FR2848559A1 - ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN NON-AQUEOUS AND NON-SILICONE ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION. - Google Patents

Abstract

The invention relates to polymers capable of forming, in a non-aqueous non-silicone medium under consideration, a dispersion of self-stabilized particles and to a process for preparing said polymers. The invention also relates to cosmetic compositions comprising said dispersion of polymer particles. .

Description

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ACRYLIC POLYMER, DISPERSION OF SAID POLYMER, STABLE IN NON-AQUEOUS AND NON-SILICONE ORGANIC MEDIUM AND
COMPOSITION COMPRISING SAID DISPERSION
TECHNICAL FIELD DESCRIPTION
The present invention relates to acrylic polymers capable of forming a dispersion of stable particles in a non-aqueous and non-silicone medium.

 The invention also relates to a process for the preparation of said polymers.

 Finally, the invention relates to a stable dispersion of particles formed by said polymer in a given non-silicone medium and the use of this dispersion in cosmetic compositions.

 It is already known to use, in the field of cosmetics, dispersions of polymer particles in organic media, as film-forming agents in various cosmetic formulations, such as mascaras, eyeliners, eye shadows. or nail polish.

 Thus, in European patent application EP 0 749 747 filed by the applicant, there is described a composition comprising a dispersion of particles of insoluble polymers in a non-aqueous medium, said dispersion being stabilized by adding stabilizing polymers.

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 The stabilizing polymers according to this document bind non-covalently through physical interactions on the insoluble polymers mentioned above.

 However, this type of composition has the following drawbacks: - It requires the addition in the non-aqueous medium of a quantity of so-called stabilizing polymers greater than that actually linked to the particles of insoluble polymers, in order to obtain a dispersion of said particles relatively stable; - When adding adjuvants, such as pigments, to these compositions, the stabilizing polymers tend to desorb particles of insoluble polymers to associate with said adjuvants, which contributes to destabilizing the dispersion, in particular by formation of agglomerates between the polymer particles.

 Document JP 11181003 describes polymers capable of forming solid particles without the addition of stabilizing polymers, but however these particles are unstable in non-aqueous organic media.

 The Applicant has surprisingly discovered new polymers capable of forming stable particles in a non-aqueous non-silicone medium, without the addition of stabilizing polymers.

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 Thus, the present invention aims to provide polymers, forming in a non-aqueous and non-silicone organic medium, a dispersion of the self-stabilized individual particles, without forming agglomerates of insoluble particles and sediments, for example, after standing of the dispersion one day at room temperature.

 An object of the present invention is therefore to provide an acrylic polymer comprising a skeleton insoluble in a non-aqueous non-silicone organic medium and a part soluble in said medium consisting of side chains covalently linked to said skeleton, said polymer being capable of being obtained by radical polymerization in the non-aqueous organic medium: - of one or more acrylic monomers, to form said insoluble skeleton; - one or more macromonomers comprising a terminal group capable of reacting during the polymerization to form the side chains, the said macromonomer (s) having a molecular weight by weight greater than or equal to 200; said soluble part representing 0.05 to 20% by weight of the polymer, and said polymer having a molecular weight by weight ranging from 10,000 to 300,000.

 Preferably, the molecular weight by weight of the polymer ranges from 20,000 to 200,000, more preferably from 25,000 to 150,000.

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 These polymers according to the invention can be in different forms, in particular in the form of random polymers.

 It is specified that, according to the invention, in the foregoing and what follows, the term “acrylic polymer” means a polymer obtained by radical polymerization between: - one or more monomers comprising at least one ethylenic unsaturation, including the homopolymer or corresponding copolymers are insoluble in the non-aqueous organic medium under consideration, that is to say that the homopolymer or the copolymers mentioned above are in solid form (or not dissolved) at a concentration greater than or equal to 5% by weight at temperature ambient in said nonaqueous organic medium; - with one or more macromonomers of which the homopolymer or the corresponding random copolymers are soluble in the organic medium under consideration, that is to say that the above-mentioned homopolymer or copolymers are completely dissolved at a concentration greater than or equal to 5% by weight and at room temperature in said non-aqueous organic medium.

 In the above and what follows, the term “non-aqueous organic medium” means a medium consisting of one or more non-aqueous compounds, said medium possibly containing at most 1% by weight of water.

 In the above and what follows, the term “non-silicone medium” means a medium consisting of one or more non-silicone compounds, comprising at least

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 at least 50% by weight of non-silicone compound (s), in particular from 50 to 100% by weight, for example from 60 to 100% or also from 65 to 95% by weight of non-silicone compound (s) ), any silicone compounds which may be present in a maximum amount of 50% by weight, in particular from 0 to 40% by weight, or even from 5 to 35% by weight, relative to the total weight of the medium.

 According to the invention, in the foregoing and the following, the term “macromonomer” means any oligomer comprising on one of its ends a terminal group capable of reacting during the polymerization reaction to form the side chains, said group may be an ethylenically unsaturated group capable of polymerizing by radical means with acrylic monomers, a reactive functional group capable of reacting with acrylic monomers or else with the skeleton being formed during polymerization.

 Thus, the polymers according to the invention are in the form of polymers comprising a skeleton (or main chain) consisting of a chain of acrylic units resulting from the polymerization of one or more acrylic monomers and comprising side chains (or grafts) resulting from the reaction of macromonomers, said side chains being covalently linked to said main chain.

 The skeleton (or main chain) is insoluble in the non-silicone medium in question while the side chains (or grafts) are soluble in said medium.

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 Thanks to the abovementioned characteristics, in a given non-silicone organic medium, the polymers have the capacity to fold in on themselves, thus forming particles of substantially spherical shape, with around the periphery of these particles the deployed side chains, which ensure the stability of these particles. Such particles resulting from the characteristics of the polymers of the invention have the particularity of not agglomerating in said medium and therefore of self-stabilizing and of forming a dispersion of particularly stable polymer particles.

 It is specified that by stable dispersion is meant, according to the invention, a dispersion which is not capable of forming a solid deposit, or of a liquid / solid phase shift, in particular after centrifugation, for example, at 4000 revolutions / month for 15 minutes.

 In particular, the polymers of the invention are capable of forming particles of average size ranging from 10 to 400 nm, preferably from 20 to 200 nm in a given non-silicone medium.

 Preferably, the soluble part constituted by the side chains represents 0.1 to 15%, even more preferably 0.1 to 10%, or better still 0.2 to 10% of the total weight of the polymer.

 Preferably, the macromonomers according to the invention have a molecular weight ranging from 200 to 20,000, preferably from 500 to 15,000.

 As stated previously, the polymers are capable of being obtained by polymerization

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 one or more acrylic monomers with one or more macromonomers in a given non-aqueous and non-silicone organic medium.

 The non-aqueous and non-silicone organic medium mentioned above is a liquid medium comprising at least one non-aqueous non-silicone liquid compound with a content mentioned above and can be defined with respect to the overall solenility parameter of Hansen 8.

 The global solubility parameter 8 according to Hansen's solubility space is defined in the article Solubility parameter values by Eric A. Grulke of the book Polymer Handbook, 3rd edition, Chapter VII, pages 519-559 by the relation: # = (dD2 + dp2 + dH2) 1/2 in which - dD characterizes the dispersion forces of LONDON resulting from the formation of dipoles induced during molecular shocks, - dp characterizes the forces of DEBYE interactions between permanent dipoles; - dH characterizes the forces of specific interactions (such as hydrogen bonds, acid / base, donor / acceptor, etc.).

 The definition of solvents in the solubility space according to Hansen is described in the article by C.M. Hansen The three dimensional solubility parameters J. Paint Technol. 39, 105 (1967).

 The non-aqueous non-silicone organic medium can consist of at least one non-silicone liquid compound chosen from the group consisting of:

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 - non-aqueous non-silicone liquid compounds having an overall solubility parameter according to the Hansen solubility space of less than 17 (MPa) 1/2, with the exception of silicone compounds; - monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1/2; and - mixtures thereof.

 Among the non-aqueous non-silicone liquid compounds having an overall solubility parameter according to the Hansen solubility space of less than or equal to 17 (Mpa) 1/2, mention may be made of liquid fatty substances, in particular oils, which can be chosen from natural or synthetic oils, carbonaceous, hydrocarbon-based, fluorinated, optionally branched, alone or as a mixture. Among these oils, mention may be made of vegetable oils formed by esters of fatty acids and of polyols, in particular triglycerides, such as sunflower, sesame or rapeseed oil, or esters derived from acids or d 'long chain alcohols (that is to say having from 6 to 20 carbon atoms), in particular the esters of formula RCOOR' in which R represents the residue of a higher fatty acid containing from 7 to 19 carbon atoms and R 'represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, such as palmitates, adipates and benzoates, in particular diisopropyl adipate. Mention may also be made of linear, branched and / or cyclic alkanes which may be volatile and in particular paraffin oils, of petrolatum, or hydrogenated polyisobutylene,

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 isododecane, or 'ISOPARS', volatile isoparaffins. Mention may also be made of esters, ethers and ketones.

 Mention may be made, in particular, as liquid compounds having a global solubility parameter according to the Hansen solubility space less than or equal to 17 (Mpa) 1/2: - linear, branched or cyclic esters, having more than 6 atoms of carbon ; - ethers having more than 6 carbon atoms; and - ketones having more than 6 carbon atoms.

 By monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 is meant aliphatic fatty monoalcohols having at least 6 carbon atoms, the hydrocarbon chain not comprising a group of substitution. As monoalcohols according to the invention, there may be mentioned oleic alcohol, decanol, dodecanol, octadecanol and linoleic alcohol.

 The choice of monomers constituting the backbone of polymers and macromonomers, as well as the size of the polymer, of the side chains as well as the proportion of the side chains will be made according to the non-aqueous and non-silicone medium so as to obtain a dispersion of particles. polymers in said medium, this choice can be made by a person skilled in the art.

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dans laquelle : - R1 désigne un atome d'hydrogène ou un groupe méthyle ; - R2 représente un groupe alkyle linéaire ou ramifié, comprenant de 1 à 6 atomes de carbone, ou un groupe alkyle cyclique comprenant de 3 à 6 atomes de carbone, lesdits groupes pouvant comporter dans leur chaîne un ou plusieurs hétéroatomes choisis parmi 0, N et S, et pouvant comporter un ou plusieurs substituants choisis dans un groupe constitué par OH, les atomes d'halogène (F, Cl, Br, I), ou - R2 représente un groupe alkyle linéaire ou ramifié comportant de 1 à 6 atomes de carbone, substitué par au moins un groupe polyoxyéthylène, ledit groupe étant constitué par la répétition de 5 à 30 motifs oxyéthylène ;
A titre d'exemples de R2, on peut citer le groupe méthyle, éthyle, propyle, butyle, isobutyle, méthoxyéthyle, éthoxyéthyle, méthoxy-polyoxyéthylène. As examples of acrylic monomers capable of constituting, after polymerization, the insoluble skeleton of the polymer, mention may be made of the acrylic monomer (s) chosen from the following monomers and their salts: - (meth) acrylates of formula:

in which: - R1 denotes a hydrogen atom or a methyl group; - R2 represents a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, or a cyclic alkyl group comprising from 3 to 6 carbon atoms, said groups possibly comprising in their chain one or more heteroatoms chosen from 0, N and S, and possibly comprising one or more substituents chosen from a group consisting of OH, the halogen atoms (F, Cl, Br, I), or - R2 represents a linear or branched alkyl group containing from 1 to 6 carbon atoms , substituted by at least one polyoxyethylene group, said group consisting of the repetition of 5 to 30 oxyethylene units;
Examples of R2 that may be mentioned include the methyl, ethyl, propyl, butyl, isobutyl, methoxyethyl, ethoxyethyl, methoxy-polyoxyethylene group.

 - the (meth) acrylamides of formula:

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dans laquelle : - R3 désigne un atome d'hydrogène ou un groupe méthyle ; - R4 et R5, identiques ou différents, représentent un atome d'hydrogène ou un groupe alkyle, linéaire ou ramifié, comportant de 1 à 6 atomes de carbone ; ou - R4 représente un atome d'hydrogène et R5 représente un groupe 1,1-diméthyl-3-oxobutyle.

in which: - R3 denotes a hydrogen atom or a methyl group; - R4 and R5, identical or different, represent a hydrogen atom or an alkyl group, linear or branched, having from 1 to 6 carbon atoms; or - R4 represents a hydrogen atom and R5 represents a 1,1-dimethyl-3-oxobutyl group.

 As examples of alkyl groups which may constitute R4 and R5, mention may be made of n-butyl, t-butyl and n-propyl.

- the vinyl esters of formula: R6-COO-CH = CH2 in which: - R6 represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or a cyclic alkyl group comprising from 3 to 6 carbon atoms and / or an aromatic group, for example of the benzene, anthracene and naphthalene type; - ethylenically unsaturated monomers comprising at least one carboxylic or sulfonic acid function, such as acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, l fumaric acid, maleic acid, styrenesulfonic acid, acid

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 acrylamidopropanesulfonic, vinylbenzoic acid, vinylphosphoric acid and the salts thereof; - ethylenically unsaturated monomers comprising at least one hydroxyl function 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; and mixtures thereof.

 It is understood that these non-polymerized acrylic monomers can be soluble in the non-aqueous and non-silicone medium in question, but become insoluble after polymerization in an appropriate amount, which is the objective of the present invention.

 The macromonomers constituting, after reaction, the side chains of the polymer according to the invention, comprises a terminal group capable of reacting during the polymerization with the monomers

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 acrylic or the growing chain to form said chains.

 This terminal group can be an ethylenically unsaturated group, in particular a group chosen from vinyl, allyl, methallyl, (meth) acryloyl, vinylbenzoyl, vinylbenzyl, C1-C4 alkenyl, C1-C6 cycloalkenyl groups. This group can be a reactive group capable of reacting with the backbone or the monomers constituting it (such as OH, NH2, COOH, anhydride).

 By way of examples, there may be mentioned: - polyolefins, such as those based on polyethylene, polypropylene, polyethylenepolypropylene, polyethylene-polybutylene, polyisoprene, polybutadiene, poly (ethylene / butylene) -polyisoprene and more particularly poly methacrylate ( ethylene / butylene) sold under the name Kraton Ligard L-12T3 by Kraton Polymers; - Homopolymers or copolymers of linear or branched alkyl acrylate or methacrylate of 8 to 22 carbon atoms, such as macromonomers based on poly (ethyl-2-hexyl acrylate), poly (dodecyl acrylate).

 Preferably, the macromonomers of the invention have a glass transition temperature less than or equal to 25 C, preferably less than or equal to 0 C.

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 Particularly advantageous polymers according to the invention are those obtained by polymerization: - of methyl acrylate monomer and of polyethylene / polybutylene macromer (Kraton L-1253) in isododecane; isononylisononanoate or a C12-C15 alkyl benzoate (Finsolv TN); - methoxyethyl acrylate monomer and polyethylene / polybutylene macromonomer (Kraton L-1253) in isododecane.

 The present invention also relates to a nonaqueous dispersion comprising a nonaqueous organic medium and particles consisting of at least one polymer, said medium and said polymer being as defined above.

 Advantageously, the polymer particles are in the form of nanometric particles, having an average size which can range from 10 to 400 nm, preferably from 20 to 200 nm.

 Because of this very small size, the particles used in the constitution of the dispersion are particularly stable and therefore unlikely to form agglomerates. The dispersion of the invention is therefore a stable dispersion in the non-aqueous non-silicone medium considered and does not form sediment, when it is placed for a prolonged period (for example, 24 hours) at room temperature.

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 The invention also relates to a process for the preparation of a polymer or of a dispersion of polymer particles, as described above, said process comprising a step consisting in carrying out radical copolymerization, in a non-aqueous organic medium, corresponding to the definition given above, of one or more acrylic monomers as defined above with one or more macromonomers as defined above.

 The non-aqueous organic medium consists of at least one non-silicone liquid compound defined by the Hansen solubility space, as explained initially.

 Conventionally, the copolymerization can be carried out in the presence of a polymerization initiator. The polymerization initiators can be radical initiators.

 In general, such a polymerization initiator can be chosen from peroxidized organic compounds such as dilauroyl peroxide, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate; diazotized compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile.

 The reaction can also be initiated using photoinitiators or by radiation such as UV, neutrons or plasma.

 In general, to implement this process, at least part of the non-aqueous, non-aqueous medium is introduced into a reactor of a size appropriate to the quantity of polymer that will be produced.

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 silicone, part of the acrylic monomers, which will constitute, after polymerization, the insoluble skeleton, all of the macromonomer (which will constitute the side chains of the polymer) and part of the polymerization initiator. At this stage of introduction, the reaction medium forms a relatively homogeneous medium.

 The reaction medium is then stirred and heated to a temperature to obtain a polymerization of the monomers and macromonomers. After a certain time, the initially homogeneous and clear medium leads to a dispersion with a milky appearance. A mixture consisting of the remaining part of the monomer and of the polymerization initiator is then added. After an adequate time during which the mixture is heated with stirring, the medium stabilizes in the form of a milky dispersion, the dispersion comprising particles of polymers stabilized in the medium in which they were created, said stabilization being due to the presence side chains soluble in said medium.

 The dispersion of polymer particles according to the invention can be used in any type of composition and in particular in a cosmetic, pharmaceutical and / or hygienic composition, such as a care or make-up composition for the skin or keratin materials or else a hair composition or a sun composition.

 The invention therefore relates to a composition comprising, in a cosmetically medium,

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 pharmaceutically and / or hygienically acceptable, a dispersion of particles of a polymer as defined above.

 Depending on the desired application, the composition may contain the usual adjuvants which are incorporated into cosmetic, pharmaceutical and / or hygienic compositions.

 Among these adjuvants, mention may be made of fatty substances, and in particular waxes, oils, gums and / or pasty fatty substances, hydrocarbon and / or silicone, and pulverulent compounds such as pigments, fillers and / or nacre.

 Among the waxes which may be present in the composition according to the invention, mention may be made, alone or as a mixture, of hydrocarbon waxes such as beeswax; Carnauba, Candellila, Ourrury, Japanese wax, cork fiber or cane wax; paraffin and lignite waxes; microcrystalline waxes; lanolin wax; montan wax; ozokerites; polyethylene waxes; waxes obtained by Fischer-Tropsch synthesis; hydrogenated oils, fatty esters and glycerides concrete at 25 C. It is also possible to use silicone waxes, among which mention may be made of alkyls, alkoxys, and / or polymethylsiloxane esters.

 Among the oils which may be present in the composition according to the invention, mention may be made, alone or as a mixture, of hydrocarbon oils such as paraffin oil or

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 petrolatum; perhydrosqualene; acara oil; sweet almond, calophyllum, palm, castor, avocado, jojoba, olive or germ of cereal oil; esters of lanolic acid, oleic acid, lauric acid, stearic acid; alcohols such as oleic alcohol, linoleic or linolenic alcohol, isostearic alcohol or octyl dodecanol. Mention may also be made of silicone oils such as PDMS, optionally phenylated such as phenyltrimethicones. Mention may also be made of volatile oils, such as cyclotetradimethylsiloxane, cyclopentadimethylsiloxane, cyclohexadimethylsiloxane, methylhexyldimethylsiloxane, hexamethyldisiloxane or isoparaffins.

 The pigments can be white or colored, mineral and / or organic. Mention may be made, among mineral pigments, of titanium, zirconium or cerium dioxides, as well as oxides of zinc, iron or chromium, ferric blue. Among the organic pigments, mention may be made of carbon black and of barium, strontium, calcium and aluminum lakes.

 The nacres can be chosen from mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride as well as colored titanium mica.

 The fillers can be mineral or synthetic, lamellar or non-lamellar. Mention may be made of talc, mica, silica, kaolin, nylon and polyethylene powders, Teflon, starch,

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 micatitane, natural mother-of-pearl, boron nitride, hollow microspheres such as Expancel (Nobel Industrie), polytrap (Dow Coming) and silicone resin microbeads (Tospearls from Toshiba, for example).

 The composition can also comprise any additive usually used in the cosmetic field, such as antioxidants, perfumes, essential oils, preservatives, cosmetic active agents, moisturizers, vitamins, essential fatty acids, sphingoceryls, filters. sunscreen, surfactants, liposoluble polymers such as polyalkylenes, in particular polybutene, polyacrylates and silicone polymers compatible with fatty substances. Of course, those skilled in the art will take care to choose this or these optional additional compounds, and / or their quantity, in such a way that the advantageous properties of the composition according to the invention are not, or not substantially altered by the addition considered.

 The compositions according to the invention can be in any form acceptable and customary for a cosmetic, hygienic or pharmaceutical composition.

 The compositions according to the invention can be in the form of an oil-in-water or water-in oil emulsion, a lotion, a foam, a spray.

 Among the applications preferentially targeted by the present invention, one can more particularly mention:

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 the field of hair products (washing, care or beauty of the hair), the compositions according to the invention being in particular in the form of aerosols, foam, shampoos, conditioners, styling or treating lotions or gels, shaping or styling or fixing lacquers or lotions; - the field of make-up products, in particular for making up the eyelashes, the compositions being in the form of mascara or eyeliner; lipstick or lip gloss or foundation, or blush or eyeshadow; the field of skin and body care products, in particular sun or self-tanning products.

 Finally, the subject of the present invention is a cosmetic treatment method for the care and / or cleaning and / or make-up of keratin materials, consisting in applying to the keratin materials, a composition as defined above.

 The invention will now be described in more detail in the light of the following examples given by way of illustration and not limitation.

DETAILED DESCRIPTION OF THE INVENTION EXAMPLES.

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 The present examples illustrate the preparation of polymers in accordance with the invention, capable of forming a dispersion of particles in a considered organic medium.

 In these examples, after preparation of said dispersion, the average molar masses by weight (Mw) and by number (Mn) of the polymer are determined, the glass transition temperature, the dry matter content (or dry extract) and the size. polymer particles.

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

 The measurement of the glass transition temperature (Tg) is carried out according to standard ASTM D3418-97, by differential enthalpy analysis (DSC "Differential Scanning Calorimetry) on a calorimeter, over a temperature range between -100 ° C. and + 150 ° C. a heating speed of 10 C / min in 150 l aluminum crucibles.

The crucibles are prepared in the following manner: 100 (100 μl of the dispersion obtained are introduced into an aluminum crucible of 150 l and the solvent is allowed to evaporate for 24 hours at room temperature and at 50% RH. Renew the operation then introduce the crucible into the Mettler DSC30 calorimeter
The dry matter content (or dry extract), i.e. the non-volatile matter content, can be measured in different ways, you can

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 cite for example the methods by drying in an oven or the methods by drying by exposure to infrared radiation.

 Preferably, the quantity of dry matter, commonly called dry extract of the compositions according to the invention, is measured by heating the sample by infrared rays of 2 m to 3.5 m wavelength. The substances contained in said compositions which have a high vapor pressure, evaporate under the effect of this radiation. Measuring the weight loss of the sample makes it possible to determine the dry extract of the composition. These measurements are carried out using a commercial infrared dryer LP16 from Mettler. This technique is fully described in the device documentation provided by Mettler.

The measurement protocol is as follows:
About 1 g of the composition is spread over a metal dish. This, after introduction into the desiccator, is subjected to a temperature set point of 120 ° C. for one hour. The wet mass of the sample, corresponding to the initial mass and the dry mass of the sample, corresponding to the mass after exposure to radiation, are measured using a precision balance.

The dry matter content is calculated as follows:
Dry extract = 100 x (dry mass / wet mass).

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 The particle sizes can be measured by different techniques, one can quote in particular the techniques of light diffusion (dynamic and static), the methods by Coulter counter, the measurements by speed of sedimentation (connected to the size via the law of Stokes) and microscopy. These techniques make it possible to measure a particle diameter and for some of them a particle size distribution.

 Preferably, the sizes and size distributions of the particles of the compositions according to the invention are measured by static light scattering using a commercial particle size analyzer of the MasterSizer 2000 type from Malvern. The data is processed on the basis of Mie diffusion theory. This theory, exact for isotropic particles, makes it possible to determine in the case of non-spherical particles, an effective diameter of particles. This theory is notably described in the work of Van de Hulst, H.C., "Light Scattering by Small Particles," Chapters 9 and 10, Wiley, New York, 1957.

IV, -< D[4,3] = IL où Vi représente le volume des particules de diamètre effectif di. Ce paramètre est notamment décrit dans la documentation technique du granulomètre. The composition is characterized by its mean effective diameter by volume D [4.3], defined as follows:

IV, - <D [4.3] = IL where Vi represents the volume of the particles of effective diameter di. This parameter is described in particular in the technical documentation of the granulometer.

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 The measurements are carried out at 25 ° C., on a dispersion of dilute particles, obtained from the composition as follows: 1) dilution by a factor of 100 with water, 2) homogenization of the solution, 3) rest of the solution for 18 hours, 4) recovery of the homogeneous whitish supernatant.

 The effective diameter is obtained by taking a refractive index of 1.33 for water and an average refractive index of 1.42 for particles.

EXAMPLE 1.

 This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methyl acrylate and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253).

The procedure for this particular polymer is as follows:
75 g of heptane, 50 g of isododecane, 12.75 g of methyl acrylate and 2.25 g of macromonomer of the polyethylene / polybutylene copolymer type (Kraton L-1253) are loaded into a 500 mL reactor. and 0.8 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S).

 The reaction mixture is stirred and heated to room temperature at 90 ° C. over 1 hour.

After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. We maintain the

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 heating with stirring for an additional 15 minutes, then a mixture consisting of 35 g of methyl acrylate and 0.5 g of Trigonox 21S is added dropwise for 1 hour.

 The heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium.

 At the end of this distillation operation, a dispersion of polymer particles thus prepared, stable in isododecane, is obtained.

The characteristics of the polymer and of the particles formed by said polymer are as follows:
Granulometry: 73.5 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 C; - Dry extract: 55.1% in isododecane, produced by thermobalance; - Glass transition: 8 C by DSC Mettler; - Molecular mass weight Mw = 44300 - Molecular mass number Mn = 8900 - Polydispersity index (Mw / Mn) = 4.99.

- Molecular mass of the macromonomer used Mw = 4000
The stability of the dispersion obtained is demonstrated by the implementation of the following stability protocol:

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8 ml of the dispersion produced are placed in a hemolysis tube and centrifuged at 4000 rpm for 15 minutes using a Jouan C100-S5 centrifuge. After 15 minutes, we see that there is no phase shift, which shows that the dispersion is stable.

EXAMPLE 2.

 This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methoxyethyl acrylate and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253).

The procedure for this particular polymer is as follows:
75 g of heptane, 50 g of isododecane, 12.75 g of methoxyethyl acrylate and 2.25 g of macromonomer of the polyethylene / polybutylene copolymer type (Kraton L-1253) are loaded into a 500 mL reactor. and 0.8 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S).

 The reaction mixture is stirred and heated to room temperature at 90 ° C. over 1 hour.

After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. Heating is continued with stirring for an additional 15 minutes and then added dropwise during

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 1 hour a mixture consisting of 35 g of methoxyethyl acrylate and 0.5 g of Trigonox 21S.

 The heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium.

 At the end of this distillation operation, a dispersion of polymer particles thus prepared, stable in isododecane, is obtained.

The characteristics of the polymer and of the particles formed by said polymer are as follows:
Granulometry: 91.4 nm with polydispersity of 0.05 carried out on Malvern Autosizer Lo-C at 25 C; - Dry extract: 56.4% in isododecane, produced by thermobalance; - Glass transition: -40 C by DSC Mettler; - Molecular mass weight Mw = 71200 - Molecular mass number Mn = 19300 - Polydispersity index (Mw / Mn) = 3. 7 - Molecular mass of the macromonomer used Mw = 4000
After the implementation of the stability protocol in accordance with Example 1, it is found that the dispersion obtained is stable.

EXAMPLE 3

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This example illustrates the preparation of a polymer forming a dispersion of particles in a carbon solvent, said polymer being obtained by polymerization of methyl acrylate and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253).

The procedure for this particular polymer is as follows:
200 g of heptane, 200 g of isononyl isononanoate, 28 g of methyl acrylate and 12 g of macromonomer of the polyethylene / polybutylene copolymer type (Kraton L-1253) and 3 are charged into a 1 L reactor. 2 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S).

 The reaction mixture is stirred and heated to room temperature at 90 ° C. over 1 hour.

After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. The heating is maintained with stirring for an additional 15 minutes, then a mixture consisting of 160 g of methyl acrylate and 2 g of Trigonox 21S is added dropwise for 1 hour.

 The heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium.

 At the end of this distillation operation, a dispersion of particles of polymer thus prepared, stable in isononyl isononanoate, is obtained.

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The characteristics of the polymer and of the particles formed by said polymer are as follows:
Particle size: 220 nm with polydispersity of 0.04 carried out on Malvern Autosizer Lo-C at 25 C; - Theoretical dry extract: 50% in isononyl isononanoate - Glass transition: 12 C by DSC Mettler; - Molecular mass weight Mw = 98909 - Molecular mass number Mn = 25731 - Polydispersity index (Mw / Mn) = 3. 84 - Molecular mass of the macromonomer used Mw = 4000 After the implementation of the stability protocol in accordance with Example 1, it can be seen that the dispersion obtained is stable.

EXAMPLE 4
This example illustrates the preparation of a polymer forming a dispersion of particles in a carbonaceous solvent, said polymer being obtained by polymerization of methyl acrylate and the macromonomer corresponding to a polyethylene / polybutylene copolymer (Kraton L-1253).

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The procedure for this particular polymer is as follows:
200 g of heptane, 200 g of C12-15 alkyl benzoate better known under the name of Finsolv TN, 28 g of methyl acrylate and 12 g of macromonomer of the copolymer type are charged into a 1 L reactor. polyethylene / polybutylene (Kraton L-1253) and 3.2 g of tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S).

 The reaction mixture is stirred and heated to room temperature at 90 ° C. over 1 hour.

After 15 minutes at 90 ° C., a change in appearance of the reaction medium is observed, which changes from a transparent appearance to a milky appearance. The heating is maintained with stirring for an additional 15 minutes, then a mixture consisting of 160 g of methyl acrylate and 2 g of Trigonox 21S is added dropwise for 1 hour.

 The heating is then left for 4 hours at 90 ° C. and then the heptane is distilled from the reaction medium.

At the end of this distillation operation, a dispersion of polymer particles thus prepared, stable in C12-15 alkyl benzoate (Finsolv TN), is obtained.
The characteristics of the polymer and of the particles formed by said polymer are as follows: - Grain size. 50 nm with 0.04 polydispersity carried out on Malvern Autosizer Lo-C at 25 C;

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 - Theoretical dry extract: 50% in C12-15 alkyl benzoate (Finsolv TN) - Glass transition: 12 C by DSC Mettler; - Molecular mass weight Mw = 93984 - Molecular mass number Mn = 29923 - Polydispersity index (Mw / Mn) = 3.14 - Molecular mass of the macromonomer used Mw = 4000.

After the implementation of the stability protocol in accordance with Example 1, it is found that the dispersion obtained is stable.

Example 5 Composition of Mascara
A mascara was prepared having the following composition: Beeswax 8 g Paraffin wax 3 g Carnauba wax 6 g Hectorite modified with chloride 5.3 g of di-stearyl di-methyl benzyl ammonium (Bentoneo 38V from Elementis ) Propylene carbonate 1.7 g Filler 1 g pigments 5 g Dispersion of polymer from Example 4 12 g in MA Isododecane qs 100

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The mascara, after application to the eyelashes, is considered very satisfactory.

EXAMPLE 6 Lipstick Stick
The following lipstick composition is prepared: Polyethylene wax 15 Dispersion of polymer from Example 3 10% in MA Hydrogenated polyisobutene (Parlam from Nippon Oil Fats)
26% Isododecane qs 100 Pigments 8. 6%
The composition obtained after application to the lips has good cosmetic properties.

Example 7: W / O Foundation
A foundation composition is prepared comprising the following compounds:

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Phase A Cetyl Dimethicone copolyol 3 g (ABIL EM 90 from the company
Goldschmidt)
Isostearyl succinate 0.6 g diglyceryl (IMWITOR 780K from the company
Condea)
Isododecane 18.5 g
Pigment mixture (10 g iron oxides and hydrophobic titanium oxides)
Dispersion of 8.7 g polymer in MA Example 2
Polyamide powder (NYLON-12 8 g Dupont de Nemours)
Perfume qs Phase B Water qs 100
Magnesium sulfate 0.7 g
Preservative (Methylparaben) Qs Phase C Water 2 g
Preservative (Diazolinyl urea) Qs
The composition obtained has good cosmetic properties.

Example 8
A compacted powder is prepared having the following composition: Composition A: - Talc 30 g - Bismuth oxychloride 10 g - Zinc stearate 4 g - Nylon powder 20 g - Dispersion of Example 1 5 g Composition B: - Oxides of iron 2 g - Vaseline oil 6 g

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The powder is obtained in the following manner: the composition A is ground in a KENWOOD type grinder for approximately 5 minutes with gentle stirring, the composition B is added and the whole is ground for approximately 2 minutes at the same speed, then 3 minutes at a faster speed. The preparation is then sieved through a 0.16 mm sieve, then this mixture is compacted in cups.

 A compacted powder is obtained having good cosmetic properties.

 The composition obtained is easy and pleasant to apply. It is found that the film does not migrate into fine lines of the skin, even after having been worn for several hours.

EXAMPLE 9 Face Gel
The following composition is prepared:. isopropyl palmitate 10 g. petrolatum (wax) 5 g. modified hectorite (clay) 0.15 g. ozokerite (wax) 5 g. oxyethylenated sorbitan septaoleate (400E) 5 g. dispersion of Example 4 (25% dry matter) 75 g
A gel is obtained having good cosmetic properties.

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Example 10: care oil
The following composition is prepared:. dispersion of Example 3 (25% dry matter) 70 g. jojoba oil 15 g. soybean oil 15 g
A care oil is obtained which can be applied to the body or the face.

Claims (19)

1. Acrylic polymer comprising a backbone insoluble in a non-aqueous non-silicone organic medium and a part soluble in said medium consisting of side chains covalently linked to said backbone, said polymer being capable of being obtained by radical polymerization in non-organic medium aqueous: - of one or more acrylic monomers, to form said insoluble skeleton; - one or more macromonomers comprising a terminal group capable of reacting during the polymerization to form the side chains, the said macromonomer (s) having a molecular weight by weight greater than or equal to 200; said soluble part representing 0.05 to 20% by weight of the polymer, and said polymer having a molecular weight by weight ranging from 10,000 to 300,000.  2. Polymer according to claim 1, for which the non-aqueous non-silicone organic medium consists of at least one non-aqueous non-silicone liquid compound chosen from the group consisting of: - non-aqueous non-silicone liquid compounds having a solubility parameter overall according to the Hansen solubility space less than 17 (MPa) 1/2; - monoalcohols having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) 1/2; and - mixtures thereof. <Desc / Clms Page number 37>  3. Polymer according to claim 2, for which the non-aqueous non-silicone liquid compound having an overall solubility parameter according to the Hansen solubility space of less than 17 (MPa) 1/2 is chosen from natural or synthetic, carbon-based oils , hydrocarbon, fluorinated, alone or as a mixture; esters; ketones; ethers; linear, branched and / or cyclic alkanes, optionally volatile.  4. Polymer according to claim 2, for which the non-aqueous non-silicone liquid compound having an overall solubility parameter according to the Hansen solubility space of less than 17 (MPa) 1/2 is chosen from the group consisting of linear esters , branched or cyclic, having more than 6 carbon atoms, ethers having more than 6 carbon atoms, ketones having more than 6 carbon atoms.  5. Polymer according to claim 2, in which the monoalcohols having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 are chosen from the group formed by fatty aliphatic monoalcohols having minus 6 carbon atoms.  6. Polymer according to any one of claims 1 to 5, forming particles in said non-aqueous organic medium with an average size of 10 to 400 nm, preferably from 20 to 200 nm. <Desc / Clms Page number 38>  7. Polymer according to any one of claims 1 to 6, in which the acrylic monomer (s) are chosen from the group consisting of the following monomers and their salts: - (meth) acrylates of formula:

 in which: - R1 denotes a hydrogen atom or a methyl group; - R2 represents a linear or branched alkyl group, comprising from 1 to 6 carbon atoms, or a cyclic alkyl group comprising from 3 to 6 carbon atoms, said groups possibly comprising in their chain one or more heteroatoms chosen from 0, N and S, and possibly comprising one or more substituents chosen from a group consisting of OH, the halogen atoms (F, Cl, Br, I), or - R2 represents a linear or branched alkyl group containing from 1 to 6 carbon atoms , substituted by at least one polyoxyethylene group, said group consisting of the repetition of 5 to 30 oxyethylene units; - the (meth) acrylamides of formula:

 in which : <Desc / Clms Page number 39>  - R3 denotes a hydrogen atom or a methyl group; - R4 and Rs, identical or different, represent a hydrogen atom or an alkyl group, linear or branched, having from 1 to 6 carbon atoms; or - R4 represents a hydrogen atom and R5 represents a 1,1-dimethyl-3-oxobutyl group. 2-hydroxyethyl, 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate; R6-COO-CH = CH2 in which: - R6 represents a linear or branched alkyl group, comprising from 1 to 6 atoms, or a cyclic alkyl group comprising from 3 to 6 carbon atoms and / or an aromatic group, for example of benzene, anthracene, and naphthalene type; - ethylenically unsaturated monomers comprising at least one carboxylic or sulfonic acid function, such as acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, l fumaric acid, maleic acid, styrenesulfonic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof, - ethylenically unsaturated monomers comprising, minus a hydroxyl function such as 2-hydroxypropyl methacrylate, methacrylate - vinyl esters of formula: <Desc / Clms Page number 40>  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; and mixtures thereof.  8. Polymer according to any one of claims 1 to 7, in which the macromonomer (s) are chosen from the group consisting of: polyolefins, such as those based on polyethylene, polypropylene, polyethylenepolypropylene, polyethylene-polybutylene, polyisoprene, polybutadiene , poly (ethylene / butylene) -polyisoprene and more particularly poly (ethylene / butylene) methacrylate marketed under the name Kraton Ligard L-12T3 by Kraton Polymers; - Homopolymers or copolymers of linear or branched alkyl acrylate or methacrylate comprising from 8 to 22 carbon atoms, such as macromonomers based on poly (2-ethylhexyl acrylate), or poly (dodecyl acrylate).  9. Polymer according to any one of the preceding claims, capable of being obtained by polymerization: <Desc / Clms Page number 41>  - Methyl acrylate monomer and polyethylene / polybutylene macromer (Kraton L-1253) in isododecane; isononylisononanoate or a C12-C15 alkyl benzoate (Finsolv TN); - methoxyethyl acrylate monomer and polyethylene / polybutylene macromonomer (Kraton L-1253) in isododecane.  10. A nonaqueous dispersion comprising a nonaqueous organic medium and particles consisting of at least one polymer, said medium and said polymer being as defined in claims 1 to 9.  11. Dispersion according to claim 10, said dispersion being a stable dispersion in the non-aqueous non-silicone medium in question.  12. A method of preparing a polymer according to claim 1 to 9 or a dispersion according to claim 10 or 11, comprising a step consisting in carrying out a radical copolymerization, in a non-aqueous organic medium, of one or more monomers acrylics with one or more macromonomers, said medium, said monomer (s), said macromonomer (s) being as defined in claims 1 to 9.  13. The preparation method according to claim 12, in which the copolymerization is initiated in the presence of a radical initiator. <Desc / Clms Page number 42>  14. The preparation method according to claim 13, wherein said initiator can be chosen from peroxidized organic compounds such as dilauroyl peroxide, dibenzoyl peroxide, tertbutyl peroxy-2-ethylhexanoate, diazotized compounds such as azobisisobutyronitrile, l 'azobisdiméthylvalero nitrile.  15. Composition comprising, in a cosmetically, pharmaceutically and / or hygienically acceptable medium, a dispersion of particles of a polymer according to claim 10 or 11.  16. Composition according to claim 15, comprising, in addition, fatty substances chosen from the group formed by waxes, oils, gums, pasty fatty substances, hydrocarbon or silicone.  17. Composition according to claim 15 to 16, comprising, in addition, pigments, fillers and / or nacres.  18. Composition according to any one of claims 15 to 17, being in the form of a composition for caring for or making up the skin or keratin materials, or else a hair composition or a sunscreen composition.  19. Cosmetic treatment process for the care and / or cleaning and / or makeup of <Desc / Clms Page number 43>  keratin materials consisting in applying to the keratin materials, a composition according to any one of claims 15 to 18.