Patent Publication Number: US-2006008431-A1

Title: Copolymer functionalized with an iodine atom, compositions comprising the copolymer and treatment processes

Description:
This application claims benefit of U.S. Provisional Application No. 60/586,311, filed Jul. 9, 2004, the contents of which are incorporated herein by reference. This application also claims benefit of priority under 35 U.S.C. § 119 to French Patent Application No. 04 51182, filed Jun. 15, 2004, the contents of which are also incorporated by reference. 
    
    
      The present disclosure relates to novel copolymers and to compositions, such as cosmetic, pharmaceutical or dermatological topical compositions, including these copolymers.  
      In the field of cosmetics, compositions for obtaining a deposit, such as an adhesive or film-forming deposit, on keratin materials, such as the hair, the skin, the eyelashes or the nails, are often sought. For example, these compositions may provide color (i.e., in makeup or hair coloring compositions), sheen or a matt effect (i.e., in skincare or skin makeup compositions), physical properties such as shaping (i.e., in hair compositions, such as styling compositions), and protective or care properties (i.e., in care compositions, for example moisturizing or anti-UV compositions). Good remanance and good staying power of the cosmetic deposit over time, and also good adhesion to the support, are generally sought. Such deposits should be able, generally, to withstand mechanical attack such as rubbing or transfer on contact with another object; water, sweat, tears, rain, sebum and oils. This is particularly important for makeup, for example, lipsticks, where prolonged staying power of color and gloss, and transfer resistance of color are sought. This is also important for makeup such as foundations, eye shadows and face powders, where staying power of the color supplied by the composition is sought, while simultaneously maintaining the transfer resistance and also the matt effect exhibited by the initial shade for as long as possible, despite the secretion of sebum and sweat by the wearer. In addition, makeup compositions that are comfortable to wear and do not have an excessively tacky texture are desired.  
      The above-recited properties often conflict with one another. To achieve a composition that reconciles these properties within the same composition, a mixture of several different polymers, of different chemical nature, is generally used, with each polymer providing at least one of the desired characteristics. However, polymers, having different chemical natures, within such a mixture are not necessarily compatible with one another. This may result in the polymer mixture exhibiting demixing problems within the composition.  
      It is known to add random polymers, such as conventional acrylic polymers obtained by standard free-radical polymerization via random mixing of monomers, to a composition containing a mixture of polymers, in an attempt to solve the demixing problem. However, these random polymers are known to exhibit dispersity in the polymer chains of the composition, which itself can lead to demixing. Thus, the addition of these random polymers does not solve this problem satisfactorily.  
      In addition, the process of atom transfer radical polymerization (ATRP) is known and described in U.S. Pat. No. 5,807,937. ATRP allows the preparation of certain polymers that may be functionalized at their end, for example, with a bromine or chlorine atom. However, this process requires the use of metal catalysts, trace amounts of which may remain in the polymers thus prepared. If these polymers are used for cosmetic applications, the presence of trace amounts metal catalyst in the polymer may pose a problem. In addition, Br and Cl atoms are not always labile enough to be easily replaced with more desired functions.  
      Further, polymers that are functionalized at their end and are obtained by degenerative transfer (DT) are known and described in document No. WO99/20659. Free-radical polymerization controlled via DT allows the synthesis of functionalized (co)polymers of controlled molar mass and architecture. However, most polymers that have been prepared via this technique are homopolymers.  
      The present disclosure relates to novel copolymers that are cosmetically acceptable and functionalized on at least one of their ends with an atom that is labile enough to be readily replaced.  
      Further, copolymers of the present disclosure may avoid the prior art problems of demixing within the formula while at the same time providing desired cosmetic properties.  
      One aspect of the present disclosure is a copolymer functionalized on at least one of its ends with an iodine atom, and comprising at least two different monomers. One of the monomers of the at least two different monomers is chosen from soluble monomers, and the other of the at least two different monomers is chosen from insoluble monomers, as defined below.  
      Another aspect of the disclosure is a copolymer that may be obtained via free-radical polymerization controlled by degenerative transfer at the iodine atom: 
          of at least one free-radical initiator,     of at least one transfer agent comprising at least one iodine atom, and     of at least two different monomers, wherein one is chosen from soluble monomers and the other from insoluble monomers, as defined below.        

      Another aspect of the disclosure is a cosmetic or dermatological composition comprising, in a physiologically acceptable medium, at least one copolymer as defined above.  
      Copolymers according to the present disclosure may be easy to use in organic cosmetic media, such as solvent-based media and/or cosmetic oil media, while at the same time retaining advantageous rheological properties.  
      Further, the copolymers according to the disclosure exhibit good liposolubility in cosmetic solvents and/or cosmetic oils.  
      For the purpose of the present disclosure, the term, “soluble polymer” means a polymer that does not form a precipitate when dispersed in a solvent. In one embodiment of the present disclosure, the copolymer is soluble at a concentration of at least 3% by weight in isododecane at 25° C. and 1 atm, such as at least 5% or at least 10% by weight.  
      The copolymers of the present disclosure may be in various forms, such as in the form of a block or gradient polymer. In one embodiment, the copolymer of the present disclosure is in the form of a gradient polymer. In this embodiment, the copolymer may, for example, be utilized in high concentrations in the cosmetic compositions of the disclosure.  
      In a gradient copolymer, the composition within the polymer chain follows a composition gradient. In one embodiment of the disclosure, the gradient copolymer has a low composition polydispersity, meaning that all of the copolymer chains have an approximately analogous composition (i.e. sequence of monomers) and are therefore of homogeneous composition. As a result, cosmetic compositions comprising these copolymers do not exhibit the drawbacks and/or limitations of the compositions of the prior art.  
      The copolymer according to the disclosure may be linear gradient copolymer, represented by the formula: 
 
F-[M 1 M 2 ] gradient -I 
          in which F represents a residue derived from the transfer agent (the radical R defined below) or from the initiator; I is an iodine atom; and M 1  and M 2  are monomers or a mixture of monomers.        

      According to one embodiment, the copolymers according to the disclosure may also be in block polymer form. For example, the polymers of the present disclosure may be in the form of a polymer comprising at least two different successive blocks, such as two successive blocks of different chemical nature. Each block of the copolymer according to the disclosure may be derived from one or more types of monomer. Therefore each block may consist of a homopolymer or a copolymer. If a block is a copolymer, this copolymer may be a random, alternating or gradient copolymer. As a result, the monomer distribution within each block may be random or controlled, depending on the nature and/or reactivity of the monomers.  
      If the copolymer of the present disclosure is a block copolymer, it may be a diblock polymer of the AB type; or a triblock polymer, i.e. of the type ABA, BAB or ABC, wherein C is different from A and B; or multiblock polymers containing more than three blocks, i.e. of the type (AB)n, (ABA)n, (BAB)n, (ABC)n or ABCD, wherein A, B, C and D are of different chemical nature. In one embodiment of the present disclosure, the copolymer comprises at least 2 or 3 successive blocks, wherein the two successive blocks are different. For example, the copolymer may be of the AB, ABA or ABC type.  
      If the copolymer according to the present disclosure is a linear block copolymer, it may be represented schematically by the formula: F-[(M 1 ) n -(M 2 ) m ]I, in which n and m are integers greater than 1.  
      According to one embodiment of the disclosure, the copolymers according to the disclosure may also be in the form of a star polymer, wherein each branch of the star may be in gradient or block form. Star polymers are obtained when the transfer agent utilized is polyfunctional and includes at least three iodine atoms.  
      If the copolymer is a a star copolymer, it may be represented by the formula F-[M 1 M 2 -I] n , wherein: M 1  and M 2  are different and represent a single monomer or a monomer mixture, and are arranged in a gradient (F-[(M 1 M 2 ) grad -I] n′ ) or block (F-[(M 1 ) n (M 2 ) m -I] n′ ) form; and n′ represents the number of branches in the star, and is an integer greater than 2, such as from 3 to 8.  
      If n′ is equal to 2, the polymer obtained is linear and difunctional.  
      According to yet another embodiment, the copolymer according to the present disclosure may be a grafted copolymer, the skeleton of which may be in gradient or block form. Grafted polymers may be obtained when one or more of the monomers M 1  and/or M 2  is a macromonomer as defined below.  
      According to the present disclosure, the copolymers may be in block, gradient, linear-chain, grafted or star form.  
      In one embodiment, the copolymer is a linear, gradient or block copolymer.  
      The number-average molecular mass of the copolymer according to one embodiment of the present disclosure may be from 2000 g/mol to 1,000,000 g/mol, such as from 3000 g/mol to 500,000 g/mol, from 4000 g/mol to 200,000 g/mol, or from 5000 g/mol to 50,000 g/mol.  
      As used in the present disclosure, the number-average molecular mass (Mn) is determined via liquid gel permeation chromatography (GPC) using a THF eluent and a refractometric detector. Calibration is performed using linear polystyrene standards.  
      The copolymers of the present disclosure may be obtained by free-radical polymerization controlled by degenerative transfer at the iodine atom. For purposes of this disclosure, the term, “controlled free-radical polymerization” denotes polymerization for which the side reactions that usually lead to the termination or transfer of the the propagating species are rendered highly unlikely, relative to propagation reactions carried out by means of a free-radical control agent. However, when the concentration of free radicals become high relative to the monomer concentration, these side reactions become determining factors and generally result in a polymer having a broader mass distribution.  
      During controlled free-radical polymerization, the polymer chains of the gradient copolymers of the disclosure grow simultaneously, and thus incorporate the same ratio of comonomers over time. Therefore, all of the chains have the same or similar structure, resulting in low composition dispersity. Further, these chains also have a low mass polydispersity index. As mentioned above, gradient copolymers are copolymers having a concentration gradient of the various monomers along the chain. The distribution of the polymer chains of the comonomers depends on the relative concentrations of the comonomers during the synthesis. The gradient copolymers according to the disclosure comprise at least two different monomers, the concentration of which changes gradually along the polymer chain in both a systematic and predictable manner. Therefore, all of the polymer chains have at least one monomer Mi for which, irrespective of the normalized position x on the polymer chain, there is a non-zero probability of finding this same monomer along the chain. One of the defining characteristics of a gradient copolymer is the fact that at any instant in the polymerization, all of the chains are subjected to the presence of all of the monomers. Thus, in the reaction medium, the concentration of each monomer is always non-zero, at any instant in the polymerization.  
      This fact makes it possible to differentiate between gradient copolymers and block polymers in which the evolution of the monomers along the polymer chain is not systematic: for example, for a diblock copolymer AB, within the sequence A, the concentration of the monomer B is always zero.  
      In the case of random polymers, the concentration gradient of the monomers along the polymer chain will not be gradual, systematic and predictable.  
      Moreover, among gradient copolymers in general, copolymers with a natural gradient and copolymers with an artificial gradient may be distinguished.  
      A copolymer with a natural gradient is a gradient copolymer batch-synthesized starting with an initial mixture of the comonomers. The distribution in the chain of the various monomers follows a law deduced from the relative reactivity and the initial monomer concentrations. These copolymers constitute the simplest class of gradient copolymers, because the initial mixture defines the final property of the product.  
      A copolymer with an artificial gradient is a copolymer whose monomer concentration is varied during the synthesis. In this case, the relative concentration of monomers in the chain of the copolymer changes due to a sudden and abrupt change of the monomers and/or monomer concentration in the reaction medium. Further, one or more monomers may disappear, to the benefit of one or more others.  
      Moreover, in a gradient copolymer, the relative distribution of the compositions between the various chains of the copolymer is narrow. In particular, there is no overlap between the peak for the gradient copolymer and those for the respective homopolymers. This means that the material obtained by gradient polymerization includes polymer chains having the same composition, whereas by standard random polymerization, various kinds of chain coexist, including those of the respective homopolymers.  
      Factors which impact the gradient include the relative reactivity coefficients of each monomer (known as r i  for the monomer Mi). These reactivity coefficients depend primarily on the type of synthetic process (homogeneous or dispersed) and solvents used. However, these coefficients are also impacted by the initial concentrations of each of the monomers, and by changes in monomer concentration, i.e. through the addition of monomers during the polymerization.  
      In a non-limiting embodiment of the present disclosure, the copolymers are prepared according to a degenerative transfer (DT) or a degenerative iodine transfer (DIT) process. These processes allow the formation of copolymers that are functionalized (i.e. mono- or multi-functionalized), on at least one of their ends, with an iodine atom. This process is described in patent application No. WO 99/20659.  
      In the DT or DIT processes, the chosen monomers are reacted with at least one polymerization initiator in the presence of an iodine-containing transfer agent.  
      The at least one polymerization initiator may be chosen from any initiator known to those skilled in the art for use in free-radical polymerization processes. Non-limiting examples of such initiators include azo type compounds, such as azobisisobutyronitrile; peroxide type compounds, such as organic hydroperoxides or peroxides containing 6-30 carbon atoms, for example benzoyl or didecanoyl peroxide; as well as redox couples, peresters, percarbonates or persulfates.  
      In a non-limiting embodiment of the present disclosure, the at least one initiator is chosen from organic peroxides containing from 8 to 30 carbon atoms, such as the didecanoyl peroxide sold under the reference PERKADOX® SE-10 by the company Akzo Nobel.  
      Further non-limiting examples of the at least one initiator include 2,5-bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane (TRIGONOX 141 from the company Akzo Nobel) and tert-butyl peroxy-2-ethylhexanoate (TRIGONOX 21S from the company Akzo Nobel).  
      The at least one iodine containing transfer agent may be represented by the formula R-I, in which R is a linear, branched or cyclic, saturated or unsaturated alkyl radical containing from 1 to 30 carbon atoms. R may optionally comprise 1 to 4 additional iodine atoms, one or more fluorine atoms, and/or one or more functional groups chosen from CN and COOH.  
      In a non-limiting embodiment of the present disclosure, R is chosen from alkyls containing 1 to 6 carbon atoms, and may comprise one or more halogen atoms, such as fluorine, and/or a CN function. For example, R may be a perfluoro C1-C6 alkyl or a C1-C6 alkyl bearing a CN function.  
      Non-limiting examples of the at least one transfer agent that may be mentioned include iodo-1-perfluorohexane, iodoacetonitrile (ICH 2 —CN), iodo-1-methane, diiodomethane, iodoform or triiodomethane, iodo-1-perfluoroisopropane, diiodoperfluorohexane, iodo-1-phenylethane, iodo-1-propane, iodo-1-isopropane, iodo-1-phenyl, 1,4-diiodophenyl and iodo-1-tert-butane.  
      Further, the at least one transfer agent may be macromolecular and may be in the form of a polymer, homopolymer or copolymer, obtained via a prior step of degenerative iodine transfer polymerization, and thus functionalized with at least one iodine atom.  
      According to one embodiment of the disclosure, transfer agents prepared by DIT are suitably used to prepare block copolymers.  
      According to one embodiment, the molar proportion r between the transfer agent and the initiator may range from 0.1 to 20, such as from 1 to 10, or from 2 to 5.  
      The molar proportion DP between the set of monomers and the transfer agent may be greater than 10, and may range from 50 to 1000, for example, from 100 to 500.  
      The copolymers of the present disclosure may be prepared, for example, by a person skilled in the art according to the following procedure:  
      1) A mixture of the various monomers is prepared, optionally in a solvent, preferably in a reactor, and is stirred. A free-radical polymerization initiator and a transfer agent are added. The mixture is preferably under an atmosphere of inert gas relative to a free-radical polymerization, such as nitrogen or argon.  
      The optional polymerization solvent may be chosen from cosmetic solvents and/or oils as defined below. For example, the polymerization solvent may be chosen from alkyl acetates such as butyl acetate or ethyl acetate, aromatic solvents such as toluene or alkanes such as isododecane, heptane or isohexadecane.  
      In general, a polymerization solvent in which the monomers and the resulting polymer are soluble is chosen.  
      2) The mixture is brought to the desired polymerization temperature and is stirred. The polymerization temperature may, for example, be within a range from 20° C. to 120° C., such as from 40° C. to 90° C.  
      The choice of the polymerization temperature may be optimized as a function of the chemical composition of the monomer mixture.  
      3) The polymerization medium is optionally modified during the polymerization, before reaching 90% conversion of the initial monomers, by supplemental addition of one or more monomers, such as a monomer from the initial mixture, or the same monomer combination as in the initial mixture. This addition may be performed in various ways, including abrupt addition of a single portion of additional monomer(s), or via continuous addition of monomer(s) over the time period during which polymerization takes place.  
      4) The polymerization reaction terminates when the desired degree of conversion is reached. The overall composition of the copolymer depends on the amount of conversion. In a non-limiting embodiment of the present disclosure, the polymerization is terminated after having reached at least 50% conversion. In other non-limiting embodiments, the polymerization reaction is terminated after reaching at least 60% or at least 90% conversion.  
      5) After the polymerization reaction is terminated, residual monomers which may remain can be removed by known methods, such as by evaporation, or by addition of an amount of standard polymerization initiator such as peroxide or azo derivatives.  
      6) If a block copolymer is desired, the additional monomer(s), and optionally the transfer agent and the initiator, may be added in an additional step, to form a second block.  
      The copolymer of the present disclosure may be obtained by free-radical polymerization either in bulk or in solution in an organic medium. The monomers may be added simultaneously, batch-wise, semi-continuously or consecutively.  
      For batch polymerization, the optional solvent, the monomers and the initiator may be mixed together in a reactor and heated to the required temperature.  
      For semi-continuous polymerization, all or some of the optional solvent, some of the monomers, i.e. from 1% to 20% by weight relative to the total weight of monomer, some of the initiator, i.e. from 1% to 20% by weight relative to the total weight of initiator, and optionally some of the transfer agent, i.e. from 0.1% to 20% by weight relative to the total weight of transfer agent, are introduced into a reactor and the mixture is heated to the required temperature. The remaining solvent of the monomers and the initiator is introduced by flow addition during the polymerization. The remaining constituents may then be introduced via identical or different, simultaneous or separate flow additions.  
      In a non-limiting embodiment of the present disclosure, a block copolymer is formed by a process in which the first block is formed by polymerization of the first monomer or mixture of first monomers, after which the the second monomer or mixture of monomers is added batch-wise or semi-continuously.  
      In a non-limiting embodiment of the present disclosure, a copolymer having a composition gradient is prepared via a process where the monomers are introduced batch-wise or semi-continuously. The polymerization of the first monomer, or mixture of first monomers, is started, and the second monomer, or mixture of second monomers, is added simultaneously, batch-wise, or semi-continuously, before the polymerization of the first monomer is complete.  
      Finally, according to one embodiment, the copolymer of the present disclosure comprises at least two different monomers, wherein at least one is chosen from “soluble” monomers, and the other is chosen from “insoluble” monomers.  
      For the purpose of the present disclosure, the term “soluble monomer,” means any monomer whose homopolymer is soluble, i.e. does not form a precipitate in the solvent, at a concentration of at least 3% by weight in isododecane at 25° C. and 1 atm.  
      In various non-limiting embodiments of the present disclosure, the at least one soluble monomer is chosen from monomers whose homopolymer is soluble at a concentration of at least 5% by weight, for example, 10% by weight, in isododecane at 25° C. and 1 atm.  
      For the purpose of the present disclosure, the term “insoluble monomer,” means any monomer whose homopolymer is insoluble at a concentration of at least 3% by weight in isododecane at 25° C. and 1 atm.  
      In various non-limiting embodiments of the present disclosure, the soluble monomers may be from the following monomers: 
      (i) (meth)acrylates of formula CH 2 ═CHCOOR or CH 2 ═C(CH 3 )COOR in which R represents: 
        a linear or branched alkyl group containing 8 to 30 carbon atoms, wherein the alkyl group is optionally: a) intercalated with one or more hetero atoms chosen from O, N, S and P and/or; b) substituted with one or more substituents chosen from —OH, halogen atoms (i.e. Cl, Br, I and F), and groups —NR4R5, in which R4 and R5 may be identical or different and represent hydrogen or a linear or branched C1 to C6 alkyl group or a phenyl group;     a C8 to C12 cycloalkyl group, Non-limiting examples of R include octyl, decyl, lauryl, isooctyl, isodecyl, dodecyl, t-butylcyclohexyl, stearyl, 2-ethylhexyl, isobornyl, and behenyl groups;    
        (ii) tert-butyl methacrylate and isobutyl acrylate;     (iii) (meth)acrylamides of the formula CH 2 ═CHCONR 4 R 5  or CH 2 ═C(CH 3 )CONR 4 R 5  in which: 
        R4 represents a hydrogen atom or a linear or branched alkyl group containing from 1 to 6 carbon atoms; preferably, R4 is chosen from: hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, isohexyl, cyclohexyl;     R5 represents a linear or branched alkyl group containing from 8 to 18 carbon atoms, such as an octyl, isooctyl, decyl, isodecyl, cyclodecyl, dodecyl, cyclododecyl, isononyl, undecyl, lauryl, t-butylcyclohexyl, stearyl, or 2-ethylhexyl group;    
        (iv) vinyl ethers of formula R 6 O—CH═CH 2 , or vinyl esters of formula: R 6 —COO—CH═CH 2 , in which R 6  represents a linear or branched alkyl group containing from 8 to 22 carbon atoms; the salts thereof; and mixtures thereof.    

      The macromonomer may be any polymer, such as an oligomer, comprising on only one of its ends an end group, i.e., a polymerizable end group, capable of reacting during the polymerization reaction with the monomers under consideration, to form the side chains of the polymer; this end group may be an ethylenically unsaturated group capable of undergoing free-radical polymerization with the monomers constituting the skeleton. The macromonomer allows the side chains of the copolymer to be formed. The polymerizable group of the macromonomer may advantageously be an ethylenically unsaturated group capable of undergoing free-radical polymerization. The said polymerizable end group may be in particular a vinyl or (meth)acrylate group.  
      Non-limiting examples of suitable macromonomers that may be used include the following compounds: 
          (v)a) linear or branched C8-C22 alkyl (meth)acrylate homopolymers and copolymers containing a polymerizable end group chosen from vinyl or (meth)acrylate groups, including but not limited to poly(2-ethylhexyl acrylate) macromonomers containing a mono(meth)acrylate end; poly(dodecyl acrylate) or poly(dodecyl methacrylate) macromonomers containing a mono(meth)acrylate end; and poly(stearyl acrylate) or poly(stearyl methacrylate) macromonomers containing a mono(meth)acrylate end. Such macromonomers are described in patents EP 895 467 and EP 96459.     (v)b) polyolefins containing an ethylenically unsaturated end group, including but not limited to those containing a (meth)acrylate end group. Non-limiting examples of such polyolefins include the following macromonomers, it being understood that they have a (meth)acrylate end group: polyethylene macromonomers, polypropylene macromonomers, polyethylene/polypropylene copolymer macromonomers, polyethylene/polybutylene copolymer macromonomers, polyisobutylene macromonomers; polybutadiene macromonomers; polyisoprene macromonomers; polybutadiene macromonomers; and poly(ethylene/butylene)-polyisoprene macromonomers. Such macromonomers are described in U.S. Pat. No. 5,626,005, which discloses ethylene/butylene and ethylene/propylene macromonomers containing a (meth)acrylate reactive end group. Non-limiting mention is also made of poly(ethylene/butylene) methacrylate, such as the product sold under the name KRATON LIQUID L-1253 by Kraton Polymers.     (vi) ethylenic hydrocarbons containing from 2 to 10 carbons, including but not limited to ethylene, isoprene or butadiene.        

      In a non-limiting embodiment of the present disclosure, the at least one soluble monomer is chosen from: 
          (meth)acrylates of formula CH 2 ═CHCOOR or CH 2 ═C(CH 3 )COOR, in which R represents a linear or branched alkyl group containing 8 to 30 carbon atoms or a C8 to C12 cycloalkyl group;     linear or branched C8-C22 alkyl (meth)acrylate homopolymers and copolymers containing a polymerizable end group chosen from vinyl or (meth)acrylate groups containing at least one polymerizable end group;     polyolefins containing an ethylenically unsaturated end group, including those containing a (meth)acrylate end group.        

      Non-limiting examples of soluble monomers that may be utilized include isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, tert-butyl methacrylate, isobutyl acrylate; behenyl methacrylate, behenyl acrylate; and also poly(2-ethylhexyl acrylate) macromonomers containing a mono(meth)acrylate end group; poly(dodecyl acrylate) or poly(dodecyl methacrylate) macromonomers containing a mono(meth)acrylate end group; polystearyl (meth)acrylate macromonomers containing a mono(meth)acrylate end group; as well as ethylene/butylene and ethylene/propylene macromonomers containing a (meth)acrylate reactive end group.  
      In a non-limiting embodiment of the present disclosure, the at least one insoluble monomer may be chosen from the following monomers: 
          (i) (meth)acrylates of formula CH 2 ═CHCOOR or CH 2 ═C(CH 3 )COOR in which R represents:     with the exclusion of tert-butyl methacrylate and isobutyl acrylate, a linear or branched alkyl group containing 1 to 6 carbon atoms, in which the alkyl group is optionally: a) intercalated with one or more hetero atoms chosen from O, N, S and P; or b) substituted with one or more substituents chosen from —OH, halogen atoms (Cl, Br, I and F), groups —NR 4 R 5 , in which R 4  and R 5  may be identical or different, and represent hydrogen or a linear or branched C1 to C6 alkyl phenyl group, a polyoxyalkylene group having 5 to 30 repeating polyoxyalkylene groups, such as polyoxyethylene and/or polyoxypropylene;     a C3 to C6 cycloalkyl group, wherein the cycloalkyl group optionally comprises one or more hetero atoms chosen from O, N, S and/or P, and/or may be substituted with one or more substituents chosen from —OH and halogen atoms (such as Cl, Br, I and F);     a C5 to C8 aryl or C6 to C10 aralkyl group (i.e. an aryl group having a C1 to C5 alkyl group); wherein, in a non-limiting embodiment, R may be chosen from a methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, 2-hydroxyethyl, 2-hydroxybutyl, 2-hydroxypropyl, methoxyethyl, ethoxyethyl, methoxypropyl, phenyl, 2-phenylethyl, t-butylbenzyl, benzyl, furfurylmethyl or tetrahydrofurfurylmethyl, methoxypolyoxyethylene (or POE-methyl) group; POE-behenyl, trifluoroethyl; dimethylaminoethyl, diethylaminoethyl, or dimethylaminopropyl group;     (ii) (meth)acrylamides of the formula CH 2 ═CHCONR 4 R 5  or CH 2 ═C(CH 3 )CONR 4 R 5 , in which R4 and R5 may be identical or different and represent a hydrogen atom or a linear or branched alkyl group containing from 1 to 6 carbon atoms, wherein said linear or branched alkyl group is optionally: a) intercalated with one or more hetero atoms chosen from O, N, S and P; or b) substituted with one or more substituents chosen from hydroxyl groups, halogen atoms (i.e. Cl, Br, I and F) and groups —NR′ 4 R′ 5 , in which R′ and R′5 may be identical or different, and represent a C1 to C4 alkyl group; in a non-limiting alternative embodiment, R 4  represents a hydrogen atom and R 5  represents a 1,1-dimethyl-3-oxobutyl group; Non-limiting examples of suitable R4 and R5 groups include: hydrogen, methyl, ethyl, propyl, ispropyl, n-butyl, isobutyl, tert-butyl, hexyl, isohexyl, cyclohexyl, dimethylaminoethyl, diethylaminoethyl, and dimethylaminopropyl;     (iii) ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric or sulfonic acid or anhydride function, for instance acrylic acid and methacrylic acid; crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylamidopropanesulfonic acid, and the salts thereof;     (iv) the vinyl ethers of formula R 6 O—CH═CH 2  or the vinyl esters of formula R 6 —COO—CH═CH 2  in which R 6  represents a linear or branched alkyl group containing from 1 to 6 atoms;     (v) styrene and its derivatives, such as methylstyrene, chlorostyrene or chloromethylstyrene;     (vi) silicone macromonomers, such as polydimethylsiloxane, containing a mono(meth)acrylate end group, such as those of formula (IIa) below:  
                 
 
 in which: 
    R 8  denotes a hydrogen atom or a methyl group; in a non-limiting embodiment R 8  is methyl;     R 9  denotes a linear or branched, divalent hydrocarbon-based group containing from 1 to 10 carbon atoms and optionally includes one or two ether bonds —O—; i.e., ethylene, propylene or butylene; in a non-limiting embodiment R 9  is linear;     R 10  denotes a linear or branched alkyl group containing from 1 to 10 carbon atoms, i.e., from 2 to 8 carbon atoms; In a non-limiting embodiment, R 10  is methyl, ethyl, propyl, butyl or pentyl;     n denotes an integer ranging from 1 to 300, i.e., from 3 to 200 or from 5 to 100.        

      Non-limiting examples of silicone macromonomers include monomethacryloyloxypropyl polydimethylsiloxanes, such as those sold under the name PS560-K6 by UCT (United Chemical Technologies Inc.) or under the name MCR-M17 by Gelest Inc; 
          (vii) ethylenically unsaturated monomers comprising at least one tertiary amine function, such as 2-vinylpyridine or 4-vinylpyridine;     (viii) vinyl compounds of formula: CH2═CH—R 9 , CH2═CH—CH2-R 9  or CH2═CH(CH3)-CH2-R 9  
 
 in which R 9  is a hydroxyl group, a halogen (i.e. Cl or F), NH2, OR 10  in which R 10  is a phenyl group or a C1 to C12 alkyl group (i.e. the monomer is a vinyl or allylic ether); 
    (ix) ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloyloxypropyltrimethoxysilane and methacryloyloxypropyltris(trimethylsiloxy)silane;     (x) perfluorooctyl acrylate.        

      In a non-limiting embodiment of the present disclosure, the at least one insoluble monomer is chosen from: 
          (meth)acrylates of formula CH 2 ═CHCOOR or CH 2 ═C(CH 3 )COOR, in which R represents, with the exclusion of tert-butyl methacrylate and isobutyl acrylate, a linear or branched alkyl group containing 1 to 6 carbon atoms or a C3 to C6 cycloalkyl group;     (meth)acrylamides of formula CH 2 ═CHCONR 4 R 5  or CH 2 ═C(CH 3 )CONR 4 R 5 , 
 
 in which R 4  and R 5  may be identical or different, and represent a hydrogen atom or a linear or branched alkyl group containing from 1 to 6 carbon atoms; In a more specific non-limiting embodiment of the present disclosure, R 4  represents a hydrogen atom and R 5  represents a 1,1-dimethyl-3-oxobutyl group; 
    ethylenically unsaturated monomers comprising at least one carboxylic acid function,     ethylenically unsaturated monomers comprising one or more silicon atoms, such as methacryloyloxypropyl-trimethoxysilane and methacryloyloxypropyltris-(trimethylsiloxy)silane; and     perfluorooctyl acrylate.        

      Non-limiting examples of the at least one insoluble monomer includes methyl, ethyl, propyl, n-butyl, cyclohexyl or tert-butyl (meth)acrylate; isobutyl methacrylate; methoxyethyl or ethoxyethyl (meth)acrylate; trifluoroethyl methacrylate; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl acrylate; dimethylaminopropylmethacrylamide; (meth)acrylic acid; styrene, perfluorooctyl acrylate; and salts thereof.  
      In a non-limiting embodiment, the at least one insoluble monomer is chosen from methyl acrylates, methoxyethyl acrylates, methyl methacrylates, isobutyl methacrylates, 2-hydroxyethyl methacrylates, acrylic acid, methacrylic acid, dimethylaminoethyl methacrylates, perfluorooctyl acrylates, cyclohexyl methacrylates and tert-butyl acrylates, and salts thereof.  
      Non-limiting mention is made of copolymers wherein: 
          the at least one soluble monomer is chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof; and/or     the insoluble monomer is chosen from isobutyl methacrylate and methyl methacrylate, and mixtures thereof.        

      In another non-limiting embodiment of the disclosure, the copolymer(s) comprises: 
          isobornyl acrylate and isobutyl methacrylate;     isobornyl acrylate and methyl methacrylate;     isobornyl methacrylate and isobutyl methacrylate;     isobornyl methacrylate and methyl methacrylate;     isobornyl acrylate, 2-ethylhexyl acrylate; and isobutyl methacrylate;     isobornyl acrylate, isobutyl acrylate and isobutyl methacrylate;     isobornyl methacrylate, isobutyl acrylate and isobutyl methacrylate; or     isobornyl acrylate, 2-ethylhexyl acrylate and methyl methacrylate.        

      Among the salts, non-limiting mention is made of those obtained by neutralization of acid groups using mineral 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. These primary, secondary or tertiary alkylamines may comprise one or more nitrogen and/or oxygen atoms and therefore may comprise one or more alcohol functions; Non-limiting examples of such alkyamines include 2-amino-2-methylpropanol, triethanolamine, 2-dimethylaminopropanol, lysine, or 3-(dimethylamino)propylamine.  
      Further non-limiting examples of salts that may be utilized include: salts of mineral acids, such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or boric acid; and salts of organic acids, including those that comprise one or more carboxylic, sulfonic or phosphonic acid groups. These salts may be linear, branched or cyclic aliphatic acids, or aromatic acids. These acids may further comprise one or more hetero atoms chosen from O and N, which may be present, for example, in the form of hydroxyl groups. In a non-limiting embodiment of the invention, the acid is chosen from propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid.  
      The soluble monomers as defined above may be present in the copolymer in an amount ranging from 50% to 99% by weight, such as from 60% to 90%, or from 70% to 85% relative to the total weight of monomers.  
      The insoluble monomers as defined above may be present in the copolymer in an amount ranging from 1% to 50% by weight, such as from 10% to 40%, or from 15% to 30% by weight relative to the total weight of monomers.  
      The copolymer may, additionally comprise at least one additional monomer, wherein the additional monomer is chosen from one or more insoluble or soluble monomers. In a non-limiting embodiment of the disclosure, the additional monomer is a soluble monomers.  
      In another non-limiting embodiment of the disclosure, the copolymer comprises at least one monomer with a Tg of less than or equal to 20° C., i.e., from −150° C. to 20° C., from −130° C. to 18° C., or from −120° C. to 15° C., or a mixture of such monomers.  
      The at least one monomer having the Tg property disclosed above may be chosen from the soluble or insoluble monomers mentioned above.  
      The at least one monomer with a Tg≦20° C. may be present in the copolymer in an amount ranging from 1% to 99% by weight, such as from 10% to 90%, 20% to 80%, or 25% to 75% by weight, relative to the total weight of the copolymer.  
      In a non-limiting embodiment, the copolymer according to the disclosure further comprises at least one monomer with a Tg of greater than or equal to 20° C., i.e. from 25 to 150° C., from 30 to 145° C., or from 40 to 140° C., or a mixture of such monomers.  
      These monomers having a Tg of greater than or equal to 20, 25, 30, and 40° C. may be chosen from the soluble or insoluble monomers mentioned above.  
      The monomer(s) with a Tg≧20° C. may be present in an amount ranging from 1% to 99% by weight, i.e. from 10 to 90% by weight, from 20 to 80% by weight, or from 25 to 75% by weight, relative to the total weight of the copolymer.  
      For the purpose of the present disclosure, the term “monomer with a Tg” denotes monomers whose homopolymer has such a Tg. In the present disclosure, the Tg (glass transition temperature) values are theoretical Tg values determined from the theoretical Tg values of the constituent monomers of each of the blocks, which may be found in a reference manual such as the Polymer Handbook, 3 rd  edition, 1989, John Wiley, according to the following relationship, known as Fox&#39;s law:  
         1   Tg     =       ∑   i     ⁢           ⁢     (     wi   Tgi     )           
          wherein wi is the mass fraction of the monomer i in the block under consideration and Tgi is the glass transition temperature of the homopolymer of the monomer i.        

      A person skilled in the art would know how to select the monomers and the amounts thereof as a function of the desired result, on the basis of his general knowledge, for example, of the relative reactivity of each monomer. For example, the type and amount of monomers and the solvent medium may be chosen so as to obtain a copolymer that is soluble in the said solvent medium.  
      In a non-limiting embodiment of the present disclosure, the copolymers of the present disclosure are soluble in lipophilic solvent media, such as the solvents (i.e., the lipophilic solvents) and/or the carbon-based oils conventionally used in cosmetics.  
      For the purposes of this disclosure, the term “soluble,” means that the polymer does not form a precipitate in a solvent in which it is contained. In a non-limiting embodiment of the present disclosure, the copolymer is soluble at a concentration of at least 1% by weight in isododecane at 25° C. and 1 atm.  
      The gradient copolymers of the present disclosure may be present in cosmetic, dermatological, or topical compositions in an amount ranging from 0.1% to 95% by weight, i.e. from 0.5% to 90%, from 1% to 80%, from 5-70%, or from 8% to 30% by weight, relative to the total weight of the composition.  
      The copolymers of the present disclosure may be present in the composition in dissolved form, for example in an organic solvent or a cosmetic carbon-based oil.  
      Non-limiting embodiments of the copolymers of the present disclosure may be soluble in cosmetic solvents, and may be used in organic cosmetic media, while at the same time retaining advantageous rheological properties.  
      The cosmetic or dermatological compositions of the present disclosure may further comprise, in addition to the aforementioned copolymers, a physiologically acceptable medium, such as a cosmetically or dermatologically acceptable medium (i.e., a medium that is compatible with keratin materials such as facial or body skin, the lips, the hair, the eyelashes, the eyebrows and the nails).  
      The composition of the present disclosure may further comprise a solvent medium, which may be a fatty phase that may itself comprise oils and/or solvents that may be lipophilic, as well as fatty substances that are solid at room temperature, i.e. waxes, pasty fatty substances and gums, and mixtures thereof.  
      Among the constituents of the fatty phase, non-limiting mention may be made of at least one oil and/or solvent having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 , less than or equal to 18 (MPa) 1/2 , or less than or equal to 17 (MPa) 1/2 .  
      The global solubility parameter δ according to the Hansen solubility space is defined in the article “Solubility parameter values” by Eric A. Grulke in the book “Polymer Handbook”, 3 rd  edition, Chapter VII, pp. 519-559, by the relationship: 
 
δ=( dD   2   +dP   2   +dH   2 ) 1/2  
          in which 
            dD characterizes the London dispersion forces derived from the formation of dipoles induced during molecular impacts,     dP characterizes the Debye forces of interaction between permanent dipoles, and     dH characterizes the specific forces of interaction (such as hydrogen bonding, acid/base, donor/acceptor, etc.).    
               

      The definition of solvents in the Hansen solubility space is described in the article by C. M. Hansen “The three-dimensional solubility parameters”, J. Paint Technol. 39, 105 (1967).  
      Among the at least one oil and/or solvent having a global solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa) 1/2 , non-limiting mention may be made of branched or unbranched, volatile or non-volatile oils, which may be chosen from natural or synthetic oils, carbon-based oils, hydrocarbon-based oils, fluoro oils, and mixtures thereof; ethers and esters containing at least 6 carbon atoms, such as from C6 to C30 ethers and esters; ketones containing at least 6 carbon atoms, such as C6 to C30 ketones; C6 to C30 aliphatic fatty monoalcohols, the hydrocarbon-based chain of which does is un substituted.  
      For the purpose of the present disclosure, the term “non-volatile oil” means an oil that is capable of remaining on the skin at room temperature and atmospheric pressure for at least one hour, and which may have vapor pressure at room temperature (25° C.) and atmospheric pressure, of less than 0.01 mm Hg (1.33 Pa).  
      Of the aforementioned non-volatile oils, non-limiting mention may be made of carbon-based oils, including hydrocarbon-based non-volatile oils of plant, mineral, animal or synthetic origin, such as liquid paraffin (petroleum jelly), squalane, hydrogenated polyisobutylene (PARLEAM oil), perhydrosqualene, mink oil, macadamia oil, turtle oil, soybean oil, sweet almond oil, beauty-leaf oil, palm oil, grapeseed oil, sesame seed oil, corn oil, arara oil, rapeseed oil, sunflower oil, cottonseed oil, apricot oil, castor oil, avocado oil, jojoba oil, olive oil or cereal germ oil, and shea butter oil; linear, branched or cyclic esters containing more than 6 carbon atoms, for example C6 to C30 esters such as lanolic acid, oleic acid, lauric acid or stearic acid esters; esters derived from long-chain acids or alcohols (i.e. acids or alcohols containing from 6 to 20 carbon atoms), such as esters of formula RCOOR′, in which R represents a C7-C19 higher fatty acid residue and R′ represents a C3-C20 hydrocarbon-based chain, for example C12-C36 esters such as isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate or lactate, bis(2-ethylhexyl) succinate, diisostearyl malate and glyceryl or diglyceryl triisostearate; higher fatty acids, including 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, such as C16-C22 higher fatty alcohols, such as cetanol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, isostearyl alcohol or octyldodecanol; and mixtures thereof.  
      Non-limiting mention may also be made of decanol, dodecanol, octadecanol, liquid triglycerides of C4-C10 fatty acids, such as heptanoic or octanoic acid triglycerides, and caprylic/capric acid triglycerides; linear or branched hydrocarbons of mineral or synthetic origin, such as liquid paraffins and derivatives thereof, petroleum jelly, polydecenes, and hydrogenated polyisobutene such as PARLEAM; synthetic esters and ethers, including those of fatty acids, such as PURCELLIN oil, isopropyl myristate, 2-ethylhexyl palmitate, 2-octyldodecyl stearate, 2-octyldodecyl erucate or isostearyl isostearate; hydroxylated esters, such as isostearyl lactate, octyl hydroxystearate, octyldodecyl hydroxystearate, diisostearyl malate, triisocetyl citrate, and fatty alcohol heptanoates, octanoates and decanoates; polyol esters, such as propylene glycol dioctanoate, neopentyl glycol diheptanoate or diethylene glycol diisononanoate; pentaerythritol esters; and C12 to C26 fatty alcohols, such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol or 2-undecylpentadecanol.  
      Non-limiting mention may also be made of ketones that are liquid at room temperature, such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone or acetone; propylene glycol ethers that are liquid at room temperature, such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate or dipropylene glycol mono-n-butyl ether; C3-C8 short-chain esters, such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate or isopentyl acetate; ethers that are liquid at room 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; cyclic aromatic compounds that are liquid at room temperature, such as toluene and xylene; aldehydes that are liquid at room temperature, such as benzaldehyde and acetaldehyde; and mixtures thereof.  
      Among the volatile compounds, non-limiting mention may be made of non-silicone volatile oils, such as C8 to C16 Isoparaffins, including, for example, isododecane, isodecane, and isohexadecane and the oils sold under the trade names ISOPAR and PERMETHYL. In a non-limiting embodiment of the present disclosure, the volatile compound is the isododecane known as PERMETHYL 99A.  
      In addition, non-limiting mention may be made of volatile or non-volatile alkanes that are liquid at room temperature, such as decane, heptane, dodecane, isododecane, isohexadecane, cyclohexane and isodecane, and mixtures thereof.  
      These oils and/or solvents may be present in the composition in an amount ranging from 0.01% to 95%, i.e., from 0.1% to 90%, from 10% to 85%, or from 30% to 80% by weight, relative to the total weight of the composition.  
      The composition of the present disclosure may further comprise a hydrophilic medium comprising water or a mixture of water and at least one hydrophilic organic solvent. Non-limiting examples of suitable compounds that may be used in the hydrophilic medium include alcohols, such as linear or branched lower monoalcohols containing from 2 to 5 carbon atoms, i.e. ethanol, isopropanol or n-propanol; polyols, such as glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol and polyethylene glycols; hydrophilic C2 ethers; and hydrophilic C2-C4 aldehydes.  
      The water or the mixture of water and of hydrophilic organic solvents may be present in the composition of the present disclosure in an amount ranging from 0.1% to 80% by weight, or from 1% to 70% by weight, relative to the total weight of the composition.  
      The composition of the present disclosure may further comprise at least one wax and/or gum.  
      For the purposes of the present disclosure, the term “wax” means a lipophilic compound that is solid at room temperature (25° C.), can undergo a reversible solid/liquid phase change, and has a melting point ranging from 30° C. to 120° C. By bringing the wax to the liquid state (melting), the wax may become miscible with the oils that may be present in the composition, resulting in the formation of a microscopically homogeneous mixture. However, on returning the temperature of the mixture to room temperature, recrystallization of the wax in the oils of the mixture takes place. The melting point of the wax may be measured using a differential scanning calorimeter (DSC), such as the calorimeter sold under the name DSC 30 by the company Mettler.  
      Non-limiting examples of compounds which may be utilized as the aforementioned at least one wax include hydrocarbon-based waxes, fluoro waxes and/or silicone waxes. These waxes may be of plant, mineral, animal and/or synthetic origin. The waxes may have a melting point of greater than 25° C., e.g., greater than 45° C. Of these waxes, non-limiting mention may be made of beeswax, carnauba wax, candelilla wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes, such as polyethylene waxes or Fischer Tropsch waxes; and silicone waxes, such as C16 to C45 alkyl or alkoxy dimethicones.  
      Non-limiting examples of the aforementioned gums include polydimethylsiloxanes (PDMSs) of high molecular weight, cellulose gums, polysaccharides, and pasty substances that are generally hydrocarbon-based compounds, such as lanolins, derivatives thereof, or polydimethylsiloxanes.  
      The type and amount of the solid substances used in the present disclosure depend on the mechanical properties and textures desired. Non-limiting examples of the composition of the present disclosure may contain from 0.01% to 50% by weight, e.g., from 1% to 30% by weight, of the aforementioned waxes, relative to the total weight of the composition.  
      The composition of the present disclosure may further comprise one or more dyestuffs chosen from water-soluble dyes, liposoluble dyes and pulverulent dyestuffs, such as pigments, nacres and flakes that are known to those skilled in the art. These dyestuffs may be present in the composition in an amount ranging from 0.01% to 50% by weight, e.g., from 0.01% to 30% by weight, relative to the weight of the composition.  
      As used herein, the term “pigments” means white or colored, mineral or organic particles of any shape, which are insoluble in the physiological medium and are intended to color the composition. Further, the term “nacres” as used herein, means iridescent particles of any shape, which may be produced synthetically or by certain molluscs in their shell. The pigments may be white or colored, and may be mineral and/or organic. Among these mineral pigments, non-limiting mention may be made of titanium dioxide (which may be surface-treated), zirconium oxide, cerium oxide, zinc oxide, iron oxide (black, yellow or red), chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and metal powders, such as aluminium or copper powder. Among the afroementioned organic pigments, non-limiting mention may be made of carbon black, pigments of D &amp; C type, and lakes based on cochineal carmine or on barium, strontium, calcium or aluminium. Non-limiting examples of nacreous pigments that may be utilized include white nacreous pigments such as mica coated with titanium or bismuth oxychloride, colored nacreous pigments such as titanium mica coated with iron oxides, titanium mica coated with ferric blue or chromium oxide, titanium mica coated with an organic pigment disclosed above, and nacreous pigments based on bismuth oxychloride.  
      Among water-soluble dyes, non-limiting mention may be made of the disodium salt of ponceau, the disodium salt of alizarin green, quinoline yellow, the trisodium salt of amaranth, the disodium salt of tartrazine, the monosodium salt of rhodamine, the disodium salt of fuchsin, xanthophyll, and methylene blue.  
      The composition according to the disclosure may further comprise one or more fillers. Said fillers may be present in the composition in an amount ranging from 0.01% to 50% by weight, e.g., from 0.01% to 30% by weight, relative to the total weight of the composition. As used herein, the term “fillers” means colorless or white, mineral or synthetic particles of any shape, which are insoluble in the medium of the composition irrespective of the temperature at which the composition is manufactured. These fillers may serve to modify the rheology or texture of the composition. The fillers may be mineral or organic and of any shape, i.e. platelet-shaped, spherical or oblong, irrespective of the crystallographic form (for example lamellar, cubic, hexagonal, orthorhombic, etc.). Of these fillers, non-limiting mention may be made of talc, mica, silica, kaolin, polyamide (NYLON) powder (ORGASOL® from Atochem), poly-β-alanine powder, polyethylene powder, powders of tetrafluoroethylene polymers (TEFLON), lauroyllysine, starch, boron nitride, hollow polymer microspheres such as those of polyvinylidene chloride/acrylonitrile, for example EXPANCEL® (Nobel Industrie), acrylic acid copolymers (POLYTRAP from the company Dow Corning), silicone resin microbeads (for example TOSPEARLS® from Toshiba), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium hydrocarbonate, hydroxyapatite, hollow silica microspheres (SILICA BEADS® from Maprecos), glass or ceramic microcapsules, and metal soaps derived from organic carboxylic acids containing from 8 to 22 carbon atoms, e.g., from 12 to 18 carbon atoms, including, for example zinc, magnesium or lithium stearate, zinc laurate or magnesium myristate.  
      The composition may further comprise an additional polymer such as a film-forming polymer. According to the present disclosure, the term “film-forming polymer” means a polymer capable of forming, by itself or in the presence of an auxiliary film-forming agent, a continuous film that adheres to a support, i.e. a keratin materials. Among the film-forming polymers that may be used in the composition of the present disclosure, non-limiting mention may be made of synthetic free-radical polymers, polycondensate polymers, and polymers of natural origin and mixtures thereof, i.e. acrylic polymers, polyurethanes, polyesters, polyamides, polyureas and cellulose-based polymers such as nitrocellulose.  
      The composition according to the disclosure may further comprise additional ingredients that are commonly used in cosmetics, examples of which include, but are not limited to vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, fragrances, acidifying or basifying agents, preserving agents, sunscreens, surfactants, antioxidants, agents for preventing hair loss, antidandruff agents, propellants and ceramides, or mixtures thereof. Needless to say, a person skilled in the art will take care to select this or these optional additional compound(s), and/or the amount thereof, such that the advantageous properties of the compositions according to the disclosure are not, or are not substantially, adversely affected by their addition.  
      The composition according to the disclosure may be in the form of a suspension, a dispersion, a solution (e.g., an organic solution), a gel, an emulsion (e.g., an oil-in-water (O/W); a water-in-oil (W/O) emulsion, or a multiple emulsion (W/O/W or polyol/O/W or O/W/O emulsion)), a cream, a paste, a mousse, a dispersion of vesicles (i.e. of ionic or nonionic lipid vesicles), a two-phase or multi-phase lotion, a spray, a powder or a paste (e.g., a soft paste, such as a paste having a dynamic viscosity at 25° C. of about from 0.1 to 40 Pa·s at a shear rate of 200 s −1 , after measurement for 10 minutes in cone/plate geometry). Further, the composition may be anhydrous in form, e.g., as an anhydrous paste.  
      A person skilled in the art may select the appropriate form of the composition, as well as the method for preparing it, on the basis of his general knowledge, taking into account the nature of the constituents used, such as their solubility in the support, and the intended use of the composition.  
      The composition according to the disclosure may be a makeup composition, i.e. a complexion product such as a foundation, a makeup rouge, or an eye shadow; a lip product, such as a lipstick or a lip care product; a concealer product; a blush, a mascara or an eyeliner; an eyebrow makeup product such as a lip or eye pencil; a nail product such as a nail varnish or a nail care product; a body makeup product; or a hair makeup product such as a hair mascara or hair lacquer.  
      The composition of the present disclosure may be a protective or care composition for facial skin, the neck, the hands or the body, such as an anti-wrinkle composition, an anti-fatigue composition for making the skin look radiant, a moisturizing or medicated composition, an sunscreen composition, or an artificial tanning composition.  
      The composition of the present disclosure may be a hair care product, i.e. for holding a hairstyle or for shaping the hair. The hair care product may be a shampoo, a hair setting gel or lotion, a blow-drying lotion, or a fixing and styling composition such as a lacquer or spray. The lotions may be packaged in various forms, e.g., in vaporizers, pump-dispenser bottles, or aerosol containers to enable application of the composition in vaporized form or in the form of a mousse. Such packaging forms are advantageous when it is desired to obtain a spray or a mousse for fixing or treating the hair.  
      In a non-limiting embodiment the composition of the present disclosure is a makeup composition, such as a foundation or a lipstick.  
      Another aspect of the present disclosure is a cosmetic process for making up or caring for keratin materials, such as body or facial skin, the nails, the hair and/or the eyelashes, comprising providing the aforementioned composition, and applying the composition to a keratin material.  
      In a non-limiting embodiment, the present disclosure relates to a cosmetic process, comprising providing the aforementioned composition in the form of a cosmetic foundation or lipstick, and applying the composition to facial skin or the lips.  
      Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific example are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.  
      The following examples are intended to illustrate the invention in a non-limiting manner. 
    
    
     EXAMPLE 1  
     Preparation of a Gradient Copolymer of poly(isobornyl acrylate)/methyl acrylate Composition  
      10 g of isododecane, 21 g of isobornyl acrylate, 9 g of methyl acrylate, 1.338 g of iodoperfluorohexane (3×10 −3  mol) and 0.308 g of PERKADOX SE-10 (9×10 −4  mol) were introduced into a 250 ml three-necked flask. The mixture was stirred at 25° C. and, after dissolution, the three-necked flask was immersed in an oil bath and thermostatically maintained at 80° C. for 1 hour and 20 minutes, after which the degree of conversion observed was 83%.  
      A gradient copolymer of poly(isobornyl acrylate/methyl acrylate) composition was obtained, with an iodine atom at the end of each chain. The number-average molar mass (Mn) was 8800 g/mol (with a theoretical Mn of 6500 g/mol).  
      The iodo end functions were characterized by MALDI-TOF or by NMR.  
     EXAMPLE 2  
     Preparation of a Gradient Copolymer of poly(isobornyl acrylate/methyl acrylate) Composition  
      10 g of isododecane, 24 g of isobornyl acrylate, 6 g of methyl acrylate, 1.339 g of iodoperfluorohexane (3×10 −3  mol) and 0.308 g of PERKADOX SE-10 (9×10 −4  mol) were introduced into a 250 ml three-necked flask. The mixture was stirred at 25° C. and, after dissolution, the three-necked flask was immersed in an oil bath and thermostatically maintained at 80° C. for 1 hour and 40 minutes, after which the degree of conversion observed was 81%.  
      A linear and gradient copolymer of poly(isobornyl acrylate/methyl acrylate) composition was obtained, with an iodine atom at the end of each chain.  
      The number-average molar mass (Mn) was 7650 g/mol (with a theoretical Mn of 6300 g/mol).  
      The iodo end functions were characterized by MALDI-TOF or by NMR.  
     EXAMPLE 3  
     Preparation of a Gradient Copolymer of poly(isobornyl acrylate/methyl acrylate) Composition  
      10 g of isododecane, 15 g of isobornyl acrylate, 15 g of methyl acrylate, 1.339 g of iodoperfluorohexane (3×10 −3  mol) and 0.308 g of PERKADOX SE-10 (9×10 −4  mol) were introduced into a 250 ml three-necked flask. The mixture was stirred at 25° C. and, after dissolution, the three-necked flask was immersed in an oil bath and thermostatically maintained at 75° C. for 1 hour 40 minutes, after which the degree of conversion observed was 79%.  
      A gradient copolymer of poly(isobornyl acrylate/methyl acrylate) composition was obtained, with an iodine atom at each chain end. The number-average molar mass (Mn) obtained was 9500 g/mol (with a theoretical Mn of 6100 g/mol).  
      The iodo end functions were characterized by MALDI-TOF or by NMR.  
     EXAMPLE 4  
      An anhydrous foundation was prepared, comprising (% by weight):  
                                                      polyethylene wax   12%           volatile silicone oils   25%           phenyltrimethicone   20%           polymethyl methacrylate microspheres   12%           polymer of Example 1    6%           isododecane   qs               100%                       
 
      Preparation:  
      The waxes were melted and, when clear, the phenyl trimethicone was added with stirring, along with the silicone oils; the microspheres, the isododecane and the polymer were then added. The mixture was homogenized for 15 minutes and the resulting composition was cast and allowed to cool.  
      An anhydrous foundation was obtained.  
     EXAMPLE 5  
      A lipstick was prepared, comprising:  
                                                      polyethylene wax   15%           polymer of Example 2   10%               AM           hydrogenated polyisobutene (PARLEAM   25%           from Nippon Oil Fats)           pigments   10%           isododecane   qs               100%                       
 
      The composition that was obtained exhibited good cosmetic properties after application to the lips.  
     EXAMPLE 6  
     W/O Foundation  
      A foundation composition comprising the following compounds was prepared:  
      Phase A  
                                                          Phase A                   cetyl dimethicone copolyol (Abil EM 90   3   g           from Goldschmidt)           isostearyl diglyceryl succinate (IMWITOR   0.6   g           780 K from the company Condea)           isododecane   18.5   g           pigments (iron oxide and titanium oxide)   10   g           polymer of Example 1   8.7   g                                 ADM                                 polyamide powder (NYLON-12)   8   g                             fragrance   qs                                 Phase B                                     water   qs                                     100   g           magnesium sulphate   0.7   g                             preserving agent   qs                         ADM: active dry material             
 
      The composition that was obtained exhibited good cosmetic properties.  
     EXAMPLE 7  
     Preparation of a Block Copolymer of Polystyrene-b-Poly(styrene/isobornyl acrylate) Composition  
      6 g of styrene, 0.0337 g of PERKADOX SE-10 and 0.1467 g of iodoperfluorohexane were introduced into a 10 ml tube. The tube was immersed in a bath at 80° C. for 3 hours, after which the styrene conversion was 95% and the number-average molar mass (Mn) observed was 8345 g/mol (lp=2.16). 3 g of isobornyl acrylate and 0.0168 g of PERKADOX SE-10 were then introduced into the tube. The tube was then immersed in an oil bath at 90° C. for 4 hours.  
      A gradient copolymer of polystyrene-b-poly(styrene/isobornyl acrylate) composition was obtained, with an iodine atom at the end of each chain.  
      The copolymer that was obtained had a number-average molar mass (Mn) of 16,700 g/mol (Ip=1.90).  
      Shift of the UV peak of the final copolymer relative to the peak of the first block confirmed the formation of a block copolymer.  
      The iodo end functions were characterized by MALDI-TOF or by NMR.