Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/046—Aerosols; Foams
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/90—Block copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q3/00—Manicure or pedicure preparations
  • A61Q3/02—Nail coatings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
  • C08F297/026—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising acrylic acid, methacrylic acid or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
  • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

• the present invention relates to new polymers of specific structure of the ethylene copolymer type, adhesive blocks.
• the present invention also relates to a composition, in particular a cosmetic or pharmaceutical composition, in particular a hair composition, comprising said polymer of specific structure.
• the invention also relates to the use of these polymers in cosmetics for the treatment of the skin, nails or hair.
• hair styling currently the most widespread on the cosmetic market for shaping (“shaping”) and / or maintaining the hairstyle (“hairstyle”) are nebulisats (“spray”) or gels and styling gels and mousses.
• compositions contain one or more polymer resins, one of the functions of which is to create bonds between the hairs. These compounds are also called “fixatives” and are mixed with various cosmetic additives.
• vinyl polymers with high glass transition temperatures are known in cosmetics from document FR-A- 2,439,798 and are included in particular in styling compositions.
• the polymers are generally plasticized with plasticizing agents but the latter alter the styling properties of the polymer.
• such a polymer must, in a composition for the treatment of the hair, impart more staying power while retaining a natural effect.
• the aim of the present invention is to provide a polymer which meets, inter alia, the needs, criteria and requirements mentioned above and which solves the problems of polymers of the prior art.
• This object and still others are achieved, in accordance with the present invention, by a linear block ethylenic copolymer comprising: at least two blocks having different glass transition temperatures (Tg);
• a subject of the invention is also cosmetic compositions comprising said linear block ethylenic copolymers.
• the copolymers having the specific structure of the invention allows to obtain extremely interesting properties, it was not possible to obtain with the polymers of the prior art .
• these polymers have an adhesive character and they thus lead to compositions or systems having improved hold and adhesions.
• the copolymers according to the invention when used in compositions for the treatment of hair, such as hairsprays or shampoos, they provide more hold, while retaining a natural effect.
• compositions for the treatment of nails such as nail varnishes
• they increase the adhesion of the first layer.
• compositions for the treatment of the skin namely in a wide variety of compositions of • makeup
• the. copolymers according to the invention improve the adhesion to the skin, provide a comfortable feeling, do not stick to the touch, and do not pull the skin.
• the invention also relates to a cosmetic process for making up or caring for keratin materials comprising the application to keratin materials of a cosmetic composition according to the invention.
• the invention therefore also relates to the use of the copolymers according to the invention to improve the styling power and the hold of a hair spray, the use of the copolymers to improve the adhesion of a nail varnish and finally the use of the copolymers to improve the hold and the adhesion of a makeup composition.
• copolymers of the invention therefore provide a solution to the problems posed by the polymers of the prior art.
• the unexpected advantageous properties of the specific copolymers of the invention, which are basically linear polymers, arise, on the one hand, from this linear character and, on the other hand, from the specific nature of the sequences which constitute them.
• sequences of the copolymers of the invention are defined by specific glass transition temperatures. None suggested, in the prior art, that by implementing a specifically linear copolymer, and by fixing Tg conditions defined for the sequences constituting the copolymer, it would be possible, according to the invention, to obtain a combination of excellent properties for the copolymer.
• the advantageous properties of the copolymer according to the invention would come from the fact that the specific structure and the specific choice of the blocks which constitute it, favor the phase separation between the blocks. More precisely, the linear copolymers of the present invention are defined as being ethylenic copolymers. This means that the monomers from which the blocks or blocks constituting this copolymer are derived are monomers with an ethylenic type carbon-carbon unsaturated double bond.
• the copolymer according to the invention is a linear copolymer.
• the invention does not intend to cover copolymers having a non-linear structure, for example branched, star, grafted, or the like.
• the linear nature of the copolymers of the invention is important for imparting the advantageous properties described above to the compositions containing it.
• the copolymer according to the invention is a film-forming polymer, that is to say that it is suitable on its own, or in the presence of an auxiliary film-forming agent, at the temperature ranging from 20 ° C. to 30 ° C. , to form a continuous film (seen with the naked eye) and adhering to a keratinous support.
• the copolymer comprises at least two blocks or blocks which have different glass transition temperatures (Tg), and, in addition, at least one of these blocks or blocks of the copolymer has a glass transition temperature less than or equal at 20 ° C.
• the glass transition temperature Tg being an essential parameter for defining the sequences of the copolymer of the invention and, consequently, the copolymer of the invention, it is important to indicate that the glass transition temperatures of the sequences of the copolymers used in the present invention are measured by differential enthalpy analysis (DSC, “Differential Scanning Calorimetry”, in English) for the dry polymer, at a heating rate of 10 ° C./minute.
• DSC differential enthalpy analysis
• copolymers according to the invention are also defined by a specific mechanical criterion, which is "adhesion” or “tack".
• the copolymers have an adhesion or tack which is generally greater than IN, preferably greater than 2N, more preferably greater than 3N.
• Fmax is the maximum tensile force, measured using an extensometer, necessary to take off the respective surfaces, an area of 0.95 cm 2 , two rigid glass supports (A) and (B) , inert, non-absorbent, placed opposite each other. Said surfaces have been previously coated with a composition comprising copolymer to be tested, according to the invention, this coating composition has a dry matter concentration of 10% (C) (in grams per 100 grams of composition), and the surfaces of the supports are coated at a rate of 4 / C mg / cm 2 .
• C dry matter concentration
• the surfaces are then dried for 48 hours at 22 ° C, at a relative humidity of 50%, then subjected for 20 seconds to a compression of 3
• Each block of the copolymer, according to the invention comes from one type of monomer or from several different types of monomers.
• each block can consist of a homopolymer or a copolymer; this copolymer constituting the sequence can in turn be statistical or alternated.
• the copolymer comprises at least two sequences having • glass transition temperatures (Tg).
• Tg glass transition temperatures
• the difference in glass transition temperatures between these two sequences, having different glass transition temperatures is generally 40 to 120 ° C, preferably 40 to 110 ° C and more preferably 40 ° C. at 100 ° C.
• the number average mass of the copolymer is generally from 10,000 to 500,000, preferably from 50,000 to 200,000.
• the proportion of the Tg sequence less than or equal to 20 ° C. is from 99% to 40% of the polymer, preferably 95 to 55% and more preferably 90 to 50%.
• the Tg sequence less than or equal to 20 ° C has a Tg temperature from 20 to -100 ° C, preferably from 20 to -95 ° C, more preferably from 20 to -90 ° C.
• the block whose glass transition temperature is less than or equal to 20 ° C. which is a homopolymer or a copolymer, is preferably derived in whole or in part from one or more monomers, which are such that homopolymers prepared from these monomers have glass transition temperatures, less than or equal to 20 ° C.
• the block, the glass transition temperature of which is less than or equal to 20 ° C. is a homopolymer, constituted by a single type of monomer (whose Tg of the corresponding homopolymer is less than 20 ° C.).
• the monomers whose homopolymers have glass transition temperatures less than or equal to 20 ° C. and from which is or are preferably derived the sequence (s) of Tg ⁇ 20 ° C. of the copolymer of the invention are, preferably chosen from the following monomers: - ethylenic hydrocarbons of 2 to 10 C, such as ethylene, isoprene, and butadiene;
• Ri representing an alkyl group of 1 to 12 C linear or branched with the exception of the tert-butyl group, in which there are (are) optionally intercalated one or more heteroatoms chosen from 0 , N, S, said an alkyl group which may also be optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F);
• Ri groups are methyl, ethyl, propyl, butyl, isobutyl, hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl and methoxypropyl, • another example of Ri for acrylates are the C1 to C ⁇ alkyl groups 2 - POE (polyl) for acrylates are the C1 to C ⁇ alkyl
• Ri can also denote a polyoxyethylene group comprising from 5 to 30 ethylene oxide units
• R 2 representing an alkyl group. from 3 to 12 C linear or branched, in which there are (are) optionally intercalated one or more heteroatoms chosen from 0, N and S, said alkyl group being able, in addition, to be optionally substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I, F);
• R groups are hexyl, ethylhexyl, octyl, lauryl, isooctyl, isodecyl, dodecyl, methoxyethyl, methoxypropyl, ethoxyethyl, POE (polyoxyethylene with repetition of the oxyethylene unit 5 to 30 times) and alkyl (Ci to C 30 ) - POE (with repetition of the oxyethylene unit of 5 30 times);
• R 3 represents a linear or branched 2 to 12 C alkyl group
• vinyl esters are: vinyl propionate, vinyl butyrate, vinyl ethylhexanoate, vinyl neononanoate, and vinyl neododecanoate;
• Vinyl ethers and alkyl of 1 to 12 C such as vinyl ether and methyl, and vinyl ether ethyl;
• N-alkyl (1 to 12 C) acrylamides such as N-octylacrylamide.
• the monomers which are particularly preferred, are: n-butyl acrylate, ethylhexyl acrylate, isobutyl acrylate, methoxyethyl acrylate, ethoxyethyl (meth) acrylate, (meth) acrylate of n-hexyl.
• the glass transition temperature sequence less than or equal to 20 ° C may, in addition to the monomers indicated above, and whose glass transition temperature Tg of the corresponding homopolymer is less than or equal to 20 ° C, include one or more several other different monomers called additional monomers.
• an adequate Tg sequence less than or equal to 20 ° C, may be formed from a copolymer consisting of a first monomer whose Tg of the corresponding homopolymer is in the range of more than 20 ° C to 200 ° C, and preferably more than 20 ° C to 120 ° C, and a second monomer whose Tg of the corresponding homopolymer is in the range of 20 ° C to -100 ° C.
• Tg of the equivalent homopolymer greater than 20 ° C. are chosen in particular from acrylates, methacrylates, meth (acrylamide), vinyl and allylic compounds, etc.
• the additional monomers from Tg of
• CH 2 CH-R 4 , where R 4 is a hydroxyl group; a group
• a C 3 -C 5 cycloalkyl group a C 6 -C 2 aryl group; a C 7 -C 30 aralkyl group (C 1 -C 4 alkyl group); a 4 to 12-membered heterocyclic group containing one or more heratomas selected from O, N, and S; a heterocyclylalkyl group (C1-C6 alkyl) such as a furfuryl group; said cycloalkyl, aryl, aralkyl, heterocyclic or heterocyclylalkyl groups which may be optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms, and alkyl groups of 1 to 4 C • linear or branched in which is found (nt) optionally intercalated one or more heteroatoms chosen from 0, N, S and P, and said alkyl groups which may, in addition, be optionally substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (
• vinyl monomers are vinylcyclohexane, styrene and vinyl acetate.
• the acrylates of formula: CH 2 CH-COOR5, where R 5 is a tert-butyl group, a C 3 to C 5 cycloalkyl group; a C20 to C20 aryl group; a C 1 -C 30 aralkyl group (C 1 -C 4 alkyl group); a 4 to 12 membered heterocyclic group containing one or more heteroatoms chosen from O, N, and S; a heterocyclylalkyl group (alkyl of C, to C 4), such as a furfuryl group; said cycloalkyl, aryl, aralkyl, heterocyclic or heterocyclylalkyl groups which may be optionally substituted by one or more substituents chosen from hydroxyl groups, halogen atoms, and linear or branched alkyl groups of 1 to 4 C in which is found (nt ) optionally
• acrylate monomers are t-butylcyclohexyl, tert-butyl, t-butylbenzyl, furfuryl and isobornyl acrylates; - Methacrylates of formula:
• CH 2 C (CH 3 ) -COOR 6 , where R 6 is an alkyl group from 1 to 4C, linear or branched, such as a methyl, ethyl, propyl or isobutyl group, said alkyl group possibly being optionally substituted by one or more substituents chosen from hydroxyl groups and halogen atoms (Cl, Br, I and F); a C 3 -C 5 cycloalkyl group; a C 2 o C aryl group; a C 7 -C 30 aralkyl group (C 1 -C 4 alkyl group); a 4 to 12-membered heterocyclic group containing one or more heteroatoms chosen from 0, N, and S; a heterocyclylalkyl group (1-4 C alkyl), such as a furfuryl group; said cycloalkyl, aryl, aralkyl, or heterocyclic groups or heterocyclylalkyl possibly being substituted by one or more substituents chosen from
• methacrylate monomers are methyl, ethyl, n-butyl, isobutyl, t-butylcyclohexyl, t-butylbenzyl, methoxyethyl methoxypropyl and isobornyl methacrylates; -
• R and Rs which are identical or different, each represent a hydrogen atom or an alkyl group of 1 to 12 linear or branched carbon atoms, such as an n-butyl, t-butyl, isopropyl, isohexyl, isooctyl, or isononyl group , and R 'denotes H or methyl.
• (meth) acrylamide monomers are N-butylacrylamide, N-t-butylacrylamide,
• N, N-dibutylacrylamide The preferred monomers from all those mentioned above are chosen from furfuryl acrylates, isobornyl acrylates, tert-butyl tert-butylcyclohexyl, tert-butylbenzyl, methyl, n-butyl, ethyl, isobutyl methacrylates, styrene, vinyl acetate and vinylcyclolexane.
• these additional, particularly preferred, monomers are methyl methacrylate, styrene, (meth) acrylic acid, isobornyl and furfuryl acrylates. This or these additional monomers are generally present in an amount less than or equal to 50% by weight, preferably less than or equal to 45% by weight and, more preferably, less than or equal to 40% by weight of the total weight of the block. of Tg less than or equal to 20 ° C.
• the copolymer according to the invention comprises at least one hydrophilic block which comprises hydrophilic monomers.
• the hydrophilic sequence can be defined as being a water-soluble or water-dispersible sequence.
• the polymer forming the block is water-soluble if it is soluble in water, at a rate of at least 5% by weight, at 25 ° C.
• the polymer forming the block is water-dispersible, if it forms at a concentration of 5%, at 25 ° C, a stable suspension of fine particles, generally spherical.
• the average size of the particles constituting said dispersion is less than 1 ⁇ m and, more generally, varies between 5 and 400 nm, preferably from 10 to 250 nm. These particle sizes are measured by light scattering.
• the hydrophilic block is preferably a block whose glass transition temperature is greater than 20 ° C., but it can also be the block whose glass transition temperature is less than or equal to 20 ° C.
• hydrophilic monomers whose homopolymers have a glass transition temperature below 20 ° C are not common.
• the hydrophilic block in the case where it is the Tg block less than or equal to 20 ° C., is advantageously a copolymer.
• This hydrophilic block therefore therefore comprises one or more hydrophilic monomer (s) whose corresponding homopolymers have glass transition temperatures above 20 ° C. and one or more other non-hydrophilic monomer (s), chosen in particular from those whose homopolymers have Tg less than or equal to 20 ° C.
• the proportion of the various hydrophilic and non-hydrophilic monomers being preferably chosen so that the whole of the block constituted by a copolymer has a Tg greater than 20 ° C.
• the hydrophilic block When the hydrophilic block has a glass transition temperature above 20 ° C, it generally comprises from 70 to 100%, and preferably from 80 to 100%, of hydrophilic monomers of which the Tg of the corresponding homopolymers is greater than 20 ° C.
• the hydrophilic block When the hydrophilic block has a glass transition temperature less than or equal to 20 ° C., it generally comprises from 10% to less than 70%, preferably from 20% to 65% of hydrophilic monomers whose Tg of the corresponding homopolymers are higher at 20 ° C.
• hydrophilic monomers whose Tg of the corresponding homopolymer is greater than 20 ° C include cationic monomers, anionic monomers and nonionic monomers:
• cationic monomers examples include:
• organic acids may have one or more carboxylic, sulfonic, or phosphonic groups. They can be linear, branched or cyclic aliphatic acids or even aromatic acids. These acids may also contain one or more heteroatoms chosen from O and N, for example in the form of hydroxyl groups.
• One example 'of alkyl acid is acetic acid CH 3 COOH.
• polyacid is terephthalic acid.
• hydroxy acids are citric acid and tartaric acid.
• anionic monomers are: acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid; styrenesulfonic acid, acrylamidopropanesulfonic acid, vinylbenzoic acid, vinylphosphoric acid and the salts thereof.
• the neutralizer can be an inorganic base, such as LiOH, NaOH, KOH, Ca (OH) 2 , NH 4 OH, an organic base, for example a primary, secondary or tertiary ingredient, such as a primary alkylamine such as
• nonionic monomers are: - hydroxyalkyl (meth) acrylates in which the alkyl group has from 2 to 4 C atoms, in particular hydroxyethyl (meth) acrylate, vinyllactam.es, (meth ) acrylamides, (meth) acrylamides of N-C ⁇ -C 4 alkyl, such as isobutyl acrylamide; and polysaccharide (meth) acrylates such as sucrose acrylate.
• the overall copolymer is not necessarily hydrophilic.
• the linear, block ethylene copolymers according to the invention are chosen from: - bis-sequenced copolymers;
• the copolymers can comprise two blocks having a Tg ⁇ 20 ° C and one or two blocks having a Tg> 20 ° C.
• copolymers according to the invention can be prepared by anionic polymerization.
• the copolymers according to the invention are in a first mode obtained by controlled radical polymerization, but they can also, according to a second mode, be obtained by conventional radical polymerization.
• the block or block copolymers according to the invention are preferably obtained by controlled radical polymerization, described in particular in “New Method of Polymer Synthesis”, Blackie Académie & Professional, London, 1995, volume 2, page 1.
• Controlled radical polymerization makes it possible to reduce deactivation reactions of the growing radical species, in particular the termination step, reactions which, in conventional radical polymerization, interrupt the growth of the polymer chain in an irreversible and uncontrolled manner.
• the polymerization can be carried out according to the atom transfer technique, or by reaction with a nitroxide, or alternatively according to the "reversible addition-fragmentation chain tr ans fer” technique.
• 'A technique of atom-transfer radical-polymerization also known under the abbreviation ATRP, consists in blocking the radical species growing in the form of C-halide type bond (in the presence of metal / ligand complex). This type of polymerization results in a control of the mass of the polymers formed and in a low polydispersity index.
• radical polymerization by atom transfer is carried out by polymerization of one or more polymerizable monomers by the radical route, in the presence of: an initiator having at least one transferable halogen atom,; - a compound comprising a transition metal capable of participating in a step of reduction with the initiator and a polymeric chain - "dormant"; and
• a ligand which can be chosen from compounds comprising a nitrogen (N), oxygen (O), phosphorus (P) or sulfur (S) atom, capable of coordinating by a ⁇ bond to said compound comprising a transition metal, the formation of direct bonds between said compound comprising a transition metal and the polymer being formed being avoided.
• the halogen atom is preferably a chlorine or bromine atom.
• the radical polymerization technique by reaction with a nitroxide consists in blocking the growing radical species in the form of a bond of the C-0 NR 1 R 2 , R 1 and R 2 type which may be, independently of one another, an alkyl radical having from 2 to 30 carbon atoms or forming both, with the nitrogen atom, a ring having from 4 to 20 carbon atoms, such as for example a 2,2,6 ring , 6-tetramethylpiperidinyl.
• This polymerization technique is notably described in the articles
• the RAFT polymerization technique (reversiJle addition-fragmentation chain transfer) consists in blocking the growing radical species in the form of a C-S type bond. Dithio compounds such as thiobenzoates, dithiocarbamates or xanthan disulphides are used for this. This technique is notably described in application WO-A-98/58974 and in the article "A more versatile route to block copolymers and other polymers of complex architecture by living radical polymerization: the RAFT process", published in Macromolecules, 1999, volume 32, pages 2071 - 2074.
• the block or block polymers according to the invention can also be obtained using the conventional radical polymerization technique by carrying out the casting of the monomers in a sequenced manner. In this case, only control of the nature of the sequences is possible (no control of the masses). It involves first polymerizing an Ml monomer in a polymerization reactor; to follow, by kinetics, its consumption over time, then when Ml is consumed at around 95%, then to introduce a new monomer M2 into the polymerization reactor. A block structure polymer of the M1-M2 type is thus easily obtained.
• the invention also relates to cosmetic or pharmaceutical compositions comprising the copolymer of specific structure, as described above.
• compositions contain from 0.1 to 60% by weight, preferably from 0.5 to 50% by weight, and more preferably from 1 to 40% by weight of the copolymer according to the invention.
• compositions according to the invention comprise, in addition to said polymers, a physiologically acceptable medium, that is to say a medium compatible with keratin materials, such as the skin, hair, eyelashes, eyebrows and nails. .
• composition in general, it must be considered that the whole of the composition is physiologically acceptable.
• Said medium, physiologically acceptable generally comprises an appropriate solvent, physiologically acceptable, in which the copolymer, according to the invention, is in dissolved or dispersed form.
• the composition can thus comprise, as solvent forming a hydrophilic phase, water or a mixture of water and organic solvent (s) hydrophilic (s) such as alcohols and in particular linear or branched lower monoalcohols having 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerin, diglycerin, propylene glycol, sorbitol, pentethylene glycol, and polyethylene glycols.
• solvent forming a hydrophilic phase
• the hydrophilic phase can also contain C 2 ethers and hydrophilic C 2 -C 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% to 99% (in particular 0.1% to 99%) by weight, relative to the total weight of the composition, and preferably from 10% to 80% by weight.
• the composition may also comprise a fatty phase, in particular consisting of fatty substances liquid at room temperature (25 ° C. in general) and / or fatty substances solid at ambient temperature such as waxes, pasty fatty substances, gums and their mixtures. .
• fatty substances can be of animal, vegetable, mineral or synthetic origin.
• This fatty phase can, in addition, contain lipophilic organic solvents.
• oils As fatty substances liquid at room temperature, often called oils, which can be used in the invention, there may be mentioned: hydrocarbon oils of animal origin such as perhydrosqualene; vegetable hydrocarbon oils such as liquid triglycerides of fatty acids of 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids, or even sunflower, corn, soybean, grape seed, sesame oils, apricot, macadamia, castor, avocado, caprylic / capric acid triglycerides, jojoba oil, shea butter; the linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, petrolatum, polydecenes, hydrogenated polyisobutene such as parlameam; synthetic esters and ethers, in particular of fatty acids such as, for example, Purcellin oil, isopropyl myristate, ethyl-2-hexyl pal itate, octy
• composition according to the invention can also comprise one or more organic solvents, cosmetically acceptable (tolerance, toxicology and touch acceptable).
• solvents can generally be present in a content ranging from 0 to 90%, preferably from 0.1 to 90%, more preferably from 10 to
• esters of acetic acid such as methyl, ethyl, butyl, amyl, 2-methoxy-ethyl acetate, 'isopropyl
• ketones such as methyl ethyl ketone, methyl isobutyl ketone
• hydrocarbons such as toluene, xylene, hexane, heptane
• aldehydes having 5 to 10 carbon atoms
• ethers having at least 3 carbon atoms and their mixtures.
• the waxes can be hydrocarbon, fluorinated and / or silicone and be of vegetable, mineral, animal and / or synthetic origin.
• the waxes have a melting point above 25 ° C and better still above 45 ° C.
• the gums are generally high molecular weight polydimethylsiloxanes (PDMS) or cellulose gums or polysaccharides and the pasty bodies are generally hydrocarbon compounds such as lanolines and their derivatives or PDMS.
• PDMS polydimethylsiloxanes
• the nature and quantity of the solid bodies depend on the mechanical properties and the desired textures.
• the composition may contain from 0 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.
• the polymer can be combined with one or more auxiliary film-forming agents.
• a filification agent can be chosen from all of the compounds known to a person skilled in the art as being capable of fulfilling the desired function, and in particular can be chosen from plasticizing agents and coalescing agents.
• the composition according to the invention may also comprise one or more coloring materials chosen from water-soluble dyes, and pulverulent coloring materials such as pigments, nacres and flakes well known to those skilled in the art.
• the coloring matters can 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 0.01% to 30% by weight.
• the term “pigments” should be understood to mean 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 shape, in particular produced by certain molluscs in their shell or else synthesized.
• the pigments can be white or colored, mineral and / or organic.
• mineral pigments mention may be made of titanium dioxide, optionally surface-treated, zirconium or cerium oxides, as well as oxides of zinc, iron (black, yellow or red) or chromium, violet of manganese, ultramarine blue, chromium hydrate and ferric blue, metallic powders such as aluminum powder, copper powder.
• organic pigments there may be mentioned carbon black, pigments of the D & C type, and lakes based on cochineal carmine, barium, strontium, calcium, aluminum.
• the pearlescent pigments can 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, mica titanium coated with in particular blue ferric or chromium oxide, titanium mica coated with an organic pigment of the aforementioned type as well as pearlescent pigments based on bismuth oxychloride.
• the water-soluble dyes are, for example, beet juice, methylene blue.
• composition according to the invention may also further comprise 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 0.01% at 30% by weight.
• fillers it is necessary to understand 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 produced. These fillers are used in particular to modify the rheology or the texture of the composition.
• the fillers can "be mineral or organic in any form, platelet, spherical or oblong, whatever • the crystallographic form (for example sheet, cubic, hexagonal, orthorombic, etc.). Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®) (Orgasol® from Atochem), poly- ⁇ -alanine and polyethylene powders, powders of tetrafluoroethylene polymers (Teflon®) ), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride / acrylonitrile such as Expancel® (Nobel
• acrylic acid copolymers Polytrap® from Dow Corning
• silicone resin microbeads Tospearls® from Toshiba, for example
• elastomeric polyorganosiloxane particles precipitated calcium carbonate, carbonate and
• composition according to the invention may also contain ingredients commonly used in cosmetics, such as vitamins, thickeners, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sun filters , surfactants, antioxidants, hair loss agents, dandruff agents, propellants, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, trace elements, softeners, sequestrants, perfumes, alkalizing or acidifying agents, preservatives, sun filters , surfactants, antioxidants, hair loss agents, dandruff agents, propellants, or mixtures thereof.
• composition according to the invention can be in particular in the form of a suspension, dispersion, solution, gel, emulsion, in particular oil-in-water (O / W) or water-in-oil (W / O) emulsion ), or multiple (W / O / W or polyol / O / W or O / W / O), in the form of a cream, paste, foam, vesicle dispersion, in particular of ionic lipids or not, of two-phase or multiphase lotion, spray,.
• the composition can be anhydrous, for example it can be an anhydrous paste.
• the composition according to the invention can be a makeup composition such as products for the complexion (foundations), blushes or eye shadows, products for the lips, concealer products, blushes, mascaras, eyeliners, eyebrow makeup products, lip pencils or eyes, nail products, such as nail polish, body makeup products, products of 'make-up hair (mascara or hair spray).
• the composition according to the invention can also be a hair product, in particular for maintaining the hairstyle or shaping the hair.
• the hair compositions are preferably shampoos, gels, styling lotions, brushing lotions, fixing and styling compositions such as lacquers or spray.
• Lotions can be packaged in various forms, in particular in vaporizers, pump-dispensers or in aerosol containers in order 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 foam for fixing or treating the hair.
• a difunctional initiator is prepared according to the following reaction scheme:
• reaction solution is concentrated by evaporation of the THF and the residue is precipitated in water.
• the aqueous phase is then extracted three times with ethyl ether, then the ethereal phase is dried over magnesium sulfate.
• the mixture is heated, under a nitrogen atmosphere, to a temperature of 90 ° C., the nitrogen supply is cut off and this temperature is maintained for 7 h 30 hours, whereby a solution of the polymer is obtained.
• 1.3 lE-04 mol, or 10.5 g of the preceding macroinitiator, is mixed in a hermetic reactor comprising a nitrogen inlet and protected from oxygen: 2. butyl polyacrylate, 2.62E-04 mol or 2.59E-02 g of CuBr, 8.40 ml of diphenyl diether solvent; 2.62E-04 mole or 4.53E-02 g of N, N, N ', N'',N''-pentamethyldiethylenetriamine, and 3.93E-02 mole or 3.39 g ' of methyl acrylate monomer.
• the solution is dissolved in approximately 100 ml of dichloromethane. This solution of the polymer is passed over a bed of neutral alumina, then the clear solution is precipitated in 5 volumes of a methanol / water mixture (80/20). 6 g of polymer in the form of a paste are thus obtained, which corresponds to a yield of 43% by weight.
• the paste is washed with heptane while hot to remove any residual monomers therefrom.
• the average molar mass by weight and number is determined by liquid chromatography by gel permeation (solvent THF, calibration curve established with linear polystyrene standards).
• the number-average molar mass (M n ) is equal to 88,000 g / mole
• the weight-average molar mass (M p ) is equal to 102,000 g / mole.
• the copolymer has two glass transition temperatures T g , the first equal to -47 ° C attributable to the poly (butyl acrylate) block, and the second equal to 10 ° C attributable to the poly (methyl acrylate) blocks.
• the “tack” value of this polymer measured by the method described above is 3.5 N.
• An aerosol is prepared with 100 g of a 9% by weight solution of the copolymer prepared in Example 2 in ethanol and 75 g of dimethylether playing the role of propellant.
• composition is sprayed on locks of brown hair with a length of 18 cm and the hold of the hairstyle and the flexible appearance of the locks are evaluated on a panel of -5 people, using a rating scale ranging from 0 (bad) to 5 (excellent).
• the notes obtained are 4 for the holding of the hairstyle and 4 for the flexible aspect of the locks.
• the copolymer is dissolved in ethyl acetate: the polymer content of the solution obtained is 25% by weight.
• the copolymer solution of Example 2 is applied to a nail. After drying for 10 min. , a classic solvent nail polish is applied.
• the resistance of the varnish and the impact resistance are improved.

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• 2002
  • 2002-11-27 WO PCT/FR2002/004067 patent/WO2003046032A2/fr active Application Filing
  • 2002-11-27 JP JP2003547479A patent/JP2006514701A/ja active Pending
  • 2002-11-27 EP EP02803837A patent/EP1448646A2/de not_active Withdrawn
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