FR2892018A1 - Cosmetic/pharmaceutical composition, useful as a make-up composition for lips, eye, nail, body and hair, comprises a functionalized homopolymer with iodine atom at the terminal and monomer e.g. (meth)acrylate - Google Patents

Abstract

Cosmetic/pharmaceutical composition comprises at least a functionalized homopolymer (A) having at least an iodine atom at the terminal and a monomer, in a medium, where the monomer is: (meth)acrylate monomer (I); ethylene monomer (II) having ester group with silanes, silsesquioxanes, siloxanes or carbosiloxanes dendrimers; or carbonated/siliconated macromonomer (III) having at least a polymerizable terminal group, preferably a vinyl or (meth) acrylate group. Cosmetic/pharmaceutical composition comprises at least a functionalized homopolymer (A) having at least an iodine atom at the terminal and a monomer, in a medium, where the monomer is: (meth)acrylate monomer (I) of formula CH2=CHCOOR or CH2=C(CH3)COOR; ethylene monomer (II) having ester group with silanes, silsesquioxanes, siloxanes or carbosiloxanes dendrimers; or carbonated/siliconated macromonomer (III) having at least a polymerizable terminal group, preferably a vinyl or (meth) acrylate group. R : 4-32C (preferably 12-18C) alkyl, 3-32C (preferably 6-12C) (hetero)cycloalkyl or aromatic ring like 3-32C (preferably 5-12C) aryl or aralkyl (all optionally carry O, N, P, S or halo e.g. F, I, Cl or Br). An independent claim is included for a functionalized homopolymer.

Description

The present invention relates to novel polymers as well as

  compositions, in particular cosmetic or pharmaceutical compositions comprising them.

  In the field of cosmetics, it is often sought to have compositions making it possible to obtain a deposit, in particular an adhesive or film-forming deposit, on the keratin materials in question, such as the hair, the skin, the eyelashes or the nails. In particular, these compositions can provide color (make-up or hair coloring compositions), gloss or dullness (care or make-up compositions for the skin), physical properties such as the form (hair compositions in particular styling), care properties or protection (care compositions, for example hydration or UV protection). We generally seek a good remanence and held in time of the cosmetic deposit, as well as good adhesion to the support. In particular, it is desirable for this deposit to be able to withstand mechanical aggression such as friction, transfer by contact of another object; with water, sweat, tears, rain, sebum and oils. This is particularly true in make-up, particularly in the field of lipstick where it is sought the prolonged holding of color and gloss and the non-transfer of color; in the field of foundations, eye shadows and powders where it is sought to maintain the color provided, maintaining as long as possible the dullness of the initial shade despite the secretion of sebum and sweat, and the lack of transfer.

  In addition, makeup compositions must be comfortable to wear and not have a too sticky texture. To reconcile all of these properties, often antinomic, within the same composition, is generally used a mixture of several polymers, very different chemical nature, each polymer providing a desired characteristics. However, the use of a mixture of polymers having different chemical natures, not necessarily compatible, can generate demixing problems within the composition.

  The use of random copolymers, for example conventional acrylic copolymers obtained by conventional radical polymerization by random mixing of monomers, does not solve these problems satisfactorily. In fact, the random copolymers known in the prior art have a dispersity in the composition of the polymer chains, which also leads to a demixing of the polymers within the formula.

  US Pat. No. 5,807,937 discloses a method known as ATRP which makes it possible to prepare particular copolymers which can be functionalized at their end, in particular by a bromine or chlorine atom; this process, however, requires the use of metal catalysts, which can remain in trace form in the polymers thus prepared. In the case of cosmetic applications of these polymers, the presence of such atoms may possibly be a problem. In addition, these atoms are not always sufficiently labile for their replacement by more desirable functions is easily performed. Furthermore, WO99 / 20659 discloses end-functionalized polymers obtained by degenerative transfer (TD). Degenerative transfer controlled radical polymerization (TD) allows the synthesis of functionalized (co) polymers whose molecular weight and architecture are controlled. However, the polymers mentioned in this document are not always soluble, in particular in cosmetic media, especially in organic solvents and / or mineral or organic oils, usually used in cosmetics.

  The aim of the present invention is to overcome the drawbacks of the prior art by proposing new particular polymers, functionalized at at least one of their ends by a sufficiently labile atom to be easily replaced, and cosmetically acceptable, these polymers being easily transportable in lipophilic cosmetic media.

  An object of the present invention is a cosmetic or pharmaceutical composition comprising, in a physiologically acceptable medium, at least one homopolymer functionalized at at least one of its ends by an iodine atom, and comprising a monomer as defined above. after.

  The polymers according to the invention have the advantage of being easily implemented in lipophilic cosmetic media, especially in solvents and / or cosmetic oils, while retaining interesting rheological properties. In addition, the polymers according to the invention can be transported at a high level in the cosmetic compositions according to the invention, since they are highly soluble in the lipophilic media in question (up to 50% by weight for some of them). them); this makes it possible to use large quantities of polymer, in the form of a solution or dispersion, without being confronted with problems of increasing viscosity, for example. Moreover, the polymers according to the invention can make it possible to avoid the problems of demixing within the formula while at the same time making it possible to provide the desired 40 cosmetic properties. It should also be noted that the polymers according to the invention can be easily controlled in terms of their molar mass, their mass distribution and their solubility, by adapting the nature of the monomers and the operating conditions.

  The polymer according to the invention is a homopolymer, that is to say that all the repeating units constituting it are of identical chemical structure; it may be monomer (isobornyl acrylate for example) or macromonomer (poly (isobornyl acrylate) acrylate end for example). In the present description, the term macromonomer is understood to mean a repeating unit consisting, on the one hand, of a prepolymer group (repetition of monomers, said group possibly being homopolymeric or copolymeric) and, on the other hand, of a polymerizable terminal group. , usually located at one of its ends.

  Thus, the homopolymer according to the invention can also be prepared from macromonomers for which the prepolymer group is a copolymer (poly (ethylene-butylene) acrylate end, for example).

  The polymer according to the invention may be linear, grafted or star-shaped.

  It is preferably linear, and in this case can be represented, schematically, by the following formula: F- [M1] n-I wherein F represents a residue derived from the transfer agent (the radical R 'defined below), either from the initiator; I is the iodine atom, MI is a mono-mother and n is the degree of polymerization. This is particularly the case when the polymer is obtained from a mono-mother and a transfer agent of structure R'-I.

  The polymer according to the invention may, however, be a graft polymer. This can be the case when it is obtained from a R'-I structure transfer agent and a repeating unit which is a monofunctional macromonomer, i.e. having a single terminal group. polymerizable (M2). In this case, the homopolymer can be schematically represented by the following formula: ## STR2 ## wherein [M2] n represents the prepolymeric group, having identical side chains which are themselves homo- or co-polymeric.

  The polymer according to the invention may also be in stars, of schematic structure F - ([M1] n-I) m with m being the number of branches of the star and being an integer strictly greater than 2; the homopolymer therefore has at least 3 40 terminal iodine atoms and is said to be star-shaped. This is particularly the case when the polymer is obtained from a monomer M1 and a transfer agent of structure R'-O) m.

  When the polymer is obtained from a macromonomer M2 and a transfer agent of structure R '- (I) m, it is possible to obtain a star-shaped polymer whose branches are grafted. When m = 2, the homopolymer is no longer said in stars, but is difunctional. It can be linear (when obtained from M1 monomers) or grafted when obtained from M2 macromonomer.

  In all these cases, it is clear that the prepolymeric group of the macromonomer M2 may be a homopolymer, but also a copolymer (random, alternating, block and / or gradient).

  Preferably, the number-average molecular mass of the polymer according to the invention is between 500 g / mol and 1,000,000 g / mol, in particular between 1,000 g / mol and 250,000 g / mol, and even better still between 2000 g / mol and mol and 100,000 g / mol or even 5000 g / mol and 50,000 g / mol. The number average molecular weight (Mn) is determined by gel permeation liquid chromatography (GPC), eluent THF, calibration curve established with linear polystyrene standards, refractometric detector.

  The polymers according to the invention are advantageously obtained by radical polymerization controlled by degenerative transfer to the iodine atom. Controlled radical polymerization refers to polymerizations for which side reactions which usually lead to the disappearance of propagating species (termination or transfer reaction) are rendered very unlikely compared to the propagation reaction by a radical control agent. free. The imperfection of this mode of polymerization resides in the fact that when the concentrations of free radicals become important with respect to the monomer concentration, the secondary reactions become again decisive and tend to widen the distribution of the masses. With this method of polymerization, the polymer chains of the polymers according to the invention grow simultaneously and all the chains have a low mass polydispersity index.

  The polymers according to the invention are preferably prepared according to a so-called degenerative transfer (or degenerative iodine transfer or DIT) method. This process makes it possible to form functionalized polymers, in particular mono- or mufti-functionalised, at at least one of their ends, with an iodine atom. This process is described in particular in application WO99 / 20659.

  According to this method, the selected monomers are reacted with a polymerization initiator in the presence of an iodinated transfer agent.

  The polymerization initiator may be any initiator known to those skilled in the art for its use in radical polymerization processes, and in particular azo-type compounds and in particular azobisisobutyronitrile; or peroxide type such as hydroperoxides or organic peroxides having 6-30 carbon atoms, especially benzoyl peroxide or dodecanoyl peroxide; or redox couples, peresters, percarbonates or persulfates. Preferably, the initiator is chosen from organic peroxides comprising from 8 to 30 carbon atoms, such as the didecanoyl peroxide sold especially under the reference Perkadox SE-10 by the company Akzo Nobel. It is also possible to mention 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane (Trigonox 141 from Akzo No-bel) and tert-butyl peroxy-2-ethylhexanoate (Trigonox 21S from Akzo Nobel) as initiator. ).

  The transfer agent may be represented by the formula R'-I, in which R 'is a linear, branched or cyclic alkyl radical, saturated or unsaturated, comprising 1 to 30 carbon atoms, and may further comprise 1 to 7 additional iodine atoms, and / or one or more fluorine atoms, and / or one or more functions selected from CN, COOH. When the transfer agent comprises several iodine atoms, it may be of structure R '(I) m, with m being an integer greater than or equal to 2, especially equal to 3 to 8; when m> 2, this leads in particular to star polymers; when m = 2, difunctional polymers are obtained.

  Preferably, R 'is chosen from alkyls having 1 to 6 carbon atoms, optionally comprising one or more halogen atoms, especially fluorine atoms and / or a CN function; in particular, R 'can be a perfluorinated C1-C6 alkyl or a C1-C6 alkyl bearing a CN function. Iodo-1-perfluorohexane, iodoacetonitrile (ICH2-CN), iodo-1-methane, diiodomethane, iodoform or triiodomethane, iodo-1, may be mentioned especially as transfer agent. perfluoroisopropane, diiodoperfluorohexane, iodo-1-phenylethane, iodo-1-propane, iodo-1-isopropane, iodo-1-phenyl, 1,4-diiodophenyl and iodine -1-tert-butane. Preferably, iodo-1-perfluorohexane or iodoacetonitrile is used.

  Furthermore, the transfer agent may be macromolecular and be in the form of a polymer, homopolymer or polymer, obtained by a prior stage of degenerative transfer polymerization at the iodine atom, and thus functionalized by at least one iodine atom.

  The molar proportion between the transfer agent and the initiator, called "r", can vary between 0.1 and 20 with a preference between 1 and 10 and more precisely between 2 and 5. The molar ratio between the amount of monomers and that of transfer agent is preferably greater than 10, in particular between 30 and 2000, and more specifically between 50 and 500. The polydispersity index (Ip = Mw / Mn, that is to say molar mass average weight / molar mass in number) of the homopolymer is preferably between 1.1 and 4, in particular between 1.2 and 3, or even between 1.5 and 2.5.

  The degree of polymerization, DPn, is equal to the ratio between the number average molecular weight (Mn) of the polymer and the molar mass of the monomer; it is preferably greater than 10, in particular between 10 and 3000, preferably between 30 and 2000, and more precisely between 50 and 500.

  In a schematic manner, the polymers according to the invention can be pre-prepared by those skilled in the art according to the following procedure, given by way of illustration: 1 / the monomer is placed, optionally in a solvent, in a re-actor and with agitation. The radical polymerization initiator and the transfer agent are added. The mixture is preferably placed under an inert gas atmosphere with respect to a radical polymerization such as nitrogen or argon. As a possible polymerization solvent, the solvent medium of the composition, for example solvents and / or cosmetic oils as defined below, may be chosen. In particular, the polymerization solvent may be selected from alkyl acetates such as butyl acetate or ethyl acetate, aromatic solvents such as toluene or alkanes such as isododecane, polyisocyanate, polyisocyanate and the like. heptane or isohexadecane. A polymerization solvent is preferably chosen in which the monomer and the resulting polymer are soluble or dispersible. 2 / the mixture is stirred with the desired polymerization temperature. This temperature is preferably chosen in a range from 20 ° C. to 120 ° C., preferably from 40 ° C. to 90 ° C. The choice of the polymerization temperature is preferably optimized according to the monomer. 3 / the polymerization is stopped when the desired conversion rate is reached. This rate can be at least 50% conversion, especially at least 60%, preferably after reaching at least 90% conversion. However, it is possible to stop the polymerization before reaching this level of 50%. 4 / the possible residual monomers can be removed by any known method, such as by evaporation, or by adding an amount of conventional polymerization initiator such as peroxidic or azo derivatives.

  The polymer according to the invention can be obtained by radical polymerization in bulk or in solution in an organic medium, or alternatively in aqueous and / or organic dispersion, in emulsion in particular. The monomer may be added batchwise or semi-continuously. For batch polymerization, the optional solvent, the mono-mother, the transfer agent and the initiator are mixed in a reactor and heated to the required temperature. For a semi-continuous polymerization, a part of the monomer, in particular 1 to 20% by weight of the total weight of monomer, a portion of the initiator, in particular 1 to 20, is introduced into a reactor, all or part of the optional solvent. % by weight of the total weight of initiator, optionally a part of the transfer agent, especially 0.1 to 20% by weight of the total weight of transfer agent, and heated to the required temperature. The remainder of the solvent, the monomer, the transfer agent and the initiator is introduced by casting during polymerization. The remaining constituents may be introduced by separate or identical flows, simultaneous or not.

  The homopolymer that may be used in the cosmetic compositions according to the invention is therefore a homopolymer comprising monomers chosen from:

  i) (meth) acrylates of formula CH 2 CHCHCOOR or CH 2 CC (CH 3) OOOR in which R represents: a linear, saturated or unsaturated carbon group, especially an alkyl group, comprising 4 to 32 carbon atoms optionally comprising a or more, especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I); a branched, saturated or unsaturated, especially alkyl, carbon group comprising 4 to 32 carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); a cycloalkyl or heterocycloalkyl group comprising 3 to 32 carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); an aromatic group (aryl or aralkyl) comprising 3 to 32 carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I);

  In the radical R, the heteroatoms, when present, may be inter-stalled in the chain or ring, or substituted for example in the form of a group such as OH, SH or NR'R ", where R 'and R "identical or different re-present hydrogen or a linear or branched alkyl group C1 to C6 or a phenyl group.

  Particularly preferred are the (meth) acrylates in which R represents: - a linear, saturated or unsaturated, especially alkyl, carbon group comprising 6 to 28, in particular 10 to 22 or even 12 to 18, carbon atoms optionally comprising one or more , especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I); a branched, saturated or unsaturated carbon group, in particular alkyl, comprising 6 to 28, in particular 10 to 22 or even 12 to 18, carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); a cycloalkyl or heterocycloalkyl group comprising 4 to 28, especially 6 to 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I ); an aromatic group comprising 4 to 28, especially 5 to 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); );

  Mention may especially be made of (meth) acrylates - hexyl, octyl, nonyl, decyl, lauryl, dodecyl, stearyl, behenyl, methoxy-polyoxyethylene (or POE-methyl); POE-behenyl; isobutyl, tert-butyl, isooctyl, isodecyl, ethylhexyl, ethyl-2-perfluorohexyl; t-butylcyclohexyl, isobornyl, cyclohexyl, tetrahydrofurfurylmethyl, tetrahydrofurfuryl; benzyl, phenyl, 2-phenylethyl, tert-butylbenzyl, furfuryl, furfurylmethyl; More particularly, lauryl, dodecyl, stearyl, behenyl, isobutyl, tert-butyl, isooctyl, isodecyl, ethylhexyl, and isobornyl (meth) acrylates are preferred.

  ii) ethylenic monomers whose ester group contains silanes, silsesquioxanes, siloxanes, carbosiloxane dendrimers as described in patent EP 0963751. Preferred monomers are methacryloxypropyltris (trimethylsiloxy) silane, methacryloxyproprylbis (trimethylsiloxy) methylsilane, acryloxypropyltris (trimethylsiloxy) silane, acryloxypropylbis (trimethylsiloxy) methylsilane and methacryloxypropyltrimethoxysilane.

  iii) carbon or silicone macromonomers having at least one terpolymerizable group; it is any polymer comprising on one of its ends a polymerizable terminal group, in particular an ethylenically unsaturated group capable of polymerizing by a radical route and capable of reacting with itself during the polymerization reaction and which will allow the formation of a homopolymer having pendant side chains (which will form the grafts); the polymerizable group of the macromonomer may advantageously be a vinyl or (meth) acrylate ((meth) acryloxy) group.

  Among the macromonomers that may be used, mention may be made, in particular, of their salts and also of: (ii) linear and branched or cyclic C 4 -C 32 alkyl (meth) acrylate homopolymers and copolymers, especially C 6 -C 6 C28, or even C8-C18, having a polymerizable terminal group chosen from vinyl or (meth) acrylate groups, among which mention may be made of macromonomers of poly (ethyl-2-hexyl acrylate) with a mono (meth) acrylate end ; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers having a mono (meth) acrylate end; macromonomers of poly (stearyl acrylate) or poly (stearyl methacrylate) with a mono (meth) acrylate end; poly (isobornyl acrylate) macromonomers with a mono (meth) acrylate end; poly (isobornyl methacrylate) macromonomers with a mono (meth) acrylate end. Such macromonomers are described especially in patents EP895467 and EP96459. iiib) polyolefins having an ethylenically unsaturated terminal group, in particular a (meth) acrylate end group. As examples of such polyolefins, mention may be made in particular of the following macromonomers, it being understood that they have a terminal (meth) acrylate group: polyethylene macromonomers, polypropylene macromonomers, polyethylene / polypropylene copolymer macromonomers, polyethylene / polybutylene copolymer, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; poly (ethylene / butylene) -polyisoprene macromonomers. Such macromonomers are in particular described in US Pat. No. 5,625,005 which mentions ethylene / butylene and ethylene / propylene macromonomers with a reactive (meth) acrylate end group. In particular, mention may be made of poly (ethylene / butylene) methacrylate, such as that sold under the name Kraton Liquid L-1253 by Kraton Polymers. iiic) silicone macromonomers and in particular polydimethylsiloxanes, with a mono (meth) acrylate end group, such as those of the following formula: ## STR1 ## in which: R8 denotes a hydrogen atom or a methyl group; preferably methyl; - R9 denotes a divalent hydrocarbon group, linear or branched, preferably linear, having from 1 to 10 carbon atoms and optionally containing one or two -O- ether bonds; preferably ethylene, propylene or butylene; - 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. As silicone macromonomers, there may be mentioned in particular monomethacryloyloxypropyl polydimethylsiloxanes such as those sold under the name PS560-K6 by UCT (United Chemical Technologies Inc.) or as MCR-M17 by Gelest Inc.

  Particularly preferred macromonomers are macromonomers of poly (2-ethylhexyl acrylate) end-mo-no (meth) acrylate; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers having a mono (meth) acrylate end; stearyl poly (meth) acrylate macromonomers having a mono (meth) acrylate end; poly (ethylene / butylene) and poly (ethylene / propylene) macromonomers with a (meth) acrylate reactive end group; poly (isobornyl acrylate) macromonomers with a mono (meth) acrylate end; poly (isobornyl methacrylate) macromonomers with a mono (meth) acrylate end.

  The monomers and macromonomers may optionally be neutralized, before or after polymerization.

  Among the salts, mention may be made of those obtained by neutralization of acid groups using inorganic bases such as LiOH, NaOH, KOH, Ca (OH) 2, NH 4 OH or Zn (OH) 2; or with an organic base such as a primary, secondary or tertiary alkylamine, especially triethylamine or butylamine. This primary, secondary or tertiary alkylamine may comprise one or more nitrogen and / or oxygen atoms and may therefore comprise, for example, one or more alcohol functions; mention may especially be made of 2-amino-2-methyl-propanol, triethanolamine and 2-dimethylamino propanol. We can also mention lysine or 3- (dimethylamino) -propylamine.

  Mention may also be made of mineral acid salts, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and boric acid. Mention may also be made of organic acid salts, which may comprise one or more carboxylic acid, sulphonic acid or phosphonic acid groups. It may be linear, branched or cyclic aliphatic acids or aromatic acids. These acids may furthermore comprise one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups. These include propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid.

  Some of the homopolymers mentioned above are novel as such and form another object of the present invention.

  These homopolymers functionalised at at least one of their extremi-tees by an iodine atom, and comprising a monomer chosen from:

  i) (meth) acrylates of formula CH 2 CHCHCOOR "or CH 2 CC (CH 3) OOOR" in which R "represents: a linear, saturated or unsaturated, especially alkyl, carbon group comprising from 6 to 32, especially at 28 or even 12 to 18 carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); - a branched carbon group, saturated or unsaturated, especially alkyl, comprising 10 to 32, especially 12 to 28, or even 14 to 18 carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, C1, Br, I); a cycloalkyl or heterocycloalkyl group comprising 3 to 32, especially 4 to 28, or even 6 to 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (F1, Cl, Br, I); an aromatic group (aryl or aralkyl) comprising 3 to 32, especially 4 to 28, or 5 to 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I). (Ii) ethylenic monomers whose ester group contains silanes, silsesquioxanes, siloxanes, carbosiloxane dendrimers as described in patent EP 0963751. Preferred monomers are methacryloxypropyltris (trimethylsiloxy) silane, methacryloxyproprylbis (trimethylsiloxy) methylsilane acryloxypropyltris (trimethylsiloxy) silane, acryloxypropylbis (trimethylsiloxy) methylsilane and methacryloxypropyltrimethoxysilane. iii) carbon-containing macromonomers having at least one polymerizable terminal group, in particular a vinyl or (meth) acrylate group; it is possible in particular ci-ter, as well as their salts: -iiia) homopolymers and copolymers (alkyl) alkyl, linear, branched or cyclic, C4-C32, especially C6-C28, or even C8-C18 , exhibiting a polymerizable terminal group chosen from vinyl or (meth) acrylate groups, among which mention may be made of macromonomers of poly (2-ethylhexyl acrylate) with a mono (meth) acrylate end; macromonomers of poly (dodecyl acrylate) or poly (dodecyl methacrylate) with a mono (meth) acrylate end; macromonomers of poly (stearyl acrylate) or poly (stearyl methacrylate) with a mono (meth) acrylate end; poly (isobornyl acrylate) macromonomers with a mono (meth) acrylate end; poly (isobornyl methacrylate) macromonomers with a mono (meth) acrylate end.

  iiib) polyolefins having an ethylenically unsaturated terminal group, in particular a (meth) acrylate end group; mention may be made in particular of the following macromonomers, it being understood that they have a terminal (meth) acrylate group: polyethylene macromonomers, polypropylene macromonomers, polyethylene / polypropylene copolymer macromonomers, polyethylene / polybutylene copolymer macromonomers, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; poly (ethylene / butylene) -polyisoprene macromolecules. In particular, mention may be made of poly (ethylene / butylene) methacrylate.

  iii) silicone macromonomers, and especially polydimethylsiloxanes, with a mono (meth) acrylate end group, such as those of the following formula: ## STR1 ## in which: R8 denotes a hydrogen atom or a methyl group; preferably methyl; - R9 denotes a divalent hydrocarbon group, linear or branched, preferably linear, having from 1 to 10 carbon atoms and optionally containing one or two -O- ether bonds; preferably ethylene, propylene or butylene; - 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.

  Mention may in particular be made of monomethacryloyloxypropyl polydimethylsiloxanes.

  Preferably, the homopolymers according to the invention are chosen from: hexyl, octyl, nonyl, decyl, lauryl, dodecyl, stearyl, behenyl and methoxy-polyoxyethylene (or POE-methyl) (meth) acrylates; POE-behenyl; isodecyl; t-butylcyclohexyl, isobornyl, cyclohexyl, tetrahydrofurfurylmethyl, tetrahydrofurfuryl; benzyl, phenyl, 2-phenylethyl, tert-butylbenzyl, furfuryl, furfurylmethyl; poly (2-ethylhexyl acrylate) macromonomers having a mo-no (meth) acrylate end; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers having a mono (meth) acrylate end; stearyl poly (meth) acrylate macromonomers having a mono (meth) acrylate end; poly (ethylene / butylene) and poly (ethylene / propylene) macromonomers with a (meth) acrylate reactive end group; poly (isobornyl acrylate) macromonomers with a mono (meth) acrylate end; poly (isobornyl methacrylate) macromonomers with a mono (meth) acrylate end.

  The homopolymers according to the invention are very particularly soluble or dispersible in the usual cosmetic lipophilic media, such as especially lipophilic solvents and / or carbonated or silicone oils, usually used in cosmetics.

  The term "soluble" means that the polymer does not form a precipitate in the medium considered. Advantageously, the polymer according to the invention is soluble at a concentration of at least 1% by weight in isododecane, at 25 C, 1 atm., Preferably at a concentration of at least 3% by weight, or even at least 5% by weight. The term "dispersible" means that the polymer forms in the medium, at a concentration of at least 1% by weight, at 25 ° C., 1 atm., A stable suspension or dispersion of fine, generally spherical particles. The average particle size constituting said dispersion is less than 1 μm and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes can be measured by light scattering (with a Coulter Counter device).

  The homopolymers according to the invention may be present in cosmetic or pharmaceutical compositions, especially topical compositions, in an amount of 0.1 to 95% by weight, preferably 1 to 50% by weight, in particular 2 to 40% by weight, or even 5 to 35% by weight, relative to the total weight of the composition.

  The homopolymers may be present in the composition in solubilized form, for example in an organic solvent or a carbonated or silicone cosmetic oil. It has been found that the polymers according to the invention are particularly soluble in cosmetic solvents and that they can be used in organic cosmetic media, while retaining valuable rheological properties.

  The cosmetic or pharmaceutical compositions according to the invention comprise, besides said homopolymers, a physiologically acceptable medium, in particular cosmetically or pharmaceutically acceptable medium, that is to say a medium that is compatible with keratin materials such as the skin of vi-sage or body, lips, hair, eyelashes, eyebrows and nails.

  The composition may advantageously comprise a liquid fatty phase, which may itself comprise oils and / or preferably lipophilic solvents; it may further comprise solid fatty substances at ambient temperature such as waxes, pasty fatty substances, gums and mixtures thereof.

  Among the constituents of the liquid fatty phase, it is preferable to mention the oils and / or solvents having an overall solubility parameter according to the Hansen solubility space less than or equal to 20 (MPa) -2, preferably less than or equal to at 18 (MPa) '"2, even better or lower than 17 (MPa)'" 2. The overall solubility parameter 6 according to the Hansen solubility space is defined in the article "Solubility parameter values" of Eric A.Grulke of the book "Polymer Handbook", 3rd edition, Chapter VII, p.519-559 by the relation: 6 = (dD2 + dP2 + dH2) v2 in which - dD characterizes the dispersion forces of LONDON issues of the formation of 35 dipoles induced during molecular shocks, - dP characterizes the DEBYE interaction forces between permanent dipoles, and - dH characterizes the specific interaction forces (hydrogen bond, acid / base, donor / acceptor, etc. type). .) 40 The definition of solvents in the solution space Hansen is described in the article by C.M.Hansen "The three dimensional solubility parameters" J.Paint Technol. 39, 105 (1967).

  Among the oils and / or solvents having an overall solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2, mention may be made of: the volatile or non-volatile oils, which may be chosen from natural or synthetic oils, carbonated, hydrocarbon-based, fluorinated, optionally branched, alone or as a mixture; - The alkanes, linear or branched and / or cyclic, possibly volatile; esters, and in particular esters, linear, branched or cyclic, having at least 6 carbon atoms, in particular having from 6 to 30 carbon atoms; the ethers and in particular the ethers having at least 6 carbon atoms, in particular having from 6 to 30 carbon atoms; ketones and especially ketones having at least 6 carbon atoms, in particular having from 6 to 30 carbon atoms. aliphatic fatty alcohols, saturated or unsaturated, having 6 to 30 carbon atoms, the hydrocarbon chain having no substitution group.

  The term "non-volatile oil" means an oil that may remain on the skin at room temperature and atmospheric pressure for at least one hour and in particular having a vapor pressure at ambient temperature (25 ° C.) and atmospheric pressure, which is not zero, less than at 0.01 mmHg (1.33 Pa).

  Non-volatile carbonaceous oils, in particular hydrocarbon-based oils, of plant, mineral, animal or synthetic origin, such as paraffin oil (or petroleum jelly), squalane, hydrogenated polyisobutylene (Parleam oil), may especially be mentioned. ), perhydrosqualene, mink, macadamia, turtle, soy, sweet almond, calophyllum, palm, grape seed, sesame, maize, arara, rapeseed, sunflower, cotton, apricot, castor oil, avocado, jojoba, olive or cereal sprouts, butter of karite; linear esters, branched or cyclic, having more than 6 carbon atoms, especially 6 to 30 carbon atoms, such as esters of lanolic acid, oleic acid, lauric acid, stearic acid; esters derived from long chain (ie having from 6 to 20 carbon atoms) acids or alcohols, in particular esters of the formula RCOOR 'in which R represents the remainder of a higher fatty acid having from 7 to 19 carbon atoms and R 'represents a hydrocarbon chain comprising from 3 to 20 carbon atoms, in particular the C 12 -C 36 esters, such as isopropyl myristate, palmitate, isopropyl, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethyl-hexyl palmitate, 2-hexyl-decyl laurate, palmitate 2- octyl decyl, myristate or 2-octyl-dodecyl lactate, di (2-ethyl hexyl) succinate, diisostearyl malate, glycerin or diglycerin triisostearate; higher fatty acids, especially C14-C22 fatty acids, such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or isostearic acid; higher fatty alcohols, especially C16-C22, such as cetanol, oleic alcohol, linoleic or linolenic alcohol, isostearyl alcohol or octyl dodecanol; and their mixtures. Mention may also be made of decanol, dodecanol, octadecanol, liquid triglycerides of fatty acids containing from 4 to 10 carbon atoms, for instance triglycerides of heptanoic or octanoic acids and triglycerides of caprylic / capric acids; linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; synthetic esters and ethers, in particular of fatty acids, for example purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, octyl-2-dodecyl stearate, erucate octyl-2-dodecyl, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate, diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol. Mention may also be made of ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone and acetone; propylene glycol ethers which are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, isopentyl; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes that are liquid at room temperature, such as decane, heptane, dodecane, isododecane, isohexadecane or cyclohexane; aromatic cyclic compounds which are liquid at room temperature, such as toluene and xylene; room temperature liquid aldehydes such as benzaldehyde, acetaldehyde and mixtures thereof.

  Among the volatile compounds that may be mentioned are non-silicone volatile oils, in particular C 8 -C 16 isoparaffins such as isododecane, isodecane and iso-hexadecane and for example the oils sold under the trade names of ISOPAR. of PERMETHYL and in particular isododecane (PERMETHYL 99 A). In particular, the liquid fatty phase may comprise alkanes which are liquid at room temperature, volatile or otherwise, and more particularly decane, heptane, dodecane, isododecane, isohexadecane, cyclohexane and isodecane, and their mixtures. The liquid fatty phase may also comprise silicone oils, which may be volatile or non-volatile, and in particular chosen from linear or cyclic volatile or non-volatile polydimethylsiloxanes (PDMSs); polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes. As volatile silicone oils that can be used in the invention, mention may be made of linear or cyclic silicone oils having a viscosity at room temperature of less than 8 cSt and in particular having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups. having 1 to 10 carbon atoms; and in particular octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5 ), alone or in mixture.

  When the homopolymer mainly comprises, in particular at least 55% by weight, or even at least 70% by weight, relative to the total weight of monomers, of non-silicone carbonaceous monomers, the liquid fatty phase is advantageously constituted mainly of oils. and / or non-silicone solvents, which can therefore represent at least 50% by weight, in particular from 60 to 99.9% by weight, or else from 65 to 99% by weight, or else from 70 to 95% by weight, relative to the total weight of the liquid fatty phase. In this case, preferably, the silicone oils are present in a quantity strictly less than 50% by weight, in particular ranging from 0.1 to 40% by weight, or even ranging from 1 to 35% by weight, or from 5 to 30% by weight, relative to the total weight of the liquid fatty phase. Preferably, the liquid fatty phase does not comprise (0%) silicone oils; it therefore comprises 100% oils and / or non-silicone solvents.

  When the homopolymer mainly comprises, especially at least 55% by weight, or even at least 70% by weight, based on the total weight of monomers, of silicone monomers, the liquid fatty phase is advantageously mainly composed of silicone oils, which can therefore represent at least 50% by weight, in particular from 60 to 99.9% by weight, or else from 65 to 99% by weight, or else from 70 to 95% by weight, relative to the total weight of the liquid fatty phase .

  In this case, preferably, the oils and / or non-silicone solvents are present in an amount strictly less than 50% by weight, especially ranging from 0.1 to 40% by weight, or even ranging from 1 to 35% by weight, or else ranging from 5 to 30% by weight, relative to the total weight of the liquid fatty phase. In the compositions according to the invention, the liquid fatty phase may be generally present in a content ranging from 0.01 to 95%, preferably from 0.1 to 90%, more preferably from 10 to 85% by weight, relative to the total weight of the composition, and more preferably from 30 to 80%. The composition may further comprise a hydrophilic medium comprising water or a mixture of water and hydrophilic organic solvent (s) such as alcohols and especially lower linear or branched monoalcohols having 2 such as ethanol, isopropanol or n-propanol, and polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or else 02 ethers and hydrophilic 02-04 aldehydes. The water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0.1 to 80% by weight, relative to the total weight of the composition, and preferably from 1 to 70% by weight.

  The composition according to the invention may also comprise waxes and / or gums. For the purposes of the present invention, the term "wax" means a lipophilic compound, solid at room temperature (25 ° C.), with a reversible solid / liquid state change, having a melting point greater than or equal to 30 ° C. and up to 30 ° C. at 120 ° C. By bringing the wax to the liquid state (melting), it is possible to render it miscible with any oils present and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature a recrystallization of the wax is obtained in the oils of the mixture. The melting point of the wax can be measured using a differential scanning calorimeter (D.S.C.), for example the calorimeter sold under the name DSC 30 by the company METTLER. The waxes may be hydrocarbon-based, fluorinated and / or silicone-based and may be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting temperature of greater than 25 ° C. and better still greater than 45 ° C. As wax which can be used in the composition of the invention, mention may be made of beeswax, carnauba wax or candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene or Fischer Tropsch waxes, silicone waxes such as alkyl or alkoxy dimethicone containing from 16 to 45 carbon atoms. The gums are generally high molecular weight polydimethylsiloxanes (PDMS) or gums cellulose or polysaccharides and pasty bodies are generally hydrocarbon compounds such as lanolins and derivatives thereof or PDMS.

  The nature and quantity of the solid bodies depend on the mechanical properties and textures sought. As an indication, the composition may contain from 0.01 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.

  The composition according to the invention may further comprise one or more dyestuffs chosen from water-soluble dyes, liposoluble dyes, and pulverulent dyestuffs such as pigments, nacres, and flakes well known to those skilled in the art. The dyestuffs may be present in the composition in a content ranging from 0.01 to 50% by weight, relative to the weight of the composition, preferably from 0.02 to 25% by weight. By pigments, it is necessary to include particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition. By nacres, it is necessary to understand particles of any iridescent form, in particular produced by certain molluscs in their co-keel or synthesized. The pigments may be white or colored, mineral and / or organic. Among the inorganic pigments, titanium dioxide, optionally surface-treated, zirconium oxide or cerium oxides, and oxides of zinc, iron (black, yellow or red) or chromium, the violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metal powders such as aluminum powder, copper powder. Among the organic pigments, mention may be made of carbon black, D & C type pigments, and lacquers based on cochineal carmine, barium, strontium, calcium, aluminum. The pearlescent pigments may be chosen from white pearlescent pigments such as mica coated with titanium, or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxides, titanium mica coated with, inter alia, blue. ferric oxide or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bis (oxychloride) bis Among the water-soluble dyes, mention may be made of the disodium salt of culvert, the salt disodium of alizarin green, quinoline yellow, trisodium salt of amaranth, disodium salt of tartrazine, monosodium salt of rhodamine, disodium salt of fuchsin, xanthophyll, methylene blue.

  The composition according to the invention may also comprise, in addition, one or more fillers, in particular in a content ranging from 0.01% to 50% by weight, relative to the total weight of the composition, preferably ranging from 02% to 30% by weight. By fillers, it is necessary to include particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured. These fillers serve in particular to modify the rheology or the texture of the composition. The fillers can be mineral or organic of any form, platelet, spherical or oblong, irrespective of the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Ny-Ion) powders (Orgasol from Atochem), poly-R-alanine and polyethylene, tetrafluoroethylene polymer powders (Teflon). , lauroyl-lysine, ami-don, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel (Nobel Industrie), acrylic acid polymers (Polytrap of the company) Dow Corning) and silicone resin microbeads (Toshiba Tospearls, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and magnesium carbonate, hydroxyapatite, silica microspheres hollow (Silica Beads from Maprecos), microcapsules of glass or ceramic, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon atoms, for example st. arate zinc, magnesium or lithium, zinc laurate or magnesium myristate.

  The composition may further comprise an additional polymer such as a film-forming polymer. According to the present invention, the term "film-forming polymer" means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials. Among the film-forming polymers that may be used in the composition of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures, in particular acrylic polymers, polyurethanes , polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.

  The composition according to the invention may also comprise ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, anti-dandruff agents, propellants, ceramides, or mixtures thereof. 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, impaired by the addition envisaged.

  The composition according to the invention may especially be in the form of suspension, dispersion, especially organic solution, gel, emulsion, in particular oil-in-water emulsion (O / W) or water-in-oil (E). / H), or multiple (W / O / E or polyol / H / E or H / E / H), in the form of cream, paste, foam, dispersion of vesicles including ionic lipids or not, lotion biphase or multiphase, spray, powder, pulp, including soft dough (especially paste having a dynamic viscosity at 25 C of about 0.1 to 40 Pa.s under a shear rate of 200 s- after 10 minutes of measurement in cone / plane geometry). The composition may be anhydrous, for example it may be an anhydrous paste.

  Those skilled in the art may choose the appropriate dosage form, as well as its method of preparation, on the basis of its general knowledge, taking into account, on the one hand, the nature of the constituents used, in particular their solubility in the support, and on the other hand, of the application envisaged for the composition.

  The composition according to the invention may be a makeup composition, especially a complexion product such as a foundation, a blush or an eyeshadow; a lip product such as a lipstick or a lip care; a concealer product; a blush, a mascara, an eyeliner; an eyebrow makeup product, a lip pencil or an eye pencil; nail product such as nail polish or nail care; a body make-up product; a hair makeup product (mascara or hairspray). The composition according to the invention may be a composition for protecting or caring for the skin of the face, neck, hands or body, in particular an anti-wrinkle, anti-fatigue composition making it possible to give a boost to the skin. skin, a moisturizing or treating composition; an anti-solar composition or artificial tanning. The composition according to the invention may also be a hair product, in particular for the care, hygiene, maintenance of the hairstyle or shaping of the hair. The hair compositions are preferably shampoos, gels, styling lotions, blow-drying lotions, fixing and styling compositions such as lacquers or spray. The lotions may be packaged in various forms, in particular in vaporizers, pump-bottles or in aerosol containers to ensure application of the composition in vaporized form or in the form of foam. Such forms of packaging are indicated, for example when it is desired to obtain a spray, a mousse for fixing or treating hair. The composition according to the invention may also be a hair coloring composition.

  Advantageously, the composition according to the invention may be a makeup composition, especially a foundation or a lipstick.

  The subject of the invention is also a process for the cosmetic treatment of keratin materials, in particular the skin of the body or of the face, the nails, the hair and / or the eyelashes, comprising the application to the said materials of a cosmetic composition such as than previously defined.

  In particular, the subject of the invention is a cosmetic process for makeup of the skin of the face and / or the lips, comprising the application on said materials of a cosmetic composition of a foundation or lipstick such as previously defined.

  The invention is illustrated in more detail in the following examples.

  Example 1 Preparation of a Poly (Isobornyl Acrylate) Homopolymer

  30 g of isododecane, 30 g of isobornyl acrylate, 0.673 g of perfluorohexyl iodide (1.5 × 10 -3 mol) and 0.154 g of Perkadox SE-10 (0.45 g) are introduced into a 100 ml flask. 10-3 moles) at room temperature. After solubilization, the mixture is distributed in closed tubes of 10 ml (about 4 ml per tube) and bubbled with argon. The tubes are then immersed in an oil bath thermostated at 90 ° C. After 1 hour 30 minutes, 50% conversion is obtained. The number-average molecular weight (Mn) obtained is 14400 g / mol and the polydispersity index Ip is 2.59.

  EXAMPLE 2 Preparation of a Polvo Homopolymer (Isobornyl Acrylate) 3.5 g of isododecane, 30 g of isobornyl acrylate and 0.669 g of perfluorohexyl iodide (1%) are introduced into a 250 ml three-neck flask. 10-3 moles) and 0.154 g of Perkadox SE-10 (0.45 moles). After solubilization, the mixture is bubbled with argon. The flask is then immersed in an oil bath thermostated at 90 ° C. After 1 h 30 min., The reaction mixture is diluted to 50% concentration in isododecane and 80% conversion is obtained. The number-average molecular weight (Mn) obtained is 5800 g / mol and the polydispersity index Ip is 4.63.

  At the end of the reaction, part of the polymer is dried and then re-solubilized in isononyl isononanoate at 50% concentration.

  Example 3 (Comparative) Preparation of a poly (methyl acrylate) homopolymer In a 250 ml three-necked flask, 10 g of ethyl acetate, 30 g of methyl acrylate and 0.669 g of periluorohexyl iodide ( 1.5 × 10 -3 mol) and 0.154 g of Perkadox SE-10 (0.45 × 10 -3 mol). After solubilization, the mixture is bubbled with argon. The flask is then immersed in an oil bath thermostated at 70 C. After 1 hour, the reaction mixture is diluted to 50% concentration in butyl acetate. The number average molar mass (Mn) obtained is 55700 g / mol and the polydispersity index Ip is 2.05. At the end of the reaction, part of this polymer is dried and then put in isododecane. The polymer does not solubilize in this solvent. EXAMPLE 4 An anhydrous foundation is prepared comprising (% by weight): 12% - polyethylene wax - 25% volatile silicone oils - 20% phenyl trimethicone - 12% polymethyl methacrylate microspheres - Example 1 polymer 6% MA - Isododecane qsp 100% MA = active ingredient Preparation: The waxes are melted and then, when everything is clear, the phenyl trimethicone is added with stirring, and the silicone oils; the microspheres, isododecane and the polymer are then added. The mixture is homogenized for 15 minutes and then the resulting composition is cast and allowed to cool.

An anhydrous foundation is obtained. EXAMPLE 5 A lipstick stick is prepared comprising: 15% Polyethylene wax-Polymer of Example 2 10% MA-Hydrogenated polyisobutene (Parléam from Nippon Oil Fats) 25% -Pigments 10% -Isododecane qs 100% 40 The composition obtained after application to the lips has good cosmetic properties.

Example 6: W / O Foundation Foundry A foundation composition comprising the following compounds: Phase A - Cetyl dimethicone copolyol (ABIL EM 90 from GOLDSCHMIDT) 3g - Isostearyl diglyceryl succinate 0.6 g (IMWITOR 780K from CONDEA) - Isododecane 18.5 g - Polymer of Example 1 8.7 g MA - Pigments (iron and titanium oxides) 10g - Polyamide powder (NYLON-12) 8 g - Perfume qs Phase B - magnesium sulphate 0.7 g - qs preservative - water qs 100 g The composition obtained has good cosmetic properties.

Claims (27)

  1. Cosmetic or pharmaceutical composition comprising, in a physiologically acceptable medium, at least one homopolymer functionalized at at least one of its ends by an iodine atom, and comprising a mono-mother chosen from: - i) (meth) ) acrylates of formula CH2 = CHCOOR or CH2 = C (CH3) COOR in which R represents: - a linear, saturated or unsaturated, especially alkyl, carbon group comprising 4 to 32 carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I); a branched, saturated or unsaturated carbon group, in particular alkyl, comprising 4 to 32 carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I ); a cycloalkyl or heterocycloalkyl group comprising 3 to 32 carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); an aromatic group (aryl or aralkyl) comprising 3 to 32 carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); ; ii) the ethylenic monomers whose ester group contains silanes, silsesquioxanes, siloxanes, carbosiloxanes dendrimers; iii) the macromonomers, carbon or silicone, having at least one polymerizable end group, in particular a vinyl or (meth) acrylate group.   2. Composition according to claim 1, in which R represents: a linear, saturated or unsaturated, especially alkyl, carbon group comprising 6 to 28, in particular 10 to 22 or even 12 to 18, carbon atoms optionally comprising one or more, in particular 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I); a branched, saturated or unsaturated carbon group, in particular alkyl, comprising 6 to 28, in particular 10 to 22 or even 12 to 18, carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); a cycloalkyl or heterocycloalkyl group comprising 4 to 28, especially 6 to 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I an aromatic group comprising 4 to 28, especially 5 to 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br); , I);   3. Composition according to one of the preceding claims, wherein the monomer is selected from hexyl, octyl, nonyl, decyl, lauryl, dodecyl, stearyl, behenyl, methoxy-polyoxyethylene (or POE-methyl) (meth) acrylates. ; POE-behenyl; isobutyl, tert-butyl, isooctyl, isodecyl, ethylhexyl, ethyl-2-perfluorohexyl; t-butylcyclohexyl, isobornyl, cyclohexyl, tetrahydrofurylmethyl, tetrahydrofururyl; benzyl, phenyl, 2-phenylethyl, tert-butylbenzyl, furturyl, furturylmethyl.   4. Composition according to claim 1, in which the monomer is chosen from methacryloxypropyltris (trimethylsiloxy) silane, methacryloxypropryl-bis (trimethylsiloxy) -methylsilane, acryloxypropyltris (trimethylsiloxy) silane, acryloxypropylbis (trimethylsiloxy) methylsilane and methacryloxypropyltrimethoxysilane.   5. The composition according to claim 1, wherein the carbon-containing macromonomers are chosen from, as well as their salts: - iiia) linear, branched or cyclic C4-C32 alkyl (meth) acrylate homopolymers and copolymers, in particular C6-C28, or even C8-C18, having a polymerizable end group selected from vinyl or (meth) acrylate; iiib) polyolefins having an ethylenically unsaturated terminal group, in particular a (meth) acrylate end group; iiic) silicone macromonomers, and in particular polydimethylsiloxanes, with a mono (meth) acrylate end group, such as those of the following formula: ## STR1 ## in which: R 8 denotes a hydrogen atom; hydrogen or a methyl group; preferably methyl; - R9 denotes a divalent hydrocarbon group, linear or branched, preferably linear, having from 1 to 10 carbon atoms and optionally containing one or two -O- ether bonds; preferably, ethylene, propylene or butylene, - R 10 denotes a linear or branched alkyl group having from 1 to 10 carbon atoms, especially from 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.   The composition of claim 5, wherein the monomer is selected from. poly (2-ethylhexyl acrylate) macromonomers having a mono (meth) acrylate end; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers having a mono (meth) acrylate end; poly (stearyl acrylate) or poly (stearyl methacrylate) macromonomers with a mono (meth) acrylate end; poly (isobornyl acrylate) macromonomers with a mono (meth) acrylate end; macromonomers of poly (isobornyl methacrylate) at the mono (meth) acrylate end; the following macromonomers, it being understood that they have a terminal (meth) acrylate group: polyethylene macromonomers, polypropylene macromonomers, polyethylene / polypropylene copolymer macromonomers, polyethylene / polybutylene copolymer macromonomers, macromonomers of polyethylene polyisobutylene; polybutadiene macromonomers; polyisoprene macromonomers; poly (ethylene / butylene) -polyisoprene macromonomers; monomethacryloyloxypropyl polydimethylsiloxanes.   7. Composition according to one of the preceding claims, wherein the homopolymer has a number-average molecular mass of between 500 g / mol and 1,000,000 g / mol, in particular between 1,000 g / mol and 250,000 g / mol, and even more preferably between 2000 g / mol and 100,000 g / mol, or even 5000 g / mol and 50,000 g / mol.   8. Composition according to one of the preceding claims, wherein the homopolymer is present in an amount of 0.1 to 95% by weight, preferably 1 to 50% by weight, especially 2 to 40% by weight, or even 5 to 10% by weight. to 35% by weight, relative to the total weight of the composition.   9. Composition according to one of the preceding claims, wherein the physiologically acceptable medium comprises a liquid fatty phase which comprises oils and / or solvents having an overall solubility parameter according to Hansen solubility space less than or equal to (MPa) '"2, preferably less than or equal to 18 (MPa)'" 2, even more preferably less than or equal to 17 (MPa) '12   10. The composition of claim 9, wherein the liquid fatty phase comprises at least one oil and / or solvent selected from: - oils, volatile or not, natural or synthetic, carbonaceous, hydrocarbon, fluorinated, optionally branched, alone or in mixed; - The alkanes, linear or branched and / or cyclic, possibly volatile; esters, and in particular esters, linear, branched or cyclic, having at least 6 carbon atoms, in particular having from 6 to 30 carbon atoms; the ethers and in particular the ethers having at least 6 carbon atoms, in particular having from 6 to 30 carbon atoms; ketones and especially ketones having at least 6 carbon atoms, in particular having from 6 to 30 carbon atoms. aliphatic fatty alcohols, saturated or unsaturated, having 6 to 30 carbon atoms, the hydrocarbon chain having no substitution group; silicone oils, volatile or non-volatile.   11. Composition according to one of Claims 9 to 10, in which the liquid fatty phase comprises at least one oil and / or solvent chosen from: non-volatile carbonaceous oils, in particular hydrocarbon oils, of plant or mineral origin, animal or synthetic, such as paraffin oil (or vase-line), squalane, hydrogenated polyisobutylene (Parleamam oil), perhydrosqualene, mink, macadamia, turtle, soybean oil, sweet almond oil, calophyllum, palm, grape seed, sesame, maize, arara, rapeseed, sunflower, cotton, apricot, castor oil, avocado, jojoba, olive or seeds of cereals, shea butter; linear, branched or cyclic esters having more than 6 carbon atoms, especially 6 to 30 carbon atoms, such as esters of lanolic acid, oleic acid, lauric acid and stearic acid; esters derived from acids or alcohols with a long chain (that is to say having from 6 to 20 carbon atoms), in particular esters of formula RCOOR 'in which R represents the residue of a fatty acid with 7 to 19 carbon atoms and R 'represents a hydrocarbon chain containing from 3 to 20 carbon atoms, in particular the C 12 -C 36 esters, such as isopropyl myristate, isopropyl palmitate, stearate, of butyl, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyl-decyl laurate, 2-octyl-decyl palmitate, myristate or 2-octyl-dodecyl lactate, di (2-ethyl hexyl) succinate, diisostearyl malate, glycerin or diglycerine triisostearate; higher fatty acids, especially of C14-C22, such as myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid and linolenic acid; or isostearic acid; higher fatty alcohols, especially C16-C22, such as cetanol, oleic alcohol, alcoollinoleic or linolenic, isostearyl alcohol or octyl dodecanol; decanol, dodecanol, octadecanol, liquid triglycerides of fatty acids with 4 to 10 carbon atoms, for example triglycerides of heptanoic or octanoic acids, triglycerides of caprylic / capric acids; linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and their derivatives, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as parleam; esters and synthetic ethers, in particular of fatty acids, for example purcellin oil, isopropyl myristate, 2-ethylhexyl palmitate, octyl-2-dodecyl stearate, octyl-2-dodecyl erucate, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, heptanoates, octanoates and decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentyl glycol diheptanoate and diethylene glycol diisononanoate; and pentaerythritol esters; fatty alcohols having from 12 to 26 carbon atoms, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol and 2-undecylpentadecanol. ketones which are liquid at ambient temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone; propylene glycol ethers which are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-butyl ether; short-chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, acetate isopentyl; ethers which are liquid at ambient temperature, such as diethyl ether, dimethyl ether or dichlorodiethyl ether; alkanes that are liquid at room temperature, such as decane, heptane, dodecane, isododecane, isohexadecane or cyclohexane; aromatic cyclic compounds which are liquid at ambient temperature, such as toluene and xylene; aldehydes which are liquid at ambient temperature, such as benzaldehyde and acetaldehyde, and mixtures thereof. non-silicone volatile oils, in particular C 8 -C 16 isoparaffins such as isododecane, isodecane and isohexadecane;   12. Composition according to one of claims 9 to 10, wherein the liquid fatty phase comprises at least one silicone oil selected from polydimethylsiloxanes (PDMS) volatile or not, linear or cyclic; polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, during or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenylsiloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes; linear or cyclic silicone oils having a viscosity at room temperature of less than 8 cSt and in particular having from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms; and in particular octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5 ), alone or in mixture.   13. Composition according to one of the preceding claims, wherein the homopolymer comprises at least 55% by weight, or even at least 70% by weight, relative to the total weight of monomers, of non-silicone carbon monomers and wherein the medium physiologically acceptable comprises a liquid fatty phase consisting of oils and / or non-silicone solvents, which represent at least 50% by weight, in particular from 60 to 99.9% by weight, or from 65 to 99% by weight, or from 70 to 95% by weight, relative to the total weight of the liquid fatty phase.   14. Composition according to one of claims 1 to 12, wherein the homopolymer comprises at least 55% by weight, or even at least 70% by weight, relative to the total weight of monomers, of silicone monomers and in which the physiologically acceptable medium comprises a liquid fatty phase consisting of silicone oils, which represent at least 50% by weight, in particular from 60 to 99.9% by weight, or from 65 to 99% by weight, or from 70 to 95% by weight, based on the total weight of the liquid fatty phase.   15. Composition according to one of the preceding claims, wherein the physiologically acceptable medium further comprises at least one constituent selected from water; alcohols and in particular linear or branched lower monoalcohols having from 2 to 5 carbon atoms, such as ethanol, isopropanol or n-propanol; polyols such as glycerine, diglycerine, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols; C2 ethers and hydrophilic C2-C4 aldehydes; waxes and / or gums; coloring matters such as water-soluble dyes, fat-soluble dyes, pigments, nacres, and flakes; the charges; polymers; vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-oxidants, hair loss, anti-dandruff agents, propellants, ceramides, or mixtures thereof.   16. Composition according to one of the preceding claims, in the form of a makeup composition, especially a complexion product such as a foundation, a blush or eyeshadow; a lip product such as a lipstick or a lip care; a concealer product; a blush, a mascara, an eyeliner; an eyebrow makeup product, a lip pencil or an eye pencil; nail product such as nail polish or nail care; a body make-up product; a hair makeup product (mascara or hairspray); a composition for protecting or caring for the skin of the face, neck, hands or body, in particular an anti-wrinkle, anti-fatigue composition which makes it possible to give a radiance to the skin, a moisturizing composition or contractor; an anti-sun or artificial tanning composition; a hair composition, especially for the care, hygiene, maintenance of the hairstyle or the shaping of the hair; of a hair coloring composition.   17. homopolymer functionalized at at least one of its ends by an iodine atom, and comprising a monomer chosen from: - i) (meth) acrylates of formula CH2 = CHCOOR "or CH2 = C (CH3) COOR" in which R "represents: - a linear, saturated or unsaturated, especially alkyl, carbon group comprising 6 to 32, in particular 10 to 28 or even 12 to 18, carbon atoms optionally comprising one or more, especially 1 to 5 heteroatoms chosen from O, N, P, S and halogen (FI, Cl, Br, I); a branched, saturated or unsaturated, in particular alkyl, carbon group comprising 10 to 32, especially 12 to 28, or even 14 to 18, carbon atoms; optionally comprising one or more, especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I); a cycloalkyl or heterocycloalkyl group comprising 3 to 32, in particular 4 to 28, or even 6 at 12, carbon atoms, optionally comprising one or more, especially 1 to 5 heteroatoms selected from O , N, P, S and halogen (FI, Cl, Br, I); an aromatic group (aryl or aralkyl) comprising 3 to 32, especially 4 to 28, or even 5 to 12, carbon atoms, optionally comprising one or several, especially 1 to 5 heteroatoms selected from O, N, P, S and halogen (FI, Cl, Br, I); ii) ethylenic monomers whose ester group contains silanes, silsesquioxanes, siloxanes, carbosiloxane dendrimers; iii) carbon-containing macromonomers having at least one polymerizable end group, in particular a vinyl or (meth) acrylate group, as well as their salts.   18. The homopolymer according to claim 17, wherein the monomer is chosen from: iiia) homopolymers and copolymers (alkyl), linear, branched or cyclic, C4-C32, especially C6-C28, or C8-C18, having a polymerizable end group selected from vinyl or (meth) acrylate; iiib) polyolefins having an ethylenically unsaturated terminal group, in particular a (meth) acrylate end group; iii) silicone macromonomers and in particular polydimethylsiloxanes, with a mono (meth) acrylate end group, such as those of the following formula: ## STR2 ## in which: R 8 denotes a hydrogen atom; hydrogen or a methyl group; preferably methyl; - R9 denotes a divalent hydrocarbon group, linear or branched, preferably linear, having from 1 to 10 carbon atoms and optionally containing one or two -O- ether bonds; preferably ethylene, propylene or butylene; R10 denotes a linear or branched alkyl group having from 1 to 10 carbon atoms, especially from 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.   19. Homopolymer according to claim 17, in which the monomer is chosen from: hexyl, octyl, nonyl, decyl, lauryl, dodecyl, stearyl, behenyl and methoxy-polyoxyethylene (or POE-methyl) (meth) acrylates; POE-behenyl; isodecyl; t-butylcyclohexyl, isobornyl, cyclohexyl, tetrahydrofurylmethyl, tetrahydrofururyl; benzyl, phenyl, 2-phenyl-ethyl, tert-butylbenzyl, furturyl, furturylmethyl, poly (ethyl-2-hexyl acrylate) macromonomers having a mono (meth) acrylate end; poly (dodecyl acrylate) or poly (dodecyl methacrylate) macromonomers having a mono (meth) acrylate end; stearyl poly (meth) acrylate macromonomers having a mono (meth) acrylate end; poly (ethylene / butylene) and poly (ethylene / propylene) macromonomers with a (meth) acrylate reactive end group; poly (isobornyl acrylate) macromonomers with a mono (meth) acrylate end; poly (isobornyl methacrylate) macromonomers with a mono (meth) acrylate end. methacryloxypropyltris (trimethylsiloxy) silane, methacryloxypropryl-bis (trimethylsiloxy) methylsilane, acryloxypropyltris (trimethylsiloxy) silane, acryloxypropylbis (trimethylsiloxy) methylsilane and methacryloxypropyltrimethoxysilane. monomethacryloyloxypropyl polydimethylsiloxanes. poly (mono) acrylate end-capped macromonomers, mono (meth) acrylate-terminated polypropylene macromonomers, mono (meth) acrylate-terminated polyisobutylene macromonomers; macro-monomers of polybutadiene end mono (meth) acrylate; polyisoprene macromonomers with a mono (meth) acrylate end; poly (ethylene / butylene) -polyisoprene macromonomers with a mono (meth) acrylate end.   20. Homopolymer according to one of claims 17 to 19, having a number-average molecular weight of between 500 g / mol and 1,000,000 g / mol, in particular between 1,000 g / mol and 250,000 g / mol, and even better. between 2000 g / mol and 100,000 g / mol, or even 5000 g / mol and 50,000 g / mol.   21. The homopolymer according to one of claims 17 to 20, obtainable by controlled radical polymerization by degenerative transfer to the iodine atom: at least one radical initiator, at least one agent, transfer comprising at least one iodine atom, and a monomer as defined in one of claims 17 to 19.   Homopolymer according to claim 21, wherein the polymerization initiator is selected from azo compounds and especially azobisisobutyronitrile; or peroxide type such as hydroperoxides or organic peroxides having 6-30 carbon atoms, especially benzoyl peroxide or didecanoyl peroxide; or redox pairs, peresters, percarbonates or persulfates; or 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane and tert-butyl peroxy-2-ethylhexanoate.   23. Homopolymer according to one of claims 21 to 22, wherein the transfer agent is: - of formula R'-I, wherein R 'is a linear, branched or cyclic alkyl radical, saturated or unsaturated, comprising 1 to 30 carbon atoms, and which may further comprise 1 to 7 additional iodine atoms, and / or one or more fluorine atoms, and / or one or more functions selected from CN, COOH; or - of formula R '(I) m, with m being an integer greater than or equal to 2, in particular equal to 3 to 8.   Homopolymer according to one of Claims 21 to 23, in which the transfer agent is chosen from iodo-1-perfluorohexane, iodoacetonitrile (ICH2-ON), iodo-1-methane and diiodomethane. iodoform or triiodomethane, iodo-1-perchloropropane, diiodoperiluorohexane, iodo-1-phenylethane, iodo-1-propane, iodo-1-isopropane, iodo 1-phenyl, 1,4-diiodo-phenyl and iodo-1-tert-butane.   25. Homopolymer according to one of claims 21 to 22, wherein the transfer agent is macromolecular and is in the form of a polymer, homopolymer or polymer, functionalized with at least one iodine atom.   26. Process for the cosmetic treatment of keratinous substances, in particular of the skin of the body or face, nails, hair and / or eyelashes, comprising the application to said materials of a cosmetic composition as defined in one of the following: Claims 1 to 16.   27. Cosmetic makeup process for the skin of the face and / or lips, comprising the application on said materials of a cosmetic composition as defined in one of claims 1 to 16.