Classifications

• • 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
• • 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
• • 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
  • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

• the present invention relates to new block copolymers, to their use in the cosmetic field in particular, as well as to the compositions comprising them.
• polymers with antinomic properties are often sought: obtaining good fixation without tacky; good resistance of products to humidity with good elimination in shampoo; or a makeup composition combining comfort and hold. Furthermore, these polymers should preferably be transported in water, in soluble or dispersible form. This is the reason why the formulators have turned more particularly to copolymers, and in particular to block polymers or block polymers, which have advantageous mechanical properties. They can in particular allow these antithetical properties to be obtained, because they result from the association, within the same chain, of sequences of different properties: one which can provide rigidity and the other flexibility, for example . Thus, the styling properties of styling products or lacquers can be modulated.
• block copolymers which can be transported in water, mention may be made of those described in application O02 / 28358.
• block copolymers are described, a block of which is a copolymer mainly comprising nonionic hydrophilic units in admixture with hydrophobic units. These copolymers have a nonionic character. In order to make them soluble in water, the amount of hydrophilic unit is very high; this limitation does not allow access to a large range of structures.
• block polymers one block of which is a copolymer comprising acrylic acid units, and another block of which is non-ionic hydrophilic. These block polymers however exhibit a strong fluctuation in their properties as a function of humidity.
• block copolymers described in O02 / 28357 which are water-soluble, and in which all the blocks are formed from monomers non-ionic, but which also exhibit large fluctuations in their properties as a function of humidity.
• diblock or triblock copolymers which can give aqueous gelled compositions; these copolymers can in particular be of the poly (styrene / methacrylic acid) -b-poly (ethyl acrylate / methacrylic acid) type.
• these copolymers are thickeners which, in certain cases, can be considered as a drawback, in particular by making the formulation difficult. Indeed, obtaining gels is not always sought: this is the case for example for aerosols or nail varnishes, for which fluid solutions are necessary. It has therefore been found that the majority of block copolymers intended to be transported in water mainly comprise hydrophobic units and tend to form gels, which is a drawback.
• the object of the present invention is to provide block copolymers, or block polymers, which have advantageous mechanical properties, and which can be used in large quantities without appreciably influencing the thickening or gelling, therefore the viscosity, of the composition that contains them.
• the copolymers according to the invention do not form, in water, a viscoelastic gel, that is to say a gel having an elastic modulus (G ′) greater than the viscous modulus (G ′′). copolymers forming a film or a deposit are also sought, the removal of which with perfect shampooing.
• An object of the invention is therefore a linear, ethylenic, block copolymer comprising at least a first block and at least a second block, each block comprising at least one ionic hydrophilic unit, which may be different from a block to l 'other, said ionic hydrophilic unit being present in each sequence at a rate of 2 to 100% by weight relative to the weight of said sequence.
• Another object is a cosmetic or pharmaceutical composition comprising in a physiologically acceptable medium, in particular cosmetically or dermatologically acceptable, at least one copolymer as defined below.
• copolymers according to the invention have comfortable mechanical properties: they can be rigid while having a certain flexibility or elasticity, ensuring maintenance of the hair lasting over time. They can also have good adhesion without being sticky to the touch. They find a very particular application in the cosmetic field, in particular in hair or make-up. When used in nail polish, these polymers form a deposit that adheres well to the nail without easily wearing out.
• the block polymer (or block polymer) according to the invention is a linear block ethylenic polymer, advantageously film-forming.
• ethylenic polymer is meant a polymer obtained by polymerization of monomers comprising ethylenic unsaturation.
• block polymer is meant a polymer comprising at least 2 successive blocks distinct, that is to say of different chemical natures.
• the polymer according to the invention is a polymer with a linear structure.
• a polymer with a non-linear structure is, for example, a polymer with a branched, star, grafted, or other structure.
• all the monomers used to prepare a linear polymer are mono-functional, that is to say have only one polymerizable function.
• the polymerization orcers they can be monofunctional or difunctional.
• film-forming polymer is meant a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.
• Each block, or block, of the polymer according to the invention is derived from one type of monomer or from several different types of monomer. This means that each block can consist of a homopoly era or a copolymer; this copolymer constituting the sequence which may in turn be statistical or alternating or with a gradient; the distribution of the monomers within each sequence can therefore be random or controlled depending on the nature and / or the reactivity of the monomers and / or the preparation process used.
• the block polymer according to the invention therefore comprises at least two blocks, advantageously two blocks (diblock) or three blocks (triblock), each of the blocks comprising at least one ionic hydrophilic monomer, present in each block in an amount of at least 2%. by weight relative to the weight of the sequence.
• said hydrophilic ionic monomer may in fact be a mixture of different hydrophilic ionic monomers.
• the ionic hydrophilic monomer (s) may be identical, totally or partially, or different, from one sequence to another.
• the ionic hydrophilic monomers are present in each block in an amount of 2 to 100% by weight, relative to the weight of the block, in particular from 3 to 70% by weight, even better from 5 to 50% by weight, or even from 8 to 30% by weight.
• a monomer is said to be hydrophilic if the corresponding homopolymer is hydrophilic, that is to say if it is water-soluble or water-dispersible.
• the omopolymer is water-soluble if it is soluble in water, at a rate of at least 5% by weight, at 25 ° C.
• the omopolymer is water dispersible if it forms in water, at a concentration of 5% by weight, at 25 ° C, a stable suspension or dispersion of fines. 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 (with a Coulter Counter type device).
• the hydrophilicity of a monomer can also be defined by the value of the logarithm of the apparent partition coefficient octanol-1 / water, also called log P; a monomer can be considered to be hydrophilic when this value is less than or equal to 2, for example between -8 and 2, preferably less than or equal to 1.5, in particular less than or equal to 1, and in particular between -7 and 1, or even between -6 and 0.
• log P values are known and are determined according to a standard test which determines the concentration of the monomer in octanol and water.
• the values can in particular be calculated using the ACD software (Advanced Chemistry Development) Software solaris V4.67; they can also be obtained from Exploring QSAR: hydrophobic, electronic and steric constants (ACS professional reference book, 1995). There is still a website which provides estimated values (address: http: //esc.syrres .com / interkow / kowdemo.htm).
• the final polymer comprises in each of its sequences at least one hydrophilic monomer present at least 2% by weight relative to the weight of the block.
• hydrophilic monomers it is possible to hydrolyze the polymer when it comprises units of the (meth) acrylic ester type, capable of being hydrolyzed to give units having a carboxylic acid function; this may be the case when the polymer comprises units of the (meth) acrylate type of methyl, ethyl, hydroxyethyl, tert-butyl, benzyl, trimethoxysilyl or ethyltrimeth ⁇ xysilyl.
• Hydrolysis can thus be carried out once the polymer has been synthesized, under acidic conditions (for example in the presence of sulfuric acid, hydrochloric acid or trifluoroacetic acid) or basic conditions (for example in the presence of hydroxides of alkaline earth metals such as soda or potash, alkali metal alcoholates such as potassium t-butoxide, or amines such as ammonia).
• acidic conditions for example in the presence of sulfuric acid, hydrochloric acid or trifluoroacetic acid
• basic conditions for example in the presence of hydroxides of alkaline earth metals such as soda or potash, alkali metal alcoholates such as potassium t-butoxide, or amines such as ammonia.
• the hydrolysis generally takes place between 5 and 100 ° C, preferably between 15 and 80 ° C.
• the hydrolyzed polymer can then be purified by repeated precipitation.
• the ionic hydrophilic monomers present in the final polymer can be chosen from anionic, cationic and / or amphoteric hydrophilic monomers.
• each of the blocks comprises at least one anionic hydrophilic monomer and / or at least one cationic hydrophilic monomer.
• at least one block can comprise both at least one cationic hydrophilic monomer and at least one anionic hydrophilic monomer.
• anionic hydrophilic monomers mention may in particular be made of ethylenically unsaturated monomers comprising, for example, at least one carboxylic acid (COOH), phosphonic (P0 3 H 2 ) or sulfonic (S0 3 H) function, such as by example those of formula (I) below:
• - Ri is a hydrogen atom or a hydrocarbon radical, linear or branched, of type C p H 2 p + ⁇ , with p being an integer between 1 and 12, inclusive;
• RI can represent a methyl, ethyl, propyl, butyl radical.
• Ri represents hydrogen or a methyl radical.
• - Z is a divalent group chosen from -COO-, -CONH-, -CONCH 3 -, -OCO- or -0-; preferably, Z is chosen from -COO- and -CONH-.
• - x is 0 or 1, preferably 1.
• -m is 0 or 1;
• - R2 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, from 1 to 30 carbon atoms, which can comprise 1 to 30 heteroatoms chosen from 0, N, S, and P;
• the heteroatom (s), when they are present, may be intercalated in the chain of said radical R2, or else said radical R2 may be substituted by one or more groups comprising them such as hydroxy or amino (NH2, NHR ' or NR'R "with R 'and R" identical or different representing a linear or branched C1-C22 alkyl, in particular methyl or ethyl).
• R2 may be: - an alkylene radical such as methylene, ethylene, propylene, n-butylene, isobutylene, tertiobutylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, n-docosanylene; - a phenylene radical -C 6 H 4 - (ortho, meta or para) optionally substituted, by a C1-C12 alkyl radical optionally comprising 1 to 8 heteroatoms chosen from 0, N, S, and P; or a benzylene radical -C6H4-CH2- optionally substituted, by a C1-C12 alkyl radical optionally comprising 1 to 8 heteroatoms chosen from 0, N, S, and P; - a radical of formula -CH 2 -CHOH-, -CH 2 - CH2-CHOH-, -
• - Y is a group chosen from -C00H, - SO3H, -OSO3H, -PO (OH) 2 and -0P0 (0H) 2 .
• the neutralization of the anionic groups can be carried out by a mineral base, 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, in particular triethylamine or butylamine.
• a mineral base such as LiOH, NaOH, KOH, Ca (OH) 2 , NH 4 OH or Zn (OH) 2
• an organic base such as a primary, secondary or tertiary alkylamine, in particular triethylamine or butylamine.
• This primary, secondary or tertiary alkylamine can comprise one or more nitrogen and / or oxygen atoms and can therefore comprise, for example, one or more alcohol functions; mention may in particular be made of amino-2-methyl-2-propanol, triethanolamine and dimethylamino2-propanol. Mention may also be made of lysine or 3- (dimethyla
• ethylenically unsaturated monomers comprising at least one primary, secondary or tertiary amine function, in particular those of formula (II) below:
• - X is (a) a group of formula -N-RgR with R6 and R7 representing, independently of one another, (i) a hydrogen atom, (ii) a linear, branched or cyclic alkyl group, saturated or unsaturated, optionally aromatic, comprising from 1 to 30 carbon atoms, possibly comprising 1 to 10 heteroatoms chosen from 0, N, S, and P; in particular a methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, lauryl, stearyl group; (iii) an alkylene oxide group of formula - (R80) y R9 with R8 representing a linear or branched C2-C4 alkyl, R9 is hydrogen or a linear or branched C1-C30 alkyl radical and y is between 1 and 250 inclusive; (iv) R6 and R7 can form with the nitrogen atom a saturated or unsaturated, optionally
• X can constitute an aromatic ring or not comprising a cationizable tertiary amine group. or can represent an aromatic heterocycle or not, containing a tertiary nitrogen, cationizable.
• X radicals mention may be made of pyridine, indolyl, isoindolinyl, imidazolyl, imidazolinyl, piperidinyl, pyrazolynyl, pyrazolynyl, pyrazolyl, quinoline, pyrazolinyl, pyridinyl, piperazinyl, pyrrolidinyl, quinidinyl, thiazolinyl, morpholineid guanid radicals. their mixtures.
• cationic hydrophilic monomers mention may be made, alone or as a mixture: - 2-vinylpyridine, 4-vinylpyridine, 1 allylamine and 1 allylpyridine; - aminoalkyl (meth) acrylates, such as [N, N-di (C1-C4) (meth) acrylates alkylamino] (C1-C6) alkyl or the (meth) acrylates of [N- (C1-C4) alkylamino] (C1-C6) alkyl and in particular the (meth) acrylate of N, N-dimethylaminoethyl, the (meth) acrylate N, N ⁇ diethylaminoethyl, 2-aminoethyl (meth) acrylate, 2- (N-tertbutylamino) ethyl (meth) acrylate; - aminoalkyl (meth) acrylamides, such as the (meth) acryl
• salts of mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, boric acid.
• salts of organic acids may contain one or more carboxylic, sulphonic or phosphonic acid 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 0 and N, for example in the form of hydroxyl groups. Mention may in particular be made of propionic acid, acetic acid, terephthalic acid, citric acid and tartaric acid.
• the neutralization of the anionic or cationic units, as well as the quaternization, can be total or partial.
• the tertiary amino groups can be quaternized by mobile halogen compounds, in particular alkyl halides such as chlorides or C1-C12 alkyl bromides, and for example methyl bromide or ethyl chloride. These groups can also be quaternized by mobile halogen compounds comprising carboxylic or sulphonic acid functions, in particular sodium chloroacetate; or by cyclic sulfones, for example propanesulfone. Amphoteric hydrophilic monomers (or betaines, having at least one charge (+) and at least one charge (-) carried by the same monomer) are thus obtained.
• mobile halogen compounds in particular alkyl halides such as chlorides or C1-C12 alkyl bromides, and for example methyl bromide or ethyl chloride.
• mobile halogen compounds comprising carboxylic or sulphonic acid functions, in particular sodium chloroacetate; or by cyclic sulfones, for example propanesul
• the quaternization can be carried out on the polymer already synthesized or on the starting monomers, before polymerization.
• the resulting polymers may therefore comprise amphoteric monomers which may correspond to formula (III) in which :
• - X ' + is a divalent group of formula - N + R' 6 R '7 with R'6 and R'7 representing, independently of one another, (i) a hydrogen atom, (ii) a linear, branched or cyclic, optionally aromatic, alkyl group comprising from 1 to 30 carbon atoms, which may comprise 1 to 8 heteroatoms chosen from 0, N, S and P; for example methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl or isobutyl; (iii) an alkylene oxide group of formula - (R80) y R9 with R8 representing a linear or branched C2-C4 alkyl, R9 is hydrogen or a linear or branched C1-C30 alkyl radical and y is between 1 and 250 inclusive; (iv) R'6 and R'7 can form a saturated or unsaturated, optionally aromatic, optionally aromatic, ring (NR '6R
• - Y ' ⁇ is a group selected from -COO, -S0 3 ⁇ , -OS0 3 ", -PO3 2" and -PO4 2-.
• R3 is a divalent carbon radical, saturated or unsaturated, optionally aromatic, linear, branched or cyclic, from 1 to 30 carbon atoms, possibly comprising 1 to 18 heteroatoms chosen from 0, N, S and.
• the heteroatom or atoms when they are present, may be intercalated in the chain of said radical R3, or else said radical R3 may be substituted by one or more groups comprising them such as hydroxy or amino; in particular R3 can be: - an alkylene radical such as methylene, ethylene, propylene, n-butylene, isobutylene, tertiobutylene, n-hexylene, n-octylene, n-dodecylene, n-octadecylene, n-tetradecylene, n-docosanylene; - a phenylene radical -C 6 H 4 - (ortho, meta or para) optionally substituted, by a
• the copolymer according to the invention comprises from 4 to 100% by weight, in particular from 8 to 80% by weight, or even from 10 to 30% by weight, relative to the total weight of the copolymer, of units hydrophilic ionic.
• the copolymer according to the invention is soluble or dispersible in water, at 25 ° C, in an amount of 5% by weight.
• the blocks of the block copolymer according to the invention may comprise one or more additional monomers chosen from non-ionic hydrophilic monomers, hydrophobic monomers and their mixtures.
• additional monomers can be identical or different from one block to another.
• This or these additional monomers are ethylenic monomers copolymerizable with the hydrophilic ionic monomer (s), whatever their coefficient of reactivity.
• the nonionic hydrophilic monomers may be present in a proportion of 0 to 98% by weight, relative to the weight of the block, in particular from 2 to 95% by weight, and even better still from 3 to 92% by weight, in at least one sequence, even in each sequence.
• the hydrophobic monomers may be present in a proportion of 0 to 98% by weight, relative to the weight of the block, in particular from 2 to 95% by weight, and even better still from 3 to 92% by weight, in at least a sequence, even in each sequence.
• nonionic or hydrophobic hydrophilic monomers capable of being copolymerized with the ionic hydrophilic monomers to form the polymers according to the invention, there may be mentioned, alone or as a mixture,:
• ethylene hydrocarbons having 2 to 10 carbons such as ethylene, isoprene, or butadiene
• R 2 is hydrogen or methyl (CH 3 ) and R 3 represents: - a linear or branched alkyl group, from 1 to 30 carbon atoms, in which there are (are) optionally intercalated one or more heteroatoms chosen from 0, N, S and P; said alkyl group possibly also being optionally substituted by one or more substituents chosen from OH, halogen atoms (Cl, Br, I and F), and the groups - Si (R 4 R 5 R S ) and - If (R 4 R 5 ) 0, in which R 4 , Rs and R 6 , which are identical or different, represent a hydrogen atom, a C1-C6 alkyl group or a phenyl group; in particular R 3 may be a methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl group, in particular ethyl-2-hexyl,
• R 7 and R 6 identical or different, represent: - a hydrogen atom; or - a linear or branched alkyl group of 1 to 30 carbon atoms, in which there are optionally intercalated one or more heteroatoms chosen from 0, N, S and P; the said alkyl group possibly also being optionally substituted by one or more substituents chosen from -OH, the halogen atoms (Cl, Br, I and F), and the groups -Si (R4R5R6) and -Si (R 4 R 5 ) 0, in which R 4 , R 5 and R 6 represent a hydrogen atom, a C 1 -C 6 alkyl group or a phenyl group; in particular R6 or R7 may be a methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, hexyl, ethylhexyl, octyl,
• Examples of such additional monomers are (meth) acrylamide, N-ethyl (meth) acrylamide, N-butylacrylamide, Nt-butylacrylamide, N-isopropylacrylamide, N, N-dimethyl (meth) acrylamide, N, N-dibutylacrylamide, N-octylacrylamide, N-dodecylacrylamide, N-undecylacrylamide, and N- (2-hydroxypropylmethacrylamide).
• R9 is a hydroxyl group; halogen (Cl or F); an NH 2 group; a group -OR10 where Rio represents a phenyl group or an alkyl group at C 12 (the monomer is a vinyl or allylic ether); an acetamide group (NHCOCH3); an OCORn group where Ru represents a linear or branched alkyl group of 2 to 12 carbons (the monomer is a vinyl or allyl ester), C3-C12 cycloalkyl, C3-C20 aryl or C4-C30 arallyl; or alternatively R 9 is chosen from: - a linear or branched alkyl group, comprising 1 to 30 carbon atoms, in which there are (are) optionally intercalated one or more heteroatoms chosen from O, N, S and P; said alkyl group possibly also being optionally substituted by one or more substituents chosen from -
• Examples of such additional monomers are vinylcyclohexane, and styrene (hydrophobic); N-vinylpyrrolidone and N-vinylcaprolactam (non-ionic hydrophiles); vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ethylhexanoate, vinyl neononanoate and vinyl neododecanoate (hydrophobic); vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether.
• (meth) acrylic, (meth) acrylamides or silicone vinyl monomers such as methacryloxypropyltris (trimethylsiloxy) silane or acryloxypropylpoly-dimethylsiloxane, or silicone (meth) acrylamides.
• the more particularly preferred additional monomers in particular nonionic hydrophilic
• the Tg is given in parenthesis for information: - (meth) acrylates and (meth) acrylamides of hydroxyalkyl in which the alkyl group contains 2 to 4 carbon atoms, in particular 2-hydroxyethyl acrylate (Tg ⁇ 15 ° C), 2-hydroxyethyl methacrylate (55 ° C), methacrylate of 2-hydroxy ⁇ ropyle, 4-hydroxybutyl methacrylate, N- (2-hydroxypropyl) (meth) acrylamide; - (meth) acrylates and (meth) acrylamides of alkoxy (C ⁇ _ 4 ) alkyl (C ⁇ - 4 ) such as (meth) acrylates and (meth) acrylamides of methoxyethyl, 2-ethoxyethyl, methoxypropyl and di- (2-ethoxye
• the copolymers according to the invention can comprise at least one block comprising monomers chosen from isobornyl acrylate, cyclohexyl acrylate (19 ° C), ethyl acrylate (10 ° C), methyl methacrylate (100 ° C), cyclohexyl methacrylate (83 ° C), ethyl methacrylate (65 ° C), butyl methacrylate (20 ° C) and styrene (100 ° C).
• monomers chosen from isobornyl acrylate, cyclohexyl acrylate (19 ° C), ethyl acrylate (10 ° C), methyl methacrylate (100 ° C), cyclohexyl methacrylate (83 ° C), ethyl methacrylate (65 ° C), butyl methacrylate (20 ° C) and styrene (100 ° C).
• the copolymers according to the invention can be copolymers comprising two blocks (diblocks), such as: - poly (acrylic acid-butyl co-acrylate) -b-poly (methyl methacrylate-co-acrylic acid) , and - poly (methacrylic acid-butyl co-acrylate) -b-poly (methyl methacrylate-co-methacrylic acid).
• the copolymers according to the invention can be copolymers comprising three blocks (triblocks), such as: - poly (methyl methacrylate co acrylic acid) -b-poly (acrylic acid butyl acrylate) -b-poly (methyl methacrylate co acrylic acid), - poly (methyl methacrylate co (meth) acrylic acid) -b-poly (methacrylic acid co butyl acrylate) -b-poly (methyl methacrylate co methacrylic acid), - poly (methyl acrylate co acrylic acid) -b-poly (acrylic acid co butyl acrylate) -b-poly (methyl acrylate co acrylic acid), - poly (acrylic acid co butyl acrylate) -b-poly (methyl methacrylate co acrylic acid) -b-poly (acrylic acid co butyl acrylate); - (acrylic polyacid) -b-poly (acrylic acid butyl acrylate) -b-pol
• At least one of the blocks of the copolymer according to the invention has a glass transition temperature (Tg) less than or equal to 20 ° C. Also preferably, at least one of the blocks of the copolymer according to the invention has a glass transition temperature (Tg) greater than or equal to 20 ° C.
• Tg glass transition temperature
• the method of measuring Tg is explained before the examples.
• the copolymer according to the invention can comprise both a block having a Tg greater than or equal to 20 ° C and a block having a Tg less than 20 ° C.
• the copolymer obtained has a so-called "elastomeric" character. It may be a diblock copolymer, comprising only these two blocks or a triblock copolymer or comprising three distinct blocks, for example a central block of Tg below 20 ° C and two blocks at the ends of Tg higher or equal to 20 ° C; or a central sequence of Tg greater than or equal to 20 ° C and two sequences at the ends of Tg less than or equal to 20 ° C.
• the copolymer can comprise at least two distinct blocks, both having a Tg greater than or equal to 20 ° C. Said block copolymer then has a so-called "rigid" character.
• Tg sequences greater than 20 ° C can be obtained by homopoly erization of monomers whose homopolymers have a Tg> 20 ° C or by copolymerization of monomers of Tg> 20 ° C, but also by copolymerization of monomers of Tg> 20 ° C to which monomers of Tg ⁇ 20 ° C can be added.
• Tg sequences below 20 ° C can be obtained by homopolymerization of monomers of Tg ⁇ 20 ° C or copolymerization of monomers of Tg ⁇ 20 ° C, but also by copolymerization of monomers of Tg ⁇ 20 ° C to which one can add monomers of Tg> 20 ° C.
• the total content of the copolymer in monomers, the homopolymer of which has a Tg greater than 20 ° C. is preferably greater than or equal to 50% by weight, in particular of the order of 70% to 100% by weight, relative to the total weight of the block copolymer.
• Said block copolymer then also has a so-called "rigid" character.
• the copolymer can comprise at least two distinct blocks, both having a Tg less than or equal to 20 ° C. Said block copolymer then has a so-called "adhesive" character.
• the total content of the copolymer in monomers, the homopolymer of which has a Tg of less than 20 ° C. is preferably greater than or equal to 60% by weight, in particular of the order of 70% to 100% by weight, relative to the total weight of the block copolymer.
• Said block copolymer then has a so-called "adhesive" character.
• the copolymer according to the invention comprises at least one hydrophilic block which has a Tg greater than or equal to 0 ° C, for example between 0 and 250 ° C, in particular between 50 ° C and 200 ° C.
• the weight average molecular weight Mw of the block copolymer according to the invention is preferably between 4,000 and 1,000,000, preferably between 10,000 and 800,000, more preferably between 20,000 and 500,000, especially between 60,000 and 350,000.
• the weight-average molecular mass Mw of each block or sequence is between 2000 and 500,000, preferably between 5,000 and 400,000, and better between 10,000 and 300,000.
• the polymers according to the invention can be diblock polymers of type AB; or alternatively triblock polymers of the ABA, BAB, ABC type with C different from A and B; or also multiblock polymers having more than three blocks, for example of the type (AB) n, (ABA) n, (BAB) n, (ABC) n, ABCD, with A, B, C and D of different chemical nature.
• the polymer according to the invention comprises at least 3 successive blocks, two successive blocks being different: for example of the ABA or ABC type.
• Said polymers can be prepared according to methods known to those skilled in the art. Among these methods, mention may be made of anionic polymerization; controlled radical polymerization, for example with xanthans, dithiocarbamates or dithioesters; polymerization using nitroxide type precursors; radical atom transfer polymerization (ATRP); group transfer polymerization.
• the block copolymers according to the invention can be obtained by living or pseudo-living radical polymerization known as still controlled, described in particular in "New Method of Polymer Synthesis", Blackie Académie & Professional, Kunststoff, 1995, volume 2, page 1.
• Controlled radical polymerization designates polymerizations for which the secondary reactions which usually lead to the disappearance of the propagating species (termination reaction or transfer) are made very unlikely compared to the propagation reaction thanks to a free radical control agent.
• the imperfection of this mode of polymerization lies in the fact that when the concentrations of free radicals become high relative to the concentration of monomer, the secondary reactions become decisive again and tend to widen the distribution of the masses
• the polymerization living or pseudo-living is a polymerization for which the growth of polymer chains ceases only with the disappearance of the monomer.
• the number average mass (Mn) increases with the conversion.
• Such polymerizations lead to copolymers whose mass dispersity is low, that is to say to polymers with a polydispersity index by mass (Ip) generally less than 2.
• Anionic polymerization is a typical example of living polymerization.
• Pseudo-living polymerization is, in turn, associated with controlled radical polymerization.
• - radical polymerization controlled by nitroxides mention may be made of: - radical polymerization controlled by nitroxides.
• We can in particular refer to patent applications O96 / 24620 and WO00 / 71501 which describe the tools of this polymerization and their implementation, as well as the articles published by Fischer (Chemical Reviews, 2001, 101, 3581), by Tordo and Gnanou (J. Am. Che.
• the polymer chains of the copolymers grow simultaneously and therefore incorporate at all times the same ratio of co-monomers. All the chains therefore have the same or similar structures, hence a low dispersity in composition. These chains also have a low mass polydispersity index.
• the polymerization can be carried out according to the atom transfer technique (Atom Transfer Radical Polymerization or "ATRP", in English), or by reaction with a nitroxide, or even according to the technique of "reversible addition- fragmentation chain transfer "(" RAFT ”) or finally by the reverse “ATRP” technique, called “reverse ATRP”.
• the radical polymerization technique by atom transfer consists in blocking the growing radical species in the form of a C-halide bond (in the presence of a metal / ligand complex). This type of polymerization results in a control of the mass of the polymers formed and in a low mass dispersity index.
• radical polymerization by transfer of atoms 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 halogen compound comprising a transition metal capable of participating in a reduction step with the initiator and a “dormant” polymer chain, this will be called “chain transfer agent”; and - a ligand which can be chosen from compounds comprising a nitrogen (N), oxygen (0), phosphorus (P) or sulfur (S) atom, capable of being coordinated 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.
• an initiator having at least one transferable halogen atom
• - a halogen compound comprising a transition metal capable of participating in a reduction step with the initiator and a “dormant” polymer chain, this will be called “chain transfer agent”
• the halogen atom is preferably a chlorine or bromine atom. This process is in particular described in application WO 97/18247 and in the article by Matyjasezwski et al. published in JACS, 117, page 5614 (1995).
• 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 a R type where R a and Rb can be, independently of one another, a alkyl radical having from 2 to 30 carbon atoms or forming one and the other, with the nitrogen atom, a ring having from 4 to 20 carbon atoms, such as for example a ring 2, 2, 6, 6-tetramethylpiperidinyl.
• This polymerization technique is described in particular in the articles "Living free radical polymerization: a unique technique for preparation of controlled macromolecular architectures" CJ Hawker; Chem. Res.
• the RAFT (reversible addition-fragmentation chain transfer) polymerization technique consists in blocking the growing radical species in the form of a CS-type bond.
• Dithio compounds such as dithioesters (-C (S) S-), such as dithiobenzoates, dithiocarbamates (-NC (S) S-) or dithiocarbonates (-OC (S) S-) (xanthates) are used for this. ).
• dithioesters such as dithiobenzoates, dithiocarbamates (-NC (S) S-) or dithiocarbonates (-OC (S) S-) (xanthates) are used for this.
• These compounds make it possible to control the chain growth of a wide range of monomers.
• the dithioesters inhibit the polymerization of vinyl esters, while the dithiocarba ates are very weakly active vis-à-vis methacrylates, which limits to some extent the application of these compounds.
• the polymerization generally takes place in several stages according to the following general scheme: - a) in a first stage, the first monomer or mixture of monomers is polymerized to form a macroinitiator or precursor; - b) the polymers can be purified by precipitation and then dried under vacuum, - c) in a second step, the polymerization of the second block consisting of a monomer or a mixture of monomers is carried out at the end of the macroinitiator.
• Steps b and c are repeated as many times as necessary according to the number of sequences, which is the case for the production of diblock polymers of type AB, triblocks of type ABC or multiblocks (AB) ⁇ or (ABC) n with A , B and C of different chemical natures.
• a difunctional initiator is generally used to produce symmetrical triblock polymers of ABA or BAB type.
• the chain transfer agents and solvents may be the same or different in step a) and step b).
• 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). This involves first polymerizing an Ml monomer in a polymerization reactor; to follow, by kinetics for example, its consumption over time and 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.
• copolymers according to the invention can be present in the compositions according to the invention in an amount of 0.1% to 60% by weight, preferably 0.5% to 50% by weight, in particular 1% to 30% by weight, or even 2% to 20% by weight, relative to the total weight of the composition.
• compositions can be present in the composition in dissolved form, for example in water or an organic solvent, or else in the form of an aqueous or organic dispersion.
• they are in the form of a dispersion of polymer particles in water, said particles possibly having a size of 5 to 400 nm, in particular 10 to 250 nm, measured by light scattering (with a Coulter type device Counter).
• One of the characteristics of the copolymers according to the invention is that they do not form a viscoelastic gel, in water at 25 ° C., at a concentration of 5% by weight, in particular at a concentration of 10% by weight, or even of 20% by weight.
• the copolymers according to the invention are such that a solution of these copolymers, at 20% by weight in water, has a viscosity at 25 ° C of between 1 and 10,000 centipoises (or mPa.s), in particular from 2 to 5,000 mPa.s and in particular from 5 to 3,000 mPa.s.
• the viscosity is measured using a Brookfield viscometer, with a needle-like module (spindle).
• spindle needle-like module
• a person skilled in the art knows how to choose the “speed / time” pair and the needle type mobile from among the needles varying from number 00 to 07, based on their general knowledge, so as to be able to measure low-viscous liquid compounds.
• 35% torque and a 02 needle are used.
• the rheological behavior of the copolymers according to the invention can also be illustrated by the value of their elastic (G 1 ) and viscous (G ") moduli.
• G 1 elastic
• G ' ⁇ G " an elastic modulus lower than the viscous modulus
• the elastic module is between 0.1 and 20 Pa
• the viscous module is between 0.1 and 20 Pa.
• These modules are determined at 25 ° C, at 1 Hz, with a constrained rheometer (HAAKE RS 150) equipped with a sandblasted titanium body fitted with an anti-evaporation device, a planetary measuring body with a diameter of 6 cm and a 2 ° angle.
• the shear rate or stress frequency is 1 Hz (s -1 ).
• compositions according to the invention comprise, in addition to said polymers, a physiologically acceptable medium, in particular cosmetically or dermatologically acceptable, that is to say a medium compatible with keratin materials such as the skin of the face or body, hair, eyelashes, eyebrows and nails.
• a physiologically acceptable medium in particular cosmetically or dermatologically acceptable, that is to say a medium compatible with keratin materials such as the skin of the face or body, hair, eyelashes, eyebrows and nails.
• the composition can thus comprise, a hydrophilic medium comprising water or a mixture of water and organic solvent (s) hydrophilic (s) such as alcohols and in particular linear or branched lower monoalcohols having from 2 to 5 carbon atoms such as ethanol, isopropanol or n-propanol, and polyols such as glycerin, diglycerin, propylene glycol, sorbitol, pentylene glycol, and polyethylene glycols, or even C ethers 2 and hydrophilic C 2 -C 4 aldehydes.
• the water or the mixture of water and hydrophilic organic solvents may be present in the composition according to the invention in a content ranging from 0.1% to 99% by weight, relative to the total weight of the composition, and preferably 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, mention may be made of: hydrocarbon oils of animal origin such as perhydrosqualene; vegetable hydrocarbon oils such as liquid triglycerides of fatty acids with 4 to 10 carbon atoms such as the triglycerides of heptanoic or octanoic acids, or even sunflower, corn, soybean, grape seed, sesame, apricot, macadamia oils, castor, avocado, triglycerides of caprylic / capric acids, jojoba oil, shea butter; 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 palmitate, oct
• composition according to the invention can also comprise one or more organic solvents, physiologically acceptable. These solvents can generally be present in a content ranging from 0.1 to 90%, preferably from 0.5 to 85%, more preferably from 10 to 80% by weight, relative to the total weight of the composition, and better still from 30 to 50%.
• ketones which are liquid at room temperature such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, isophorone, cyclohexanone, acetone
• propylene glycol ethers which are liquid at room temperature such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol mono n-butyl ether
• short chain esters (having from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate, isopentyl acetate
• ethers liquid at 25 ° C such as diethyl ether, dimethyl ether or dichlorodiethyl ether
• alkanes liquid at 25 ° C such as decane, heptane, dodecane
• wax within the meaning of the present invention is meant a lipophilic compound, solid at room temperature (25 ° C.), with reversible solid / liquid state change, having a melting point greater than or equal to 25 ° C. up to 'at 120 ° C.
• melting By bringing the wax to the liquid state (melting), it is possible to make it miscible with the oils which may be present and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, one recrystallizes the wax in the oils of the mixture.
• the melting point of the wax can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name DSC 30 by the company METLER.
• DSC differential scanning calorimeter
• the waxes can be hydrocarbon, fluorinated and / or silicone and be of vegetable, mineral, animal and / or synthetic origin. In particular, the waxes have a melting point greater than 30 ° C and better still greater than 45 ° C.
• wax which can be used in the composition of the invention mention may be made of beeswax, Carnauba or Candellila wax, paraffin, microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene or Fischer Tropsch waxes, silicone waxes such as alkyl or alkoxy-dimethicone having from 16 to 45 carbon atoms.
• 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 are a function of the mechanical properties and of the desired textures.
• the composition may contain from 0.1 to 50% by weight of waxes, relative to the total weight of the composition and better still from 1 to 30% by weight.
• the composition according to the invention can also comprise, in a particulate phase, pigments and / or nacres and / or fillers usually used in cosmetic compositions.
• the composition can also comprise other coloring materials chosen from water-soluble dyes or liposoluble dyes well known to those skilled in the art.
• pigments it is necessary to understand particles of any shape, white or colored, mineral or organic, insoluble in the physiological medium, intended to color the composition.
• fillers it is necessary to understand colorless or white, mineral or synthetic particles, lamellar or non-lamellar, intended to give body or rigidity to the composition, and / or softness, mattness and uniformity. makeup.
• the pigments can be present in the composition in an amount of 0.01 to 25% by weight of the final composition, and preferably in an amount of 3 to 10% by weight. They can be white or colored, mineral or organic. Mention may be made of titanium, zirconium or cerium oxides, as well as zinc, iron or chromium oxides, ferric blue, chromium hydrate, carbon black, ultramarines (aluminosilicate polysulphides) , manganese pyrophosphate and certain metallic powders such as those of silver or aluminum.
• D&C pigments and the lacquers commonly used to give the lips and the skin a makeup effect which are calcium, barium, aluminum, strontium or zirconium salts.
• the nacres can be present in the composition in an amount of 0.01 to 20% by weight, preferably at a rate of the order of 3 to 10% by weight.
• mother-of-pearl we can cite mother-of-pearl natural, mica coated with titanium oxide, iron oxide, natural pigment or bismuth oxychloride as well as colored titanium mica.
• liposoluble or water-soluble which may be present in the composition, alone or as a mixture, at a rate of 0.001 to 15% by weight, preferably 0.01 to 5% by weight and in particular from 0.1 to 2% by weight, relative to the total weight of the composition, there may be mentioned the disodium salt of culvert, the disodium salt of alizarin green, quinoline yellow, the trisodium salt of amaranth, the disodium salt of tartrazine, the salt monosodium rhodamine, disodium fuchsin salt, xanthophyll, methylene blue, cochineal carmine, halo-acid, azo, anthraquinone dyes, copper or iron sulfate, Sudan brown, Sudan red and annatto, as well as beet juice and carotene.
• the disodium salt of culvert the disodium salt of alizarin green, quinoline yellow
• the trisodium salt of amaranth the dis
• 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 0.02% at 30% by weight.
• the fillers can be mineral or organic of any shape, platelet, spherical or oblong.
• talc Mention may be made of talc, mica, silica, kaolin, polyamide (Nylon®), poly- ⁇ -alanine and polyethylene powders, powders of tetrafluoroethylene polymers (Teflon®), lauroyl-lysine, starch, boron nitride, hollow polymeric microspheres such as those of polyvinylidene / acrylonitrile such as Expancel® (Nobel Industrie), acrylic acid copolymers (Polytrap® from Dow Corning) and silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles , precipitated calcium carbonate, magnesium carbonate and hydrocarbon, hydroxyapatite, hollow silica microspheres (Silica Beads® from Maprecos), glass or ceramic microcapsules, metal soaps derived from organic carboxylic acids having from 8 to 22 carbon atoms, preferably from 12 to 18 carbon
• the composition may further comprise an additional polymer such as a film-forming polymer.
• film-forming polymer means a polymer capable of forming on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.
• film-forming polymers capable of being used in the composition of the present invention mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin and their mixtures, in particular acrylic polymers, polyurethanes , polyesters, polyamides, polyureas, cellulosic polymers such as nitrocellulose.
• composition according to the invention can also comprise ingredients commonly used in cosmetics, such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, dandruff agents, propellants, ceramides, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, dandruff agents, propellants, ceramides, or mixtures thereof.
• ingredients commonly used in cosmetics such as vitamins, thickeners, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, anti-hair loss agents, dandruff agents, propellants
• composition according to the invention may be in the form of a suspension, a dispersion in particular of oil in water by means of vesicles; an oily solution possibly thickened or even gelled; an oil-in-water, water-in-oil, or multiple emulsion; a gel or foam; an oily or emulsified gel; a dispersion of vesicles, in particular lipid vesicles; a biphasic or multiphase lotion; a spray; loose, compact or poured powder; an anhydrous paste.
• This composition may have the appearance of a lotion, a cream, an ointment, a flexible paste, an ointment, a cast or molded solid and in particular in stick or in a cup, or alternatively of compacted solid.
• Those skilled in the art can choose the appropriate dosage form, as well as its method of preparation, on the basis of his general knowledge, taking into account on the one hand the nature of the constituents used, in particular their solubility in the support, and on the other hand of the application envisaged for the composition.
• the cosmetic composition according to the invention may be in the form of a care and / or make-up product for the skin of the body or the face, the lips and the hair, a sun or self-tanning product, or even a hair product. It finds in particular a particularly interesting application in the field of make-up of the skin, semi-mucous membranes, mucous membranes and / or integuments (nails, eyelashes, eyebrows, hair and hair).
• composition in particular a product for the complexion such as a foundation, a blusher or an eyeshadow; a lip product such as lipstick or lip care; a concealer; a blush, a mascara, an eyeliner; an eyebrow makeup product, a lip or eye pencil; a nail product such as nail polish or nail care; a body makeup product; a hair makeup product (mascara or hair spray).
• the composition according to the invention may be a composition for protecting or caring for the skin of the face, neck, hands or body, in particular an anti-wrinkle, anti-fatigue composition making it possible to give the skin a radiant boost, a moisturizing or treating composition; an anti-sun or artificial tanning composition.
• 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 foam form.
• the subject of the invention is also a cosmetic process for making up or caring for keratin materials, in particular the skin of the body or of the face, nails, hair and / or eyelashes, comprising the application to said materials of a cosmetic composition as defined above.
• the invention also relates to an adhesive composition
• an adhesive composition comprising a copolymer in accordance with the invention.
• the copolymer is advantageously present in a content of at least 5% by weight relative to the total weight of the composition.
• the adhesive composition can comprise additives such as tackifying resins, plasticizers, such as oils, in which case it will constitute a hot-melt pressure-sensitive adhesive composition (known by the abbreviation HMPSA).
• HMPSA hot-melt pressure-sensitive adhesive composition
• the copolymers of the invention contribute to improving the mechanical properties of the adhesive compositions, in particular when they are exposed to high temperature (for example, tape of the post-it type deposited on a window pane in direct sunlight).
• oils to be used as plasticizers in HMPSA compositions are oils of the trimellitate type, such as trioctyl trimellitate, or even predominantly naphtenic oils such as Catenex N956 from Shell. It is not recommended to use oils of paraffinic type (typically Primol 352 oil, from Exxon-Mobil), of liquid polybutene type (typically Napvis 10) because, under certain conditions, they are incompatible with the copolymer and exude from the mixture.
• paraffinic type typically Primol 352 oil, from Exxon-Mobil
• liquid polybutene type typically Napvis
• the tackifying resins are generally resins based on rosins such as Forai AX, of rosin ester such as Forai F85, the resins known under the name pure monomer such as Krystallex F85, polyterpenes such as DERCOLYTE A 115 from DRT, hydroxylated polyesters (typically Reagem 5110 from DRT), terpene styrene (typically DERCOLYTE TS 105 from DRT), terpene pentaerythritol (typically DERTOLINE P2L), resins based on terpene phenol (typically Dertophene T105 from DRT).
• rosins such as Forai AX
• rosin ester such as Forai F85
• the resins known under the name pure monomer such as Krystallex F85
• polyterpenes such as DERCOLYTE A 115 from DRT
• hydroxylated polyesters typically Reagem 5110 from DRT
• the composition of the invention can be used as an adhesive, for constituting, for example, tapes, labels and adhesive tapes, in various fields, such as hygiene, wood, bookbinding, packaging.
• the invention also relates to the use of a copolymer as defined above as an ingredient of an adhesive composition.
• the invention relates to thermoplastic compositions.
• the copolymer is advantageously present in a content of at least 1% by weight relative to the total weight of the composition.
• such compositions may further comprise one or more thermoplastic polymers, such as polymethyl methacrylate, polystyrene and polyvinyl chloride.
• thermoplastic polymers such as polymethyl methacrylate, polystyrene and polyvinyl chloride.
• the glass transition temperatures of the sequences can be theoretical Tg determined from the theoretical Tg of the constituent monomers of each of the sequences, which can be found in a reference manual such as the Polymer Handbook, 3 rd ed, 1989, John Wiley, according to the following relationship, known as Fox's Law: wi being the mass fraction of the monomer i in the sequence considered and Tgi being the glass transition temperature of the homopolymer of the monomer i. Unless otherwise indicated, the Tg indicated for the sequences are theoretical Tg.
• the average molar masses eh weight (Mw) and number (Mn) are determined by liquid chromatography by gel permeation or GPC (solvent THF, calibration curve established with linear polystyrene standards, refractometric detector).
• the GPC is carried out with STYRAGEL HR4 / 7.8 x 300 mm Columns, sold by Waters WAT044225. Detection is carried out with a WATERS 410 refractometer.
• the eluent is THF, at a flow rate of 1 ml / min.
• the volume injected is 50 microliter, at 25 ° C.
• the 1 block formed is characterized by GPC to determine the mass of the ERE sequence.
• the overall block copolymer is characterized by GPC so as to determine the mass of the total copolymer.
• the theoretical average mass by weight of a block is given by the ratio: (weight (g) of monomers constituting the block) / (weight (g) initiator).
• the relative proportion of the different monomers between the 1st block and the second block is determined by NMR.
• the polymers of the examples are synthesized by the ATRP method: - in the presence of copper (Cul) in the form of copper halide such as, for example, CuBr (of 99% purity) supplied by Aldrich or CuCl (99% purity) supplied by ACROS, - with an initiator of the RBr type, - and a ligand of the amino type.
• copper Cul
• CuBr of 99% purity
• CuCl of 99% purity supplied by ACROS
• ligand PMDETA or N, N, N ', N'',N''-pentamethyldiethylenetriamine from Fluka are used.
• the monomers are previously passed through an alumina column so as to eliminate the possible stabilizer.
• the diblock synthesis takes place using a monofunctional initiator of the ethyl 2-bromoisobutyrate type supplied by Aldrich at a degree of purity 98%.
• the polymerization proceeds in several stages: 1st stage: formation of the first block by polymerization of the monomer (or mixture of monomers) constituting the first block according to the following general diagram:
• 1st stage formation of the first block by polymerization of the monomer (or mixture of monomers) constituting the first block according to the following general diagram:
• a flow of argon is bubbled with stirring for 5 minutes, then the ligand is still introduced with stirring and under a flow of argon, copper and finally 1 initiator.
• Three vacuum / argon degassing cycles are carried out.
• the mixture is stirred, then, when it is homogeneous, it is placed in an oil bath at a temperature of 90 ° C (bath temperature).
• the polymerization takes place for a given time at 90 ° C.
• the polymer is purified by passage through an alumina column so as to separate the copper-based catalyst.
• the polymer is then precipitated in a water / methanol mixture (20/80) when cold (dry ice).
• the first block is thus obtained which plays the role of precursor (or macroinitiator) for the polymerization of the second sequence: it is a “functional” polymer comprising at its end a function capable of re-initiating the polymerization of a second monomer (or mixture of monomers) constituting the second block.
• precursor or macroinitiator
• 2 nd step formation of the second block by polymerizing the monomer (or monomer mixture) at the end of the macroinitiator (polymer-Br) or (Br- polymer-Br)
• the ligand, the solvent and the copper are then added under a stream of argon, then the monomer or mixture of monomers.
• the mixture is cooled with liquid nitrogen. Once the mixture is frozen, three vacuum-argon degassing cycles are carried out. The mixture is allowed to return to the liquid state and then the reactor in an oil bath at a temperature of 90 ° C.
• the polymer is purified by passage through an alumina column so as to separate the copper-based catalyst.
• the final polymer is then precipitated in a water / methanol mixture (20/80) when cold (dry ice).
• Example 1 Preparation of a diblock polymer poly (butyl acrylate-co-acrylic acid) -b— poly (methyl methacrylate-acrylic co-acid).
• This polymer is prepared by hydrolysis of a poly (butyl acrylate-tert-butyl co-acrylate) -b-poly (methyl methacrylate-tert-butyl co-acrylate) diblock copolymer.
• 2nd step polymerization of the methyl methacrylate / tert-butyl acrylate mixture at the end of the macro-initiator: poly (butyl acrylate-tert-butyl co-acrylate) -Br
• the macroinitiator from the first step is introduced into a container equipped with an ovoid magnetic bar and allowed to evaporate for 12 hours under reduced pressure to remove as much as possible any residual monomers.
• the CPG is carried out just before the synthesis of the second block; the macro initiator and the final block are measured under the same conditions.
• the hydrolysis is carried out with trifluoroacetic acid on the tert-butyl acrylate unit. A 6-fold excess of acid over the tert-butyl unit is used.
• a diblock copolymer is finally obtained having the following distribution: - in mole%: poly (methyl methacrylate 97.1% -co-acrylic acid 2.9%) -b-poly (butyl acrylate 81.0% -co-acrylic acid 19.0% ) - in% by weight: poly (methyl methacrylate 97.9% -co-acrylic acid 2.1%) -b-poly (butyl acrylate 88.4% -co-acrylic acid 11.6%)
• This polymer is prepared by hydrolysis of a triblock copolymer poly (methyl methacrylate-tert-butyl co-methacrylate) -b-poly (butyl acrylate-tert-butyl methacrylate) -b- poly (methyl methacrylate-co-methacrylate tert-butyl)
• the precursor is introduced into a container equipped with a magnetic ovoid bar and it is allowed to evaporate for 12 hours under reduced pressure to remove as much as possible any residual monomers.
• the poly (methyl methacrylate-tert-butyl co-methacrylate) -b-poly (butyl acrylate-co-methacrylate) is hydrolyzed.
• tert-butyl) -b-poly (methyl methacrylate-tert-butyl co-methacrylate) previously prepared.
• the hydrolysis is carried out with trifluoroacetic acid on the tert-butyl acrylate unit. A 5-fold excess of acid over the tert-butyl unit is used.
• the polymer is dissolved at 30% in dichloromethane. The reaction takes place at room temperature for 16 hours.
• a triblock polymer having the following distribution (% by weight in the triblock): poly (methyl methacrylate 3 .9-co-methacrylic acid 5.1) 15% -b- poly (butyl acrylate 86-co- methacrylic acid 14) 70% -b-poly (methyl methacrylate 34.9-co-methacrylic acid 15.1) 15%
• Viscosity in water 47.6 mPa.s (measured with a No. 02 needle with a torque of 38.1%), at 25 ° C and at a concentration of 20% by weight.
• Example 4 The polymer of Example 1 is dissolved in water, in an amount of 15 g of polymer in 100 ml of water (solution at 15% by weight). A hair composition is obtained which can be packaged in a pump bottle for application to the hair; this composition brings coi fant to the hair.
• Example 4
• Example 2 The polymer of Example 2 is dissolved in water, in an amount of 15 g of polymer in 100 ml of water (solution at 15% by weight).
• a hair composition is obtained which can be packaged in a pump bottle for application to the hair; this composition brings styling to the hair.
• Example 1 The polymer of Example 1 is dissolved in ethyl acetate, at a rate of 25 g of polymer in 100 ml of ethyl acetate (25% by weight solution). After adding the appropriate coloring materials, a nail varnish is obtained which can be applied to the nail.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• Animal Behavior & Ethology (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Birds (AREA)
• Epidemiology (AREA)
• Inorganic Chemistry (AREA)
• Cosmetics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesive Tapes (AREA)
• Graft Or Block Polymers (AREA)
• Adhesives Or Adhesive Processes (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=34944766

Family Applications (1)

Country Status (7)

Families Citing this family (20)

Family Cites Families (16)

• 2004
  • 2004-04-09 FR FR0450718A patent/FR2868784B1/fr not_active Expired - Fee Related
• 2005
  • 2005-04-08 KR KR1020067020978A patent/KR101290934B1/ko not_active IP Right Cessation
  • 2005-04-08 MX MXPA06011387A patent/MXPA06011387A/es active IP Right Grant
  • 2005-04-08 WO PCT/FR2005/050227 patent/WO2005103102A2/fr not_active Application Discontinuation
  • 2005-04-08 CN CN2005800108890A patent/CN1997680B/zh not_active Expired - Fee Related
  • 2005-04-08 JP JP2007506821A patent/JP4902526B2/ja not_active Expired - Fee Related
  • 2005-04-08 EP EP05746970A patent/EP1732964A2/de not_active Withdrawn

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events