maleic anhydride copolymers

methyl acrylate / maleic anhydride / silicone macromonomer copolymers (I)

ethyl acrylate / maleic anhydride / silicone macromonomer copolymers (I)

ethyl acrylate / maleic anhydride copolymers;

and preferably from:

methyl acrylate / acrylate copolymers

methyl acrylate / ethyl acrylate / silicone macromonomer copolymers (I)

methyl acrylate / ethyl acrylate / acrylic acid copolymers.

Advantageously, the polymer of the particles is a non-crosslinked polymer. The polymer of the particles of the dispersion preferably has a number average molecular weight of from 2,000 to 10,000,000, preferably from 150,000 to 500,000. The polymer of the particles may be present in the dispersion in a content ranging from 20% to 60% by weight, based on the total weight of the dispersion.

The stabilizing agent is a polymer comprising from 50 to 100% by weight, preferably from 60 to 95% by weight, of C 8 -C 22 alkyl acrylate, from 0 to 50% by weight, preferably from 5 to 40% by weight, of (C1-C4) alkyl (meth) acrylate and optionally the silicone macronomer (I) as described above. The stabilizing agent is preferably a random polymer.

The C 8 -C 22 alkyl acrylate may comprise a linear, branched or cyclic alkyl group such as, for example, a 2-ethyl hexyl, isobornyl, lauryl, behenyl or stearyl group.

Preferably, isobornyl acrylate and 2-ethylhexyl acrylate are used. Preferably, isobornyl acrylate is used.

Advantageously, the stabilizing agent is chosen from:

homopolymers of 2-ethyl hexyl acrylate

homopolymers of isobornyl acrylate

copolymers of isobornyl acrylate / methyl acrylate

copolymers of 2-ethylhexyl acrylate / methyl acrylate

copolymers of isobornyl acrylate / methyl acrylate / ethyl acrylate copolymers of 2-ethylhexyl acrylate / methyl acrylate / ethyl acrylate

copolymers of isobornyl acrylate / methyl acrylate / ethyl acrylate / macro mono silicone mother (I)

copolymers of 2-ethylhexyl acrylate / methyl acrylate / ethyl acrylate / silicone macromonomer (I). The stabilizing polymer preferably has a number average molecular weight ranging from 10,000 to 400,000, preferably ranging from 20,000 to 200,000. The stabilizer is in contact with the surface of the polymer particles and thus makes it possible to stabilize these particles in part. surface for maintaining these particles in dispersion in the non-aqueous medium of the dispersion. Thus, the polymer particles are surface stabilized by the stabilizing agent. The stabilizer is a polymer distinct from the polymer of the particles: the stabilizer does not form a covalent bond with the polymer of the particles.

According to a first embodiment of the invention, the silicone macromonomer (I) is present in the stabilizer of the dispersion; it is not present in the polymer of the particles.

The silicone macromonomer (I) is present in the stabilizer in a content of less than or equal to 5.5% by weight, in particular ranging from 0.1 to 5.5% by weight, relative to the total weight of the stabilizing assembly + polymer particles. In particular, the silicone macromonomer (I) may be present in the stabilizer in a content ranging from 0.1 to 35% by weight, relative to the total weight of the stabilizer.

Advantageously, the stabilizer + polymer assembly of the particles present in the dispersion comprises from 5 to 50% by weight of C8-C22 alkyl acrylate polymerized, from 44.5 to 89.5% by weight of (meth) acrylate polymerized C 1 -C 4 alkyl and 0.1 to 5.5% by weight of silicone macromonomer (I), based on the total weight of the stabilizer + polymer set of the particles.

Preferably, the stabilizer + polymer assembly of the particles present in the dispersion comprises from 6 to 30% by weight of C8-C22 alkyl acrylate polymerized and from 64.5 to 93.9% by weight of (meth) acrylate polymerized C 1 -C 4 alkyl and 0.1 to 5.5% by weight of silicone macromonomer (I), based on the total weight of the stabilizer + polymer set of the particles. According to a second embodiment of the invention, the silicone macromonomer (I) is present in the dispersion stabilizer and in the polymer of the particles.

The silicone macromonomer (I) is present in the stabilizer in a content of less than or equal to 5.5% by weight, in particular ranging from 0.1 to 5.5% by weight, relative to the total weight of the stabilizing assembly + polymer particles; and it is present in the polymer of the particles in a content of less than or equal to 28% by weight, in particular ranging from 0.1 to 28% by weight, relative to the total weight of the stabilizer + polymer set of the particles.

In particular, the silicone macromonomer (I) may be present in the stabilizer in a content ranging from 0.1 to 35% by weight, relative to the total weight of the stabilizer; and it may be present in the polymer of the particles in a content ranging from 0.1 to 38% by weight, based on the total weight of the polymer of the particles.

Advantageously, the stabilizer + polymer group of the particles present in the dispersion comprises from 5 to 50% by weight of C8-C22 alkyl acrylate polymerized, from 16.5 to 94.9% by weight of (meth) acrylate C 1 -C 4 alkyl-polymerized and 0.1 to 33.5% by weight of silicone macromonomer (I), based on the total weight of the stabilizer + polymer of the particles.

Preferably, the stabilizer + polymer group of the particles present in the dispersion comprises from 6 to 30% by weight of C8-C22 alkyl acrylate polymerized and from 36.5 to 93.9% by weight of (meth) acrylate C 1 -C 4 alkyl-polymerized and 0.1 to 33.5% by weight of silicone macromonomer (I), based on the total weight of the stabilizer + polymer of the particles. According to a third embodiment of the invention, the silicone macromonomer (I) is present in the polymer of the particles of the dispersion; it is not present in the stabilizer. The silicone macromonomer (I) is present in the polymer of the particles in a content of less than or equal to 18% by weight, in particular ranging from 0.1 to 18% by weight, relative to the total weight of the stabilizer + polymer assembly of the particles.

Advantageously, the silicone macromonomer (I) is present in a content ranging from 0.1 to 25% by weight, relative to the total weight of the polymer of the particles.

Advantageously, the stabilizer + polymer group of the particles present in the dispersion comprises from 5 to 50% by weight of C8-C22 alkyl acrylate polymerized, from 32 to 94.9% by weight of (meth) acrylate. C 1 -C 4 alkyl polymerized and from 0.1 to 18% by weight of silicone macromonomer (I), relative to the total weight of the stabilizer + polymer of the particles. Preferably, the stabilizer + polymer group of the particles present in the dispersion comprises from 6 to 30% by weight of C8-C22 alkyl acrylate polymerized and from 52 to 93.9% by weight of (meth) acrylate. C 1 -C 4 alkyl polymerized and from 0.1 to 18% by weight of silicone macromonomer (I), relative to the total weight of the stabilizer + polymer of the particles.

The polymer particles of the dispersion preferably have a mean size, especially in number, ranging from 50 to 500 nm, especially ranging from 75 to 400 nm, and better still from 100 to 250 nm. According to a particularly preferred form of the invention, use will be made of a dispersion of methyl acrylate / ethyl acrylate (50/50 weight) copolymer particles stabilized with a random copolymer stabilizer containing 75.2% by weight of acrylate. isobornyl, 3% methyl acrylate, 3% ethyl acrylate, 18.8% monomethacryloyloxypropyl polydimethylsiloxane, in isododecane.

Non-aqueous dispersion medium The non-aqueous medium of the polymer dispersion comprises a hydrocarbon oil B.

By "oil" is meant a fatty substance that is liquid at ambient temperature (25 ° C.) and atmospheric pressure (760 mmHg, ie 105 Pa).

Hydrocarbon oil is understood to mean an oil formed essentially or even consisting of carbon and hydrogen atoms, and possibly oxygen, nitrogen, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and / or amide groups.

The hydrocarbon oil B may be chosen from hydrocarbon oils having from 8 to 16 volatile or non-volatile carbon atoms. For the purposes of the invention, the term "volatile oil" means an oil capable of evaporating on contact with the skin or keratin fiber in less than one hour at ambient temperature and atmospheric pressure.

By "non-volatile oil" is meant an oil remaining on the skin or the keratin fiber at room temperature and atmospheric pressure for at least several hours and having in particular a vapor pressure strictly less than 10 -3 mm Hg (0.13 Pa). ).

Among the volatile hydrocarbon oils having from 8 to 16 carbon atoms, mention may be made of:

branched C 8 -C 16 alkanes such as C 6 -C 16 isoalkanes of petroleum origin (also called isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example the oils sold under the trade names of Isopars or Permethyls,

linear alkanes, for example such as n-dodecane (C12) and n-tetradecane (Ci 4) sold by Sasol respectively under references PARAFOL 12-97 and PARAFOL 14-97, and mixtures thereof, the undecane mixture -tridecane, mixtures n-undecane (Cn) and n-tridecane (Ci 3) obtained in Examples 1 and 2 of Application WO2008 / 155059 from Cognis, and mixtures thereof.

Among the non-volatile hydrocarbon oils having from 8 to 16 carbon atoms, mention may be made of:

short chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate;

hydrocarbon oils of vegetable origin, such as triglycerides consisting of esters of fatty acids and of glycerol, the fatty acids of which may have chain lengths varying from C ₄ to C ₂₄ , the latter being linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or else the oils of wheat germ, sunflower, grape seed, sesame, maize, apricot, castor, shea, of avocado, olive, soya, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, cassis, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or the triglycerides of caprylic / capric acids, such as those sold by Stéarineries Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel,

synthetic ethers having from 10 to 40 carbon atoms;

linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane, paraffin oils, and mixtures thereof,

synthetic esters, such as the oils of formula R 1 COOR 2 in which R 1 represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms, and R ₂ represents a hydrocarbon chain, in particular a branched hydrocarbon chain, containing from 1 to 40 carbon atoms with the proviso that R 1 + R _{2 is} ≥ 10, such as, for example, purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, benzoates of C ₁₂ to C ₁₅ alcohols, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethyl hexyl palmitate, isostearyl isostearate, 2-hexyl decyl laurate, 2-octyl palmitate, decyl, 2-octyl-dodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters,

at room temperature liquids with a branched and / or unsaturated carbon chain having from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol or 2-butyloctanol, and 2-undecylpentadecano 1.

Advantageously, the hydrocarbon oil B is preferably chosen from volatile hydrocarbon oils having 8 to 16 carbon atoms, in particular C 6 -C 16 isoalkanes and more particularly isododecane.

Preparation of the Dispersion of Polymeric Particles In general, the dispersion according to the invention may be prepared in the following manner, given by way of example. This preparation is also described in application FR 1 557 189.

The polymerization can be carried out in dispersion, that is to say by precipitation of the polymer being formed, with protection of the particles formed with a stabilizer.

In a first step, the stabilizing polymer is prepared by mixing the monomer (s) constituting the stabilizing polymer, with a radical initiator, in a solvent called synthetic solvent, and by polymerizing these monomers. In a second step, the monomer constituting the polymer is added to the stabilizing polymer formed and the polymerization of these added monomers is carried out in the presence of the radical initiator. When the non-aqueous medium is a non-volatile hydrocarbon oil, the polymerization can be carried out in an apolar organic solvent (synthetic solvent) then adding the nonvolatile hydrocarbon oil (which must be miscible with said synthesis solvent) and selectively distilling the synthesis solvent.

A synthesis solvent is thus chosen such that the monomers of the stabilizing polymer and the radical initiator are soluble therein, and the polymer particles obtained therein are insoluble so that they precipitate during their formation.

In particular, the synthesis solvent can be chosen from alkanes such as heptane or cyclohexane.

When the non-aqueous medium is a volatile hydrocarbon 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 of the particles obtained must be insoluble there.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5-20% by weight. 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 polymerization can be carried out at a temperature ranging from 70 to 110 ° C.

The polymer particles are surface-stabilized, when formed during the polymerization, by the stabilizing agent.

The stabilization can be carried out by any known means, and in particular by direct addition of the stabilizing agent, during the polymerization. The stabilizer is preferably also present in the mixture prior to polymerization of the monomers of the polymer of the particles. However, it is also possible to add it continuously, especially when the monomers of the polymer of the particles are also continuously added.

It is possible to use from 10 to 30% by weight of stabilizer relative to the total weight of monomers used (stabilizer + polymer of the particles), and preferably from 15 to 25% by weight.

(iv) Vinyl polymers grafted with a carbosiloxane dendrimer

A film-forming polymer that is suitable for the invention, when present in a composition according to the invention, can be, as stated above, chosen from vinyl polymers grafted with a carbosiloxane dendrimer.

For the purposes of the invention, the term "vinyl polymer grafted with a carbosiloxane dendrimer", a vinyl polymer comprising at least one unit derived from carbosiloxane dendrimer.

The vinyl polymer has a backbone and at least one side chain, which comprises a carbosiloxane dendrimer derived unit having 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 skeleton 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.

A vinyl polymer according to the invention may contain units derived from carbosiloxane dendrimers which may be represented by the following general formula (I): R ¹

Y-Si -Si (I) in which :

- R ¹ represents an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms;

X ¹ represents a silylalkyl group which, when i = 1, is represented by the formula (II):

in which :

. R ¹ is as defined above in formula (I),

. R ² represents an alkylene radical of 2 to 10 carbon atoms,

. R ³ represents an alkyl group of 1 to 10 carbon atoms,

. X ^{1 + 1} is chosen from: a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 5 to 10 carbon atoms and a silylalkyl group defined above of formula (II) with i = i + 1,

. i is an integer of 1 to 10 which represents the generation of said silylalkyl group, and

. a ¹ is an integer of 0 to 3;

Y represents a radical-polymerizable organic group chosen from:

. organic groups containing a methacrylic group or an acrylic group, said

in which :

R ⁴ represents a hydrogen atom or an alkyl group of 1 to 10 carbon atoms; and

R ⁵ represents an alkylene group of 1 to 10 carbon atoms, such as a methylene group, an ethylene group, a propylene group, or a butylene group, the methylene and propylene groups being preferred; and

. organic groups containing a styryl group of formula:

in which :

R ⁶ represents a hydrogen atom or an alkyl group of 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 ⁷ represents an alkyl group of 1 to 10 carbon atoms;

R ⁸ represents an alkylene group of 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 from 0 to 4; and

* c is 0 or 1, so that if c is 0, - (R ⁸ ) c- represents a bond.

In one embodiment, R ¹ may be an aryl group having 5 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. The alkyl group may preferably be methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, cyclopentyl or cyclohexyl. The aryl group may preferably be represented by a phenyl group and a naphthyl group. The methyl and phenyl groups are more particularly preferred, and the methyl group is most preferred.

According to one embodiment, R ² represents an alkylene group having 2 to 10 carbon atoms, especially a linear alkylene group, such as an ethylene, propylene, butylene or hexylene group; or a branched alkylene group, such as a methylmethylene, methylethylene, 1-methylpentylene or 1,4-dimethylbutylene group.

Ethylene, methylethylene, hexylene, 1-methylpentylene and 1,4-dimethylbutylene are most preferred.

According to one embodiment, R ³ is selected from methyl, ethyl, propyl, butyl and isopropyl groups.

In formula (II), i indicates the number of generations and thus corresponds to the number of repetitions of the silylalkyl group.

For example, when the number of generations is 1, the carbosiloxane dendrimer may be represented by the general formula shown below, wherein Y, R ¹ , R ² and R ³ are as defined above, R ¹² represents an atom of hydrogen or is identical to R ¹ ; ¹ is identical to a ^1. Preferably, the total average number of OR ³ groups in a molecule is in the range of 0 to 7.

When the number of generations is 2, the carbosiloxane dendrimer can be represented by the general formula below, wherein Y, R ^1, R ^2, R ³ and R ¹² are the same as defined above; a ¹ and a ² represent the a ¹ 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 number of generations is equal to 3, the carbosiloxane dendrimer is represented by the general formula below, in which 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 ¹ of the indicated generation. Preferably, the average total number of OR ³ groups in a molecule is in the range of 0-79.

3-a ¹

A vinyl polymer having at least one unit derived from carbosiloxane dendrimer has a side molecular chain containing a carbosiloxane dendrimer structure, and may be derived from the polymerization:

(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 containing a radically polymerizable organic group, represented by the general formula (I) as defined above.

The vinyl monomer component (A) in the vinyl polymer having at least one carbosiloxane dendrimer-derived unit is a vinyl-type monomer that contains a radical-polymerizable vinyl group.

There is no particular limitation with respect to such a 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; butyl methacrylate, butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl acrylate, 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, isobutoxymethoxymethacrylamide, Ν, Ν-dimethylmethacrylamide, or analogous vinyl monomers which contain amide groups; hydroxyethyl methacrylate, hydroxypropyl alcohol methacrylate, or vinyl-like monomers which contain hydroxyl groups; acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, or vinyl-like monomers which contain a carboxylic acid group; tetrahydrofurfuryl methacrylate, butoxyethyl methacrylate, ethyldiethylene glycol methacrylate, polyethylene glycol methacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, or a similar vinyl monomer with ether bonds; 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, dimethacrylate of 1, 6-hexanediol, neopentyl glycol dimethacrylate, trimethylolpropanetrioxyethyl methacrylate, tris (2-hydroxyethyl) isocyanurate dimethacrylate, tris (2-hydroxyethyl) isocyanurate trimethacrylate, styryl-capped polydimethylsiloxane having divinylbenzene groups on two ends, or analogous silicone compounds having unsaturated groups.

A carbosiloxane dendrimer, which is the component (B), can be represented by the formula (I) as defined above.

The following is the preferred examples of group Y of formula (I): acryloxymethyl group, 3-acryloxypropyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group a 2- (3-vinylphenyl) ethyl group, a vinyl group, an allyl group, a methallyl group, and a 5-hexenyl group.

A carbosiloxane dendrimer according to the present invention can be represented by the following average structural formulas:

Thus, according to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by the following formula:

-si- O- -

3-a ³

3-a ²

3-a ¹ in which:

. Y, R ¹ , R ² and R ³ are as defined in formulas (I) and (II) above;

. a ¹ , a ² and a ³ meet the definition of a ¹ according to formula (II); and

. R ¹² is H, an aryl group of 5 to 10 carbon atoms or an alkyl group of 1 to 10 carbon atoms.

According to one embodiment, the carbosiloxane dendrimer of the composition according to the present invention is represented by one of the following formulas:

CH, CH, CH,

I ³

H ₂ c = -CO- ^"C 3 ^H 6 -SiO-Si-C ₂ H-Si-O-Si-CH

I I I

o CH, CH,

CH, CH,

I ³

H, C = CH-C-O-C, H ₆ -SiO-Si-C ₂ H-Si-O-Si-CH,

2 I I I

O CH, CH, The vinyl polymer comprising the carbosiloxane dendrimer according to the invention can be manufactured according to the process for producing a branched silalkane siloxane described in Japanese Patent Application Hei 9-171 154.

For example, it can be produced by subjecting a hydrosilylation reaction to an organosilicon compound which contains a hydrogen atom connected to a silicon atom represented by the following general formula (IV):

R ¹ being as defined above in formula (I),

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 can be represented by vinyltris- (trimethylsiloxy) silane, vinyltris- (dimethylphenylsiloxy) silane, and 5-hexenyltris- (trimethylsilyl xyl) 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.

A vinyl polymer having at least one unit derived from carbosiloxane dendrimer may be chosen from polymers such that the unit of a derivative of a carbosiloxane dendrimer is a carbosiloxane dendritic structure represented by formula (III):

in which Z is an organic group di valent, "p" is 0 or 1, R ¹ is as defined above in formula (IV) and X ¹ is a silylalkyl group represented by formula (II) as defined above.

In a vinyl polymer having at least one unit derived from a carbosiloxane dendrimer, the ratio of polymerization between components (A) and (B), in terms of weight ratio between (A) and (B), is in a range of 0 / 100 to 99.9 / 0.1, or even 0.1 / 99.9 to 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).

A vinyl polymer having at least one unit derived from carbosiloxane dendrimer 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 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 ° C to 150 ° 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 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; 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 the preparation of raw material for cosmetics, 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. 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 silicone oil may be a dimethylpolysiloxane having both trimethylsiloxy-capped molecular ends, a copolymer of methylphenylsiloxane and dimethylsiloxane having both molecular ends capped with trimethylsiloxy groups, a methyl-3,3,3-trifluoropropylsiloxane copolymer and dimethylsiloxane having both molecular ends capped with trimethylsiloxy groups, or similar non-reactive linear silicone oils. 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.

The organic oils may be isododecane, paraffin oil, isoparaffine, 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 oil, sunflower oil, soybean oil, camellia oil, squalane, castor oil, cotton seed, coconut oil, egg yolk oil, 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 a vinyl polymer having at least one carbosiloxane dendrimer derived unit, a silicone oil, an organic oil, an alcohol, or water. The liquids may be present in the polymerization step. 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, myristylbenzenesulfonic acid, or anionic surfactants of the sodium salts. of these acids; octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, octyl dimethylbenzylammonium hydroxide, decyldimethylbenzylammonium hydroxide, dioctadecyldimethylammonium hydroxide, beef tallow hydroxide trimethylammonium, 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 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 sufficiently good sensation on the skin or touch, nor sufficient spreading properties nor a pleasant sensation.

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

A vinyl polymer that is suitable for the invention may also be one of the polymers described in the examples of application EP 0 963 751.

According to a preferred embodiment, a vinyl polymer grafted with a carbosiloxane dendrimer may be derived from the polymerization:

(Al) from 0 to 99.9 parts by weight of one or more acrylate or methacrylate monomer (s); and

(B1) from 100 to 0.1 parts by weight of an acrylate or methacrylate monomer of a tri [tri (trimethylsiloxy) silylethyl dimethylsiloxy] silylpropyl carbosiloxane dendrimer.

The monomers (Al) and (Bl) correspond respectively to monomers

(A) and (B) particular.

According to one embodiment, a vinyl polymer having at least one unit derived from carbosiloxane dendrimer may comprise a unit derived from tri [tri (trimethylsiloxy) silylethyl dimethylsiloxy] silylpropyl carbosiloxane dendrimer, corresponding to one of the formulas:

or

CH, CH,

H, C = CH-C-O-C ₃ H ₆ - Si -O-Si-C ₂ H-Si-O-Si-CH,

2 I I

O CH, CH,

According to one preferred embodiment, a vinyl polymer having at least one carbosiloxane dendrimer derived unit used in the invention comprises at least one butyl acrylate monomer.

According to one embodiment, a vinyl polymer may further comprise 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) _x - (CF 2) _y -R ¹³ are suggested by way of example 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 fluorine-substituted alkyl groups are exemplified by linear or branched polyfluoroalkyl or perfluoroalkyl groups represented by the formulas set forth 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 Fi ₃ , -nC ₈ Fi ₇ , -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 ) i ₀ F, -CH ₂ CH ₂ (CF ₂ ) i ₂ F , -CH ₂ CH 2 (CF ₂₎ I4F, -CH ₂ CH ₂ (CF ₂₎ i F _6, -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 )] - OC ₃ F ₇ are suggested as fluoroalkyloxyfluoroalkylene groups obtained by substituting fluorine atoms for atoms. of hydrogen 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 )] - OC ₃ F ₇ , -CH ₂ CH ₂ CF ₂ CF ₂ - [OCF ₂ CF (CF ₃ )] "- OC ₃ F ₇ .

The number average molecular weight of the vinyl polymer used in the present invention may range from about 3,000 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 (M2) without a fluorinated organic group,

on a vinyl monomer (III) containing fluorinated organic groups, and

a carbosiloxane dendrimer (B) as defined above of general formula (I) as defined above,

by subjecting them to copolymerization.

Thus, according to one embodiment, a composition of the invention may comprise a vinyl polymer having at least one unit derived from carbosiloxane dendrimer and originating from the copolymerization of a vinyl monomer (M1) as defined above, optionally a vinyl monomer (M2) as defined above, and a carbosiloxane dendrimer (B) as defined above,

said vinyl polymer having a copolymerization ratio between the monomer (M1) and the monomer (M2) of from 0.1 to 100: 99.9 to 0% by weight, and a copolymerization ratio of the sum of the monomers (M1) and (M2) and the monomer (B) from 0.1 to 99.9: 99.9 to 0.1% by weight.

The vinyl monomers (III) containing fluorinated organic groups in the molecule are preferably monomers represented by the general formula:

(CH ² ) = CR ¹⁵ COOR ^f . In this 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. The compounds represented by the formulas presented below are suggested as specific examples of the component (M1). 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 F ₅ , 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 (CF ₃ ) ₂ , CH ₂ = CCH ₃ COO-nC ₅ Fi i,

CH ₂ = CCH ₃ COO-nC ₆ Fi ₃ ,

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 ) ₂ F, CH 2 = CCH ₃ COO-CH ₂ (CF ₂ ) 2F,

CH 2 = CCH ₃ COO-CH ₂ (CF ₂ ) 4F, CH 2 = CCH ₃ COO-CH ₂ (CF ₂ ) 6F,

CH ₂ = CCH ₃ COO-CH ₂ (CF ₂ ) 8F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF ₃ ,

CH ₂ = CCH ₃ COO-CH ₂ CH 2 (CF 2) 2 F, CH 2 = CCH ₃ COO-CH 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) 6F,

CH 2 = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) 8F, CH 2 = CH ₃ COO-CH ₂ CH ₂ (CF ₂ ) 10F, CH ₂ = CH ₃ COO-CH ₂ CH ₂ (CF 2) 12F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF 2) 14F, CH ₂ = CCH ₃ COO-CH 2 -CH 2 - (CF ₂ ) 16F, CH 2 = CCH 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-CH2CH2CH2 (CF ₂₎ 2 H, CH ₂ = CCH ₃ COO-CH ₂ (CF ₂₎ ₄ H, CH ₂ = CCH ₃ COO (CF ₂₎ ₃ H,

CH 2 = CCH ₃ COO-CH ₂ CH ₂ CF (CF ₃ ) - [OCF 2 -CF (CF ₃ )] z-OC ₃ F ₇ ,

CH ₂ = CCH ₃ COO-CH ₂ CH ₂ CF ₂ CF ₂ - [OCF ₂ -CF (CF ₃ )] z-OC 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-nC ₄ F ₉ , CH ₂ = CHCOO-CF ₂ CF (CF ₃ ) ₂ , CH ₂ = CHCOO-nC ₅ Fn, CH ₂ = CHCOO- nC ₆ Fi ₃ ,

CH ₂ = CHCOO-CH ₂ CF ₃ , CH ₂ = CHCOO-CH (CF ₃ ) ₂ ,

CH ₂ = CHCOO-CH ₂ CH (CF ₃ ) ₂ ,

CH 2 = CHCOO-CH ₂ (CF ₂ ) 2F, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₃ F,

CH 2 = CHCOO-CH ₂ (CF ₂ ) 4F, CH 2 = CHCOO-CH ₂ (CF ₂ ) 6F,

CH ₂ = CHCOO-CH ₂ (CF ₂ ) 8F, 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 ₂ ) ₃ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF 2) 4F, CH ₂ = CHCOO-CH ₂ CH2 (CF2) 6F, CH 2 = CHCOO-CH ₂ CH ₂ (CF ₂ ) 8F, CH ₂ = HCOO-CH ₂ CH ₂ (CF ₂ ) ₁₀ F, CH ₂ -CHCOO-CH ₂ CH ₂ - (CF ₂ ) ₂ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₄ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ CF ₃ , CH ₂ = CHCOO -CH ₂ CH ₂ CH ₂ (CF ₂ ) ₂ F, CH ₂ = CHCOO-CH ₂ CH ₂ CH ₂ (CF) ₂ H, CH ₂ = CHCOO-CH ₂ (CF ₂ ) ₄ H, CH ₂ = CHCOO- CH ₂ CH ₂ (CF ₂₎ ₃ H,

CH ₂ = CHCOO-CH ₂ CH ₂ CF (CF ₃₎ - [OCF ₂ CF (CF _3)] _z -O-C ₃ F _7,

CH ₂ = CHCOO-CH ₂ CH ₂ CF ₂ CF ₂ (CF ₃ ) - [OCF ₂ -CF (CF ₃ )] ₂ -OC ₃ F ₇ .

Among these, the vinyl polymers represented by the formulas presented below are preferred:

CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ = CHCOO-CH ₂ CH ₂ (CF ₂ ) ₈ F,

CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) ₆ F, CH ₂ = CCH ₃ COO-CH ₂ CH ₂ (CF ₂ ) 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 preferred:

CH ₂ = CHCOO-CH ₂ CF ₃ , CH ₂ = CCHCOO-CH ₂ CF ₃ .

The vinyl monomers (M2) 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, 2-ethylhexanoate vinyl, vinyl laurate, vinyl stearate, and other higher fatty acid esters; styrene, vinyltoluene, benzyl acrylate, methacrylate benzyl, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone, and other vinyl aromatic monomers; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and other vinyl amino monomers, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide N-methoxymethacrylamide, isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, Ν, Ν-dimethylacrylamide, Ν, Ν-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 mono-methacrylate, 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 styrenesulphonic acid and their alkali metal salts, their salts ammonium 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 (M2), 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) isocyanurate, 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 (M1) and (M2) are copolymerized, the weight ratio between (M1) and (M2) is preferably in the range 1: 99 to 100: 0.

Y may be chosen, for example, from organic groups containing acrylic or methacrylic groups, organic groups containing alkenylaryl groups, or alkenyl groups of 2 to 10 carbon atoms.

The organic groups with acrylic or methacrylic groups and the alkenylaryl groups are as defined above.

Among the compounds (B), there may be mentioned, for example, the following compounds:

The carbosiloxane dendrimers (B) can be prepared using the preparation method for the branched siloxane / silakylene copolymers described in EP 1 055 674.

For example, they can be prepared by subjecting organic silicone compounds to alkenyl and silicone compounds comprising silicon-bonded hydrogen atoms, represented by the formula (IV) as defined above,

to a hydrosilylation reaction.

The copolymerization ratio (by weight) between the monomer (B) and the monomers (M1) and (M2) is preferably in the range of from 1: 99 to 99: 1, and even more preferably in the range of from : 95 to 95: 5.

Amino groups may be introduced into the side chains of the vinyl polymer using, included in the component (M2), 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 ammomethylpropanol 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 the component (M2), 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. A fluorinated vinyl polymer may be one of the polymers described in the examples of application WO 03/045337.

According to a preferred embodiment, a grafted vinyl polymer in the sense of the present invention may be carried in an oil or a mixture of oil (s), preferably volatile (s) in particular, chosen (s) from the oils of silicones and hydrocarbon oils and mixtures thereof.

According to another particular embodiment, a hydrocarbon oil suitable for the invention may be isododecane.

The vinyl polymers grafted with at least one unit derived from carbosiloxane dendrimer which may be particularly suitable for the present invention are the polymers sold under the names TIB® 4-100, TIB® 4-101, TIB® 4-120, TIB® 4-130. , TIB® 4-200, FA® 4002 ID (TIB® 4-202), TIB® 4-220, FA® 4001 CM (TIB® 4-230) by Dow Corning.

According to a preferred embodiment, the vinyl polymer grafted with a carbosiloxane dendrimer is the acrylate / polytrimethylsiloxymethacrylate copolymer sold under the name FA® 4002 ID Silicone Acrylate by Dow Corning. This copolymer is commonly available in solution in isododecane.

According to a preferred embodiment, a film-forming polymer according to the invention, when present in a composition according to the invention, is chosen from:

non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

aqueous latices;

the pseudoblocks fibromogens; and

vinyl polymers grafted with a carbosiloxane dendrimer.

According to a particularly preferred embodiment, a film-forming polymer according to the invention, when present in a composition according to the invention, is chosen from:

non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

aqueous latices; and the pseudoblocks filmmakers.

According to a more particularly preferred embodiment, a film-forming polymer according to the invention, when present in a composition according to the invention, is chosen from:

non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

aqueous latices;

the ethylenic polymers forming films; and

dispersions of polymeric particles.

A composition according to the invention may comprise at least one film-forming polymer as defined above in a content of between 0.2% and 6% by weight of active material, preferably between 0.5% and 3% by weight, and also more preferably between 0.75% and 1.5% by weight of active material relative to the total weight of the final composition, that is to say when the propellants are considered.

In particular, for a weight ratio between the liquid phase and the propellant gas of 15/85, a composition according to the invention may comprise at least one film-forming polymer as defined above in a content of between 0.15% and 1.5%. % by weight of active material, preferably between 0.3% and 1.2% by weight, and even more preferably between 0.45% and 0.9% by weight of active material relative to the total weight of the final composition , that is to say when the propellants are considered.

A composition according to the invention may comprise at least one film-forming polymer as defined above in a content of between 0.5% and 8% by weight of active material, preferably between 0.7% and 3% by weight, and more preferably between 0.75% and 1.5% by weight of active material relative to the total weight of the liquid phase, that is to say when the propellants are not considered. When at least one film-forming polymer is present in a composition according to the invention, the superhydrophobic particle combination as defined above and Film-forming polymers as defined above makes it possible to form a superhydrophobic deposit on the surface of keratin materials, in particular the skin.

This deposit is resistant to water, perspiration and friction. However, it has been found that this deposit remains permeable to drops of sweat.

When the drops of water and the sweat beads come into contact with such a superhydrophobic surface, they tend to shrink their contact surface and adopt an almost round or spherical shape (contact angle greater than 150 °). This characteristic at the level of the shape allows drops of water (or sweat) to "slide" on the keratin materials coated with the composition according to the invention.

Thus, water and sweat are evacuated very easily, leaving an impression of "dry" on keratin materials.

SOLVENT VOLATIL

The composition also comprises at least one volatile solvent.

For the purposes of the invention, the term "volatile solvent" means a compound which is liquid at ambient temperature (20 ° C.) and at atmospheric pressure and has a vapor pressure at 20 ° C. of greater than 0.1 mmH and preferably between 0.1 and 300 mmHg, still more preferably between 0.5 and 200 mmHg.

This volatile solvent may be a non-silicone organic solvent, a silicone organic solvent or mixtures thereof.

Preferably, the solvent is selected such that its boiling point is below 200 ° C.

A volatile solvent that is suitable for the invention can be chosen from:

volatile hydrocarbon oils such as those chosen from:

- petroleum distillates,

volatile linear alkanes, in particular C8-C16 linear alkanes, such as an undecane / tridecane mixture; C2-4 monoalcohols such as ethanol, isopropanol and propanol;

volatile alkyltrisiloxane linear oils of general formula (Ia):

- their mixtures.

Among the oils of general formula (I), mention may be made of:

3-butyl 1,1,1,3,5,5,5-heptamethyltrisiloxane,

3-propyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and

3-ethyl-1,1,1,3,5,5,5-heptamethyltrisiloxane,

corresponding to the oils of formula (I) for which R is respectively a butyl group, a propyl group or an ethyl group.

The proportion of volatile oil (s) relative to all the oils, preferably varies from 50% to 100% by weight.

According to a preferred variant, a volatile solvent that is suitable for the invention is chosen from: hydrocarbon oils having from 8 to 16 carbon atoms, and in particular C 5 -C 16 isoalkanes of petroleum origin, such as isododecane, isodecane, and isohexadecane,

linear Cs-C16 alkanes such as an undecane / tridecane mixture, and

- their mixtures.

More particularly, a volatile solvent suitable for the invention is isododecane.

As volatile hydrocarbon oils chosen from hydrocarbon-based oils, mention may be made especially of the oils sold under the trade names Isopars ™ by the company Exxonmobil Chemical or Permethyls® by the company INEOS or PRESPERSE INC.

As volatile hydrocarbon oils chosen from petroleum distillates, it is possible especially to use those sold under the name Shell® or by the company Shell.

By way of example of volatile linear alkanes, mention may be made of those described in DE 102008012457 in the name of the company COGNIS.

According to one particular embodiment, the volatile solvents that are suitable for the invention can be chosen from:

isododecane;

ethanol;

isopropanol;

hexamethyl disiloxane and

their mixtures.

According to a particular preferred embodiment, the volatile solvents that are suitable for the invention can be chosen from:

isododecane;

ethanol;

isopropanol; and

hexamethyl disiloxane. A composition according to the invention may comprise at least one volatile solvent as defined above in a content of between 5% and 89% by weight, preferably between 10% and 50% by weight, and even more preferably between 13% and 20% by weight. % by weight relative to the total weight of the final composition, that is to say when the propellants are considered.

In particular, for a weight ratio between the liquid phase and the propellant gas of 15/85, a composition according to the invention may comprise at least one volatile solvent as defined above in a content of between 8.25% and 14.25 % by weight, preferably between 9% and 13.95% by weight, even more preferably between 10.5% and 13.65% by weight, and more preferably between 12% and 13.5% by weight relative to the weight total of the final composition, that is to say when the propellants are considered.

A composition according to the invention may comprise at least one volatile solvent as defined above in a content of between 55% and 95% by weight, preferably between 60% and 93% by weight, even more preferably between 70% and 91%. by weight, and more preferably between 80 and 90% by weight relative to the total weight of the liquid phase, that is to say when the propellants are not considered. ACCEPTABLE PHYSIOLOGICAL ENVIRONMENT

As explained above, a composition according to the invention is cosmetic.

A composition according to the invention being intended for topical application to keratinous substances, in particular the skin (body and face), it contains a physiologically acceptable medium.

For the purposes of the present invention, the term "physiologically acceptable medium" means a medium compatible with keratinous substances, in particular with the skin (body and face).

Thus, the physio logically acceptable medium is in particular a cosmetically acceptable medium, that is to say without odor, color or unpleasant appearance, and that does not generate tingling, tightness or redness unacceptable to the user. PROPULSEUR AGENT

As indicated above, a composition (i.e. final composition) according to the invention comprises at least one propellant.

Among the propellants suitable for the present invention, well known to those skilled in the art, mention may be made of dimethyl ether (DME), volatile hydrocarbons such as C 3 -C 5 alkanes, such as propane, isopropane, n-butane, isobutane, n-pentane, isopentane and mixtures thereof, optionally with at least one chlorinated and / or fluorinated hydrocarbon; among these, mention may be made of the compounds sold by the company Dupont de Nemours under the trade names Fréon® and Dymel®, and in particular monofluoro trichloromethane, difluorodichloromethane, tetrafluorodichloroethane and 1,1-difluoroethane sold under the trade name Dymel ® 152 A by the company Dupont de Nemours.

It is also possible to use as propellant compressed air, nitrogen, and mixtures thereof.

Preferably, a propellant suitable for the invention is chosen from volatile hydrocarbons, more preferably from C3-5 alkanes and in particular isobutane, and mixtures thereof.

According to a particularly preferred embodiment, a propellant suitable for the invention is isobutane.

As indicated above, the weight ratio between the liquid phase and the propellant gas varies in a ratio of 5/95 to 50/50, preferably from 10/90 to 40/60, more preferably from 15/85 to 30/70, even better is 15/85 or 20/80.

According to one particular variant, when the liquid phase does not comprise any polymer (s) forming the film (s), the weight ratio between the liquid phase and the propellant gas varies in a ratio of 5/95 to 50/50, preferably 10/50. / 90 to 40/60, more preferably 15/85 to 30/70, or even better is 20/80.

According to another variant, when the liquid phase comprises at least one film-forming polymer, the weight ratio between the liquid phase and the propellant gas varies in a ratio of 5/95 to 50/50, preferably from 10/90 to 40/60. more preferably from 15/85 to 30/70, or even better is 15/85.

The propellant (s) is (are) present in the final composition according to the invention in an amount ranging from 10 to 95% by weight, preferably from 15 to 90% by weight. weight, and more preferably from 20 to 85% by weight relative to the total weight of the final composition.

Additives

A composition according to the invention may further comprise one or more additional agents chosen from antioxidants, preservatives, UV filters, thickening agents, perfumes, neutralizers, surfactants, gelling agents, sequestering agents, humectants , opacifiers, emollients, bactericides, polymers other than the thermoplastic polymers that are suitable for the invention, vitamins, or any other ingredient conventionally used in the cosmetic field, and mixtures thereof.

Similarly, a composition according to the invention may further comprise at least one dyestuff chosen for example from pigments, nacres, dyes, effect materials, and mixtures thereof.

Also, according to the desired application, a composition according to the invention may further comprise at least one active agent selected from moisture-absorbing agents, deodorant active agents, antiperspirant agents, healing agents and / or anti-inflammatory agents. age of the skin.

According to a particular embodiment, a composition according to the invention may further comprise at least one antiperspirant active agent and / or at least one deodorant active agent.

For the purposes of the invention, the term "antiperspirant active agent" is intended to mean a salt which, by itself, has the effect of reducing the flow of sweat, of reducing the sensation on the skin of moisture associated with human sweat or to hide human sweat.

Among the antiperspirant active agents, mention may be made of aluminum and / or zirconium salts, aluminum and / or zirconium complexes, and their mixtures, preferably chosen from aluminum halohydrates, aluminum halohydrates and aluminum and zirconium, complexes of zirconium hydroxychloride and aluminum hydroxychloride with or without an amino acid such as those described in US-3792068, and mixtures thereof.

Among the aluminum salts, mention may in particular be made of aluminum chlorohydrate in activated or non-activated form, aluminum chlorohydrex, chlorohydrex polyethylene glycol aluminum complex, aluminum chlorohydrexpropyleneglycol complex, aluminum dichlorohydrate, aluminum dichlorohydrex complex polyethylene glycol, aluminum complex dichlorohydrex propylene glycol, sesquichlorohydrate aluminum, sesquichlorohydrex aluminum polyethylene glycol complex, sesquichlorohydrex propylene glycol aluminum complex, aluminum sulphate buffered with sodium aluminum lactate.

Among the aluminum and zirconium salts, there may be mentioned in particular aluminum zirconium octachlorohydrate, aluminum zirconium pentachlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium trichlorohydrate.

The complexes of zirconium hydroxychloride and aluminum hydroxychloride with an amino acid are generally known under the name ZAG (when the amino acid is glycine). Among these products, mention may be made of aluminum complexes of zirconium octachlorohydrex glycine, aluminum zirconium pentachlorohydrex glycine, aluminum zirconium tetrachlorohydrex glycine and aluminum zirconium trichlorohydrex glycine.

Sesquichlorohydrate aluminum is sold in particular under the trade name REACH 301® by SUMMITREHEI S.

Among the complexes of aluminum and zirconium, mention may be made of complexes of zirconium hydroxychloride and of aluminum hydroxychloride with an amino acid such as glycine having the INCI name: ALUMINUM ZIRCONIUM TETRACHLOROHYDREX GLY for example that marketed under the name REACH AZP-908-SUF® by the company SUMMITREHEIS.

More particularly, the aluminum chlorohydrate sold under the trade names LOCRON S FLA®, LOCRON P and LOCRON L.ZA by the company CLARIANT will be used; under the trade names MICRODRY ALUMINUM CHLOROHYDRATE®, MICRO-DRY 323®, CHLORHYDROL 50, REACH 103, REACH 501 by the company SUMMITREHEIS; under the trade name WESTCHLOR 200® by WESTWOOD; under the trade name ALOXICOLL PF 40® by the company GUILINI CHEMIE; CLURON 50% ® by INDUSTRIA QUIMICA DEL CENTRO; CLOROHIDROXIDO ALUMINIO SO A 50% ® by the company FINQUIMICA.

Thus, according to a preferred embodiment, the antiperspirant active agent may be chosen from aluminum and / or zirconium salts, aluminum and / or zirconium complexes, and their mixtures, preferably chosen from aluminum halohydrates, aluminum and zirconium halohydrates, complexes of zirconium hydroxychloride and aluminum hydroxychloride with or without an amino acid, and mixtures thereof.

The antiperspirant active agents may be present in the composition according to the invention in a content of between 0.001% and 30% by weight, preferably between 0.5% and 25% by weight, relative to the total weight of the final composition. , that is to say when the propellants are considered.

Deodorant active means any substance capable of masking, absorbing, improving and / or reducing the unpleasant odor resulting from the decomposition of human sweat by bacteria

The deodorant active agents may be bacteriostatic agents or bactericidal agents acting on the germs of axillary odors, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan®), 2,4-dichloro-2'- hydroxydiphenyl ether, 3 ', 4', 5'-trichlorosalicylanilide, 1- (3 ', 4'-dichlorophenyl) -3- (4'-chlorophenyl) urea

(Triclocarban®) or 3,7,1-trimethyldodeca-2,5,10-trienol (Farnesol®); quaternary ammonium salts such as cetyltrimethylammonium salts, cetylpyridinium salts; polyols such as those of glycerol type, 1,3-propanediol (ZEMEA PROPANEDIOL® marketed by Dupont Tate and Lyle Bioproducts), 1,2-decanediol (SymClariol® from Symrise); glycerol derivatives, for example Caprylic / Capric Glycerides (CAPMUL MCM® from Abitec), Caprylate or Glycerol caprate (DERMOSOFT GMCY® and DERMOSOFT GMC® respectively from STRAETMANS), Polyglyceryl-2 Caprate (DERMOSOFT DGMC® from STRAETMANS ) biguanide derivatives such as polyhexamethylene biguanide salts; chlorhexidine and its salts; 4-Phenyl-4,4-dimethyl-2-butanol (SYMDEO MPP® from Symrise); cyclodextrins; chelating agents such as Tetrasodium Glutamate Diacetate (CAS # 51981-21-6) sold under the trade name DISSOLVINE GL-47-S® by Akzo Nobel, EDTA (Ethylendiamino Tetraacetic acid) and DPTA (1,3-acid); diaminopropanetraacetic).

Among the deodorant active agents according to the invention, mention may also be made of: zinc salts such as zinc salicylate, zinc phenolsulfonate, zinc pyrrolidone carboxylate (more commonly known as zinc pidolate), zinc sulphate, zinc chloride, zinc lactate, zinc gluconate, zinc ricinoleate, zinc glycinate, zinc carbonate, zinc citrate, zinc laurate, zinc oleate, zinc orthophosphate, zinc stearate, zinc tartrate, acetate zinc or mixtures thereof;

odor absorbers such as zeolites, especially metallic zeolites, the cyclodextrins, the metal oxide silicates such as those described in the application US2005 / 063928; transition metal-modified metal oxide particles as described in US2005084464 and US2005084474, aluminosilicates such as those described in EP1658863, particles of chitosan derivatives such as those described in US6916465;

- sodium bicarbonate;

salicylic acid and its derivatives such as n-octanoyl-5-salicylic acid; - Moon ;

triethyl citrate; and

- their mixtures.

Thus, according to a preferred embodiment, the deodorant active agent can be chosen from:

bacteriostatic agents or bactericidal agents acting on the germs of axillary odors, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 2,4-dichloro-2'-hydroxydiphenyl ether, 3 ', 4' 5'-trichlorosalicylanilide, 1- (3 ', 4'-dichlorophenyl) -3- (4'-chlorophenyl) urea or 3,7,11-trimethyldodeca-2,5,10-trienol;

quaternary ammonium salts such as cetyltrimethylammonium salts, cetylpyridinium salts;

polyols such as those of the glycerin, 1,3-propanediol or 1,2-decanediol type;

glycerin derivatives, for example Caprylic / Capric

Glycerides, Caprylate or Glycerol Caprate, Polyglyceryl-2 Caprate; biguanide derivatives, such as polyhexamethylene biguanide salts;

- chlorhexidine and its salts;

4-Phenyl-4,4-dimethyl-2-butanol;

cyclo dextrins;

chelating agents such as Tetrasodium Glutamate Diacetate, EDTA and DPTA;

zinc salts such as zinc salicylate, zinc phenol sulphonate, zinc pyrrolidone carboxylate, zinc sulphate, zinc chloride, zinc lactate, zinc gluconate, zinc ricinoleate, glycinate of zinc zinc, zinc carbonate, zinc citrate, zinc laurate, zinc oleate, zinc orthophosphate, zinc stearate, zinc tartrate, zinc acetate or mixtures thereof;

odor neutralizers such as magnesium oxide;

odor absorbers such as zeolites, in particular metallic zeolites, no silver, cyclodextrins, metal oxide silicates; transition metal-modified metal oxide particles, alumino silicates, particles of chitosan derivatives;

- sodium bicarbonate;

salicylic acid and its derivatives such as n-octanoyl-5-salicylic acid;

- Moon ;

triethyl citrate; and

- their mixtures.

The deodorant active agents may be present in the composition according to the invention in a content of between 0.001% and 20% by weight, preferably between 0.5% and 10% by weight, relative to the total weight of the final composition. that is, when the propellants are considered. A composition according to the invention may also comprise at least one oil such as glycerol; propylene glycol; triglyceride mixtures of caprylic / capric acids); fatty alcohols such as oleyl alcohol; PEG 8; esters of synthesis especially of fatty acids such as the oils of formula R1COOR2 in which R1 represents the residue of a linear or branched higher fatty acid containing from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain, especially branched, containing from 1 to 40 atoms carbon with the sum Ri + R ₂ greater than or equal to 10, for example isopropyl palmitate and isononyl isonanoate; synthetic ethers having 10 to 40 carbon atoms such as PPG stearyl ether; non-volatile polar silicone oils such as PDMS (polydimethylsiloxane) is; hydrogenated isoparaffin; non-volatile nonpolar hydrocarbon oils such as hydrogenated polydecene; mineral oils such as paraffinum liquidum, etc.

Thus, for obvious reasons, those skilled in the art will take care to choose any additional ingredients or compounds and / or their quantity, especially from those mentioned above, in view of the intended use but also in such a way that the advantageous properties of the composition according to the invention are not or not substantially impaired by the addition envisaged.

Of course, all the aforementioned additional agents or compounds are different from superhydrophobic particles as well as film-forming polymers, volatile solvents and propellants described above. These additives may be present in the composition according to the invention in an amount ranging from 0% to 30% by weight relative to the total weight of the final composition.

COMPOSITION

The compositions according to the invention can be prepared according to the techniques well known to those skilled in the art.

For example, a composition according to the invention may be in any galenical form conventionally employed for the topical applications envisaged and in particular in the form of an anhydrous composition or an inverse emulsion.

The composition according to the invention comprises less than 5% by weight of water relative to the total weight of the final composition. Preferably, the composition according to the invention comprises less than 2% by weight, or even less than 1% by weight of water relative to the total weight of the final composition.

Even more preferentially, the composition according to the invention is anhydrous.

By "anhydrous" is meant in particular that the water is not deliberately added to the composition according to the invention but may be present in trace amounts in the various compounds used in the final composition.

According to a particular embodiment, a composition according to the invention is devoid of (free) volatile cyclic silicones.

According to a particularly preferred embodiment, a composition according to the invention is devoid (free) of cyclopentasiloxane.

As indicated above, the composition according to the invention is in aerosol form. It can therefore be pressurized and packaged in an aerosol device.

The propellant (s) (propellant) may be present in the composition or, alternatively, in the container containing the composition, but separated from the composition.

It follows that a final composition according to the invention can either be contained as such in the same compartment of the container that the propellant gas is formed at the outlet of the container by placing in the presence of the liquid phase according to the invention. invention and propellant.

Thus, according to a first variant, the propellant (s) are present in the composition according to the invention.

The corresponding aerosol device is then constituted by:

(A) a container comprising a composition (final composition) as defined above,

(B) at least one means for dispensing said composition.

According to another variant, the propellant (s) are present in the container containing the composition according to the invention but separately.

The corresponding aerosol device is then constituted by:

(A) a container comprising a composition (liquid phase) as defined above, (B) at least one propellant and at least one means for dispensing said composition.

The dispensing means, which forms part of the aerosol device, is generally constituted by a dispensing valve controlled by a dispensing head, itself comprising a nozzle through which the aerosol composition is vaporized.

The compositions in accordance with the invention are packaged in an aerosol device comprising a container, also called a reservoir.

The container is pressurized and comprises the composition to be delivered. The container containing the pressurized composition may be opaque or transparent. It may be glass, polymeric material or metal, optionally covered with a layer of protective varnish.

As already mentioned above, the container contains both the propellant (s) and the other ingredients of the composition, in a single compartment, or alternatively in two separate compartments.

According to this last variant, the container may be constituted by an external aerosol can comprising an internal bag hermetically welded to a valve. The various ingredients of the composition are introduced into the inner bag and at least one propellant is introduced between the bag and the can at a pressure sufficient to release the product in the form of a spray. The container is equipped at its upper end with a valve ensuring the tightness of the system. On this valve, comes to adapt a dispensing means on which the user can press to cause the output of the product. This distribution means is also called diffuser.

The application time of a cosmetic composition according to the invention on the surface of the keratin materials, in particular the skin (face and / or body) may vary from 0.5 to 10 seconds, preferably from 1 to 5 seconds. .

A cosmetic composition according to the invention can be applied several times in a single day on the surface of keratin materials, in particular the skin (face and / or body).

According to one embodiment, a composition of the invention may advantageously be in the form of a skincare composition for the body or face, in particular the face. According to another embodiment, a composition of the invention may advantageously be in the form of a make-up composition for the makeup of the skin of the body or face, in particular of the face.

According to another embodiment, a composition of the invention may advantageously be in the form of a foundation.

According to another embodiment, a composition of the invention may advantageously be in the form of a sunscreen composition.

According to another embodiment, a composition of the invention may advantageously be in the form of a deodorant and / or antiperspirant composition.

Such compositions are especially prepared according to the general knowledge of those skilled in the art.

The superhydrophobic film obtained by application to the surface of the keratin materials of a cosmetic composition according to the invention in aerosol form can then be removed by cleaning the keratin materials with soap and water without having to scrub vigorously.

Throughout the description, the phrase "having one" should be understood as being synonymous with "having at least one", unless the opposite is specified.

Expressions "between ... and ...", "from ... to ..." and "varies from ... to ..." must be understood as inclusive, unless otherwise specified.

In the description and examples, percentages are percentages by weight. The ingredients are mixed in the order and under the conditions readily determined by those skilled in the art.

EXAMPLES

Characterization method of lotus effect

The test according to the invention is deposited on skin, suplale or other support using an aerosol.

We spray the aerosol vertically, for 2 seconds at 20 cm of a support type "suplale" (dimension 10 x 10 cm).

Allowed to dry a few minutes at room temperature (21 ° C), the deposit thus created flat on the bench (5 minutes to be sure)

Then we just put a drop of demineralized water on the dry deposit with a pipette.

And finally, we evaluate the appearance and adhesion of this drop on the surface of the deposit. The appearance of the drop, whether it is spherical (slightly oval because of gravity) if it is half-sphere or spreading)

Aspect of gout:

- Quasi- spherical -> hydrophobia

- Partially hydrophobic half-sphere

- Hydrophilic effect spreading

Adherence:

- If the drop adheres, it means that the observed phenomenon is only

Γ hydrophobicity.

- On the other hand, if the drop rolls, it is super-hydrophobic: the Lotus effect is thus observed. When we say that the drop rolls, it means that following a low stress induced, for example, by a slight movement of suplale flat, or leaning slightly, or by blowing slightly, the drop rolls.

- And finally, if the drop has an intermediate behavior, that is to say that the drop can roll, either by leaning more frankly suplale or if it can be moved with a pipette and that the drop then comes off and rolls, it is a so-called "sticky" lotus effect. The table below summarizes the different effects that can be observed.

EXAMPLE 1 Compositions in Aerosol Form According to the Invention

Beforehand, it should be noted that the weight percentages of film-forming polymers (when present) are expressed as a percentage by weight of active material.

As indicated in Tables 1 and 2 below, seven compositions according to the invention were prepared according to the procedure described below and containing the ingredients mentioned in the two aforementioned tables.

They differ according to the presence or absence of the film-forming polymer, the nature of the film-forming polymer (when present in a composition according to the invention) and / or that of the volatile solvent used, all the other ingredients remaining unchanged elsewhere. .

In addition, these compositions are such that the weight ratio between the liquid phase and the propellant gas, namely isobutane for this example, is 15/85 (presence of at least one film-forming polymer in the composition) or 20 / 80 (absence of film-forming polymer in the composition). Thus, especially for a weight ratio of 15/85, 0.75% by weight of active material of film-forming polymers relative to the total weight of the final composition corresponds to 5% by weight of film-forming polymer active material relative to the total weight of the liquid phase.

Table 1

Composition 1 Composition 2 Composition 3

INCI name / Trade name / aspect

invention invention

ACRYLIC ACID / ISOBUTYL ACRYLATE /

ISOBORNYL ACRYLATE COPOLYMER

marketed under the name Mexomer® PAS by the 0.75 - - Chimex company

(solution in isododecane)

copolymer (Methyl Acrylate) -co- (Acrylate d

Ethyl) -co- (Isobornyl Acrylate) -co- (MPDMS

12k) (37.5 / 37.5 / 20/5 synthesized by the company - 0.75 - Chimex

(Dispersion in isododecane)

ACRYLATE /

POLYTRIMETHYLSILOXYMETHACRYLATE COPOLYMER sold under the name of

FA® 4002 ID SILICONE ACRYLATE by the company - - 0,75

DOW CORNING

(Solution in isododecane)

HEXAMETHYL DISILOXANE

Marketed under the name BELSIL DM 0.65 ® - 13.25 - by WACKER

ISODODECANE 13.25 - -

ISOPROPANOL - - 13.25

SILICA SILICA sold under the name of

VM-2270® AEROGEL FINE PARTICLES by the 1 1 1

DOW CORNING company

ISOBUTANE 85 85 85

TOTAL 100 100 100 Table 2

Operating mode

1. Preparation of the aerosol juice

- Weigh the polymer (when present), SILICALATE SILICA and ethanol - Shake in order to create a cold vortex under Rayneri and under fume cup until homogenization

2. Aerosol Pressurization in a 15/85 Scheme (or in a 20/80 Scheme)

- Weigh 15g (or 20g) of juice then crimp the can of aerosol

- Add 85g (or 80g) of gas

- Shake the aerosol before use.

All compositions 1 to 7 are superhydrophobic after in vitro observation of the appearance and adhesion of a drop of water to the surface of the deposit created.

The compositions 1 to 7 in accordance with the invention make it possible to obtain a superhydrophobic deposit on the surface of the keratin materials to which they have been applied.

It is found that this deposit is resistant to perspiration, water and friction as well skin against skin as tissue against skin.

Indeed, due to the lotus effect, in case of perspiration, almost round sweat drops slip and are easily removed, leaving a "dry" deposit on the keratin materials and in particular the skin.

Claims

1. Cosmetic composition in the form of an aerosol comprising in a physiologically acceptable medium:

(a) at least one of superhydrophobic particles selected from;

superhydrophobic acrylic acid copolymer powders; and

- their mixtures;

(b) at least one volatile solvent;

(c) at least one propellant.

2. Composition according to claim 1, in which the superhydrophobic particles are chosen from:

superhydrophobic silica airgel particles and super hydrophobic acrylic acid copolymer powders, and even more preferably from superhydrophobic silica airgel particles.

3. Composition according to claim 1 or 2, wherein the superhydrophobic silica airgel particles have a specific surface per unit mass (S _M ) ranging from 600 to 1200 m ² / g and better still from 600 to 800 m ² / boy Wut.

A composition according to any one of claims 1 to 3, wherein the superhydrophobic silica airgel particles have an oil absorption capacity measured at WET POINT ranging from 5 to 18 ml / g of particles, preferably from 6 to 15 ml / g and better still from 8 to 12 ml / g.

5. Composition according to any one of claims 1 to 4, wherein the superhydrophobic silica airgel particles have a size expressed in volume mean diameter (D [0.5]), ranging from 1 to 1500 μιη, better to 1 to 1000 μιη, preferably ranging from 1 to 100 μιη, in particular from 1 to 30 μιη, more preferably from 5 to 25 μιη, better still from 5 to 20 μιη and better still from 5 to 15 μιη.

The composition of any one of claims 1 to 5, wherein the superhydrophobic silica airgel particles have a packed density of from 0.04 g / cm ³ to 0.10 g / cm ³ , preferably from 0.05 g / cm ³ to 0.08 g / cm ³ .

The composition of any one of claims 1 to 6, wherein the superhydrophobic silica airgel particles have a specific surface area per unit volume (Sv) of from 5 to 60 m ² / cm ³ , preferably 10 to 10 at 50 m ² / cm ³ and better from 15 to 40 m ² / cm ³ .

8. Composition according to any one of claims 1 to 7, wherein the superhydrophobic silica airgel particles are silylated silica airgel particles and in particular superhydrophobic silica airgel particles surface-modified with trimethylsilyl groups.

The composition of claim 1 or 2, wherein the superhydrophobic acrylic acid copolymer powders are selected from ethylene glycol dimethacrylate / lauryl methacrylate copolymer powders.

10. Composition according to any one of claims 1 to 9, wherein the superhydrophobic particles are present in a content of between 0.2% and 10% by weight, preferably between 0.5% and 5% by weight, and even more preferably between 1% and 3% by weight relative to the total weight of the final composition, that is to say when the propellants are considered.

11. Composition according to any one of claims 1 to 10, further comprising at least one film-forming polymer.

12. The composition according to claim 11, wherein the film-forming polymer is chosen from:

non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

aqueous latices;

the pseudoblocks filmmakers;

vinyl polymers grafted with a carbosiloxane dendrimer; and

- their mixtures;

preferably chosen from:

non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

aqueous latices;

the pseudoblocks filmmakers; and

vinyl polymers grafted with a carbosiloxane dendrimer; more preferably chosen from:

non-neutralized (meth) acrylic acid and N-tert-butylacrylamide copolymers;

aqueous latices; and

- the pseudoblocks filmmakers.

13. Composition according to claim 11 or 12, wherein the film-forming polymer is present in a content of between 0.2% and 6% by weight of active material, preferably between 0.5% and 3% by weight, and more preferably between 0.75% and 1.5% by weight of active material relative to the total weight of the final composition, that is to say when the propellants are considered.

14. Composition according to any one of claims 1 to 13, in which the volatile solvent is chosen from:

volatile hydrocarbon oils such as those chosen from:

hydrocarbon oils containing from 8 to 16 carbon atoms, in particular C 5 -C 16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and isohexadecane, and branched C 6 -C 16 esters such as isohexyl or isodecyic neopentanoate,

- petroleum distillates,

volatile linear alkanes, especially linear C 6 -C 16 alkanes, such as an undecane / tridecane mixture;

C2-4 monoalcohols such as ethanol, isopropanol and propanol;

volatile linear silicone oils, in particular those having a viscosity less than or equal to 8 centistokes (8 × 10 ^-6 m ² / s), and having in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, such as heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, hexamethyl disiloxane, hexamethylsiloxane;

volatile alkyltrisiloxane linear oils of general formula (Ia):

- their mixtures.

15. Composition according to any one of claims 1 to 14, in which the volatile solvent is present in a content of between 5% and 89% by weight, preferably between 10% and 50% by weight, and even more preferably between 13% and 50% by weight. % and 20% by weight relative to the total weight of the final composition, that is to say when the propellants are considered.

16. Composition according to any one of claims 1 to 15, wherein the propellant is selected from dimethyl ether, volatile hydrocarbons such as C3-5 alkanes, such as propane, isopropane, n-butane , isobutane, n-pentane, isopentane and mixtures thereof, optionally with at least one chlorinated and / or fluorinated hydrocarbon.

17. Composition according to any one of claims 1 to 16, characterized in that the weight ratio between the liquid phase and the propellant varies in a ratio of 5/95 to 50/50, preferably 10/90 to 40 / 60, more preferably 15/85 to 30/70, or even better is 15/85 or 20/80.

18. Composition according to any one of claims 1 to 17, characterized in that it further comprises at least one antiperspirant active agent and / or at least one deodorant active.

19. Composition according to Claim 18, characterized in that:

the antiperspirant active agent is chosen from aluminum and / or zirconium salts, aluminum and / or zirconium complexes, and mixtures thereof, preferably chosen from aluminum halohydrates, sodium halohydrates and aluminum and zirconium, complexes of zirconium hydroxychloride and aluminum hydroxychloride with or without an amino acid, and mixtures thereof; and the deodorant active agent is chosen from:

bacteriostatic agents or bactericidal agents acting on the germs of axillary odors, such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, 2,4-dichloro-2'-hydroxydiphenyl ether, 3 ', 4' 5'-trichlorosalicylanilide, 1- (3 ', 4'-dichlorophenyl) -3- (4'-chlorophenyl) urea or 3,7,1-trimethyldodeca-2,5,10-trienol;

polyols such as those of the glycerin, 1,3-propanediol or 1,2-decanediol type;

glycerol derivatives, for example Caprylic / Capric Glycerides, Caprylate or Glycerol Caprate, Polyglyceryl-2 Caprate;

biguanide derivatives, such as polyhexamethylene biguanide salts;

- Chlorhexidine and its salts;

4-Phenyl-4,4-dimethyl-2-butanol;

cyclodextrins;

chelating agents such as Tetrasodium Glutamate Diacetate, EDTA and

DPTA;

odor absorbers such as zeolites, in particular metallic zeolites, no silver, cyclodextrins, metal oxide silicates; transition metal-modified metal oxide particles, aluminosilicates, particles of chitosan derivatives;

- sodium bicarbonate;

salicylic acid and its derivatives such as n-octanoyl-5-salicylic acid;

- Moon ;

triethyl citrate; and

- their mixtures.

20. A cosmetic composition for preparing a cosmetic composition as defined in any one of claims 1 to 19, comprising in a physiologically acceptable medium:

(a) at least one of the superhydrophobic particles selected from:

superhydrophobic acrylic acid copolymer powders; and

- their mixtures; and

(b) at least one volatile solvent chosen from:

volatile hydrocarbon oils such as those chosen from:

hydrocarbon oils containing from 8 to 16 carbon atoms, in particular C 5 -C 16 isoalkanes of petroleum origin (also known as isoparaffins), such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and isohexadecane, and branched C 6 -C 16 esters such as isohexyl or isodecyl neopentanoate,

- petroleum distillates,

C2-4 monoalcohols such as ethanol, isopropanol and propanol;

volatile alkyltrisiloxane linear oils of general formula (Ia):

- their mixtures;

characterized in that the composition comprises a volatile solvent content of between 55% and 95% by weight, preferably between 60% and 93% by weight, even more preferably between 70% and 91% by weight, and even more preferably between 80% and 93% by weight. and 90% by weight relative to the total weight of the liquid phase, that is to say when the propellants are not considered.

21. Aerosol device consisting of:

(A) a container comprising a composition as defined in any one of claims 1 to 19; and

(B) at least one means for dispensing said composition.

22. Aerosol device consisting of:

(A) a container comprising a composition as defined in claim 20;

(B) at least one propellant and at least one means for dispensing said composition.

23. A cosmetic process for making up and / or caring for keratin materials, in particular the skin of the face and / or of the body, characterized in that keratin materials, in particular facial skin and / or or the body, a composition according to one of claims 1 to 19 or a composition according to claim 20 carried by at least one propellant.

24. Use in an aerosol cosmetic composition of at least superhydrophobic particles as defined according to any one of claims 1 to 10 and at least one film-forming polymer as defined according to any one of the claims. 12 to 13 to obtain a dry film, of good behavior and / or resistant to water and / or resistant to perspiration and / or resistant to friction.