WO2007099269A2 - Cosmetic composition comprising an acrylic acid homopolymer and an acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer, and the use thereof as a hair care product - Google Patents

Cosmetic composition comprising an acrylic acid homopolymer and an acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer, and the use thereof as a hair care product Download PDF

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Publication number
WO2007099269A2
WO2007099269A2 PCT/FR2007/050873 FR2007050873W WO2007099269A2 WO 2007099269 A2 WO2007099269 A2 WO 2007099269A2 FR 2007050873 W FR2007050873 W FR 2007050873W WO 2007099269 A2 WO2007099269 A2 WO 2007099269A2
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Prior art keywords
methacrylate
acrylate
composition according
weight
acrylic acid
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PCT/FR2007/050873
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French (fr)
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WO2007099269A3 (en
Inventor
Ludivine Laurent
Cécile Bebot
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L'oreal
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Priority claimed from FR0601939A external-priority patent/FR2898054A1/en
Application filed by L'oreal filed Critical L'oreal
Publication of WO2007099269A2 publication Critical patent/WO2007099269A2/en
Publication of WO2007099269A3 publication Critical patent/WO2007099269A3/en

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    • 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
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers

Definitions

  • Cosmetic composition comprising a homopolymer of acrylic acid and a copolymer of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), and its use as a hair product .
  • the present invention relates to a cosmetic composition
  • a cosmetic composition comprising, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of acrylate hydroxyester (s) or methacrylate (s).
  • the present invention also relates to a cosmetic hair treatment method using the aforementioned composition, and a use of this cosmetic composition as a hair product, for example as a styling product.
  • Hair styling products are usually used to build, structure the hairstyle and give it a lasting hold.
  • the corresponding compositions generally comprise one or more film-forming polymers in a cosmetically acceptable medium. These polymers allow the formation of a sheathing film on the hair, thus ensuring the maintenance of the hairstyle.
  • the fixing polymer films thus formed have the disadvantage of being relatively friable, which limits in time the holding of the hairstyle, and causes the formation on the hair of unsightly residues.
  • a plasticizer in the styling products based on film-forming polymers a plasticizer. This effectively improves the behavior of the hairstyle over time and limit the formation of residues during the day.
  • the non-friability of the polymer films is generally related to the fixing polymer concentration in the styling product (or degree of fixation): if the polymer concentration is decreased fixing for reduce the rigidity of the hairstyle, then the polymer film becomes more friable and the behavior of the hairstyle is less good.
  • the present invention makes it possible in particular to prepare hair styling products that provide significantly improved hairstyling durability, including in products with flexible fixation, that is to say with a low concentration of fixing polymer.
  • compositions according to the invention have been found to provide a very marked improvement in the cosmetic properties of the hair after disentangling: the hair is much softer and less dry than after the application of a conventional fixing product.
  • the subject of the present invention is therefore a cosmetic composition
  • a cosmetic composition comprising, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), characterized in that the weight ratio between the amount of copolymer of acrylate (s) or methacrylate (s) and of acrylate (s) or methacrylate hydroxyester (s) ) on the one hand and the amount of acrylic acid homopolymer on the other hand is between 0, 1 and 10.
  • Another subject of the invention consists of a cosmetic hair treatment method using a composition according to the invention as described below.
  • the subject of the invention is also the use of the composition according to the invention for the cosmetic treatment of the hair, in particular for shaping and / or maintaining the hairstyle.
  • the cosmetic composition comprises, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of acrylate hydroxyester ( s) or methacrylate (s).
  • cosmetically acceptable medium is meant a medium compatible with keratin materials and in particular the hair.
  • the cosmetically acceptable medium comprises water and / or at least one cosmetically acceptable solvent chosen from C 1 -C 4 lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol. -butanol; polyols such as propylene glycol; polyol ethers; C 5 -C 10 alkanes; C 3 -4 ketones such as acetone and methyl ethyl ketone; C 1 -C 4 alkyl acetates such as methyl acetate, ethyl acetate and butyl acetate; dimethoxyethane, diethoxyethane; and their mixtures.
  • C 1 -C 4 lower alcohols such as ethanol, isopropanol, tert-butanol or n-butanol.
  • -butanol polyols such as propylene glycol
  • polyol ethers such as C 5 -C 10 alkane
  • composition according to the invention comprises at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), that is to say a copolymer obtained by copolymerization of at least two monomers:
  • said copolymer is obtained by copolymerization of at least three monomers: at least one first monomer chosen from acrylic acid and methacrylic acid,
  • said second monomer comprises at least one C 1 or C 2 alkyl acrylate or methacrylate.
  • said second monomer can then be methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and mixtures of these compounds.
  • said third monomer is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, and mixtures of these compounds.
  • the composition according to the invention comprises a mixture of at least two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) as described above.
  • It may be a mixture of at least two copolymers with at least two monomers as described above, a mixture of at least two copolymers with at least three monomers as described above, or a mixture of at least one copolymer with at least two monomers and at least one copolymer with at least three monomers as described above.
  • the composition according to the invention comprises a mixture of two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s). ), each of the copolymers being obtained by copolymerization of at least three monomers as described above, namely: at least one first monomer chosen from acrylic acid and methacrylic acid,
  • the composition according to the invention comprises a mixture of two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s). ), comprising a first copolymer obtained by copolymerization of at least three monomers as described above: at least one first monomer chosen from acrylic acid and methacrylic acid, - at least one second monomer chosen from acrylates and C1 to C4 alkyl methacrylates, and
  • At least one third monomer chosen from C1 to C4 hydroxyalkyl acrylates and methacrylates and a second copolymer obtained by copolymerization of at least two monomers: at least one first monomer chosen from C1-C4 alkyl acrylates and methacrylates, and at least one second monomer chosen from C1-hydroxyalkyl acrylates and methacrylates; at C4; said second copolymer does not contain monomers consisting of unsaturated carboxylic acids.
  • composition according to the invention comprises a mixture of at least two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), the two copolymers of this
  • the mixture preferably has different glass transition temperatures.
  • the glass transition temperature (Tg) is measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418-97.
  • One of the two copolymers preferably has a Tg ranging from 35 ° C. to 250 ° C., more preferably from 40 ° C. to 150 ° C. and even more preferentially from 75 ° C. to 100 ° C.
  • the second copolymer preferably has a Tg ranging from -20 ° C to 35 ° C, more preferably from 0 ° C to 35 ° C and even more preferably from 15 ° C to 30 ° C.
  • the difference of Tg between the two copolymers is preferably greater than or equal to 10 ° C, more preferably greater than or equal to 20 ° C and even more preferably greater than or equal to 30 ° C.
  • the copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s) usable (s) in the compositions according to the invention can (can) ) be a block copolymer (s), statistical or alternating. Preferably, it is a random copolymer.
  • the copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) is an anionic copolymer.
  • it comprises hard sequences and soft sequences, that is to say sequences with two glass transition temperatures (Tg), one of the Tg being between 15 and 35 ° C, preferably between 20 and 30 ° C, the other Tg being between 90 and 1 10 ° C, preferably between 95 and 105 ° C.
  • Tg glass transition temperatures
  • the hard sequence comprises at least one monomer chosen from methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and methacrylic acid, and more advantageously, the hard sequence comprises all these monomers.
  • the soft sequence comprises at least one monomer selected from ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, methacrylic acid and more preferably, the soft sequence comprises all these monomers.
  • the molecular weight of this copolymer is between 10,000 g / mol and 200,000 g / mol. Even more preferentially, it is between 20,000 g / mol and 100,000 g / mol.
  • the copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s) can be in a wide variety of forms, for example in the form of solutions or emulsions in water or any other solvent. They can be synthesized by any known method for preparing a copolymer from its different monomers.
  • copolymers and copolymer mixtures that may be used in the compositions according to the invention, mention may be made, inter alia, of the products sold under the name Acudyne by the company Rohm & Haas, such as, for example, and in a nonlimiting manner, the products proposed under the name ACUDYNE DHR, ACUDYNE 258, ACUDYNE 180.
  • the composition according to the invention preferably contains at least 0.01% by weight of copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) , relative to the total weight of the composition.
  • it contains from 0.01% to 20% by weight of copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), and even more preferably from 0.1 to 10% by weight, more preferably from 0.5 to 8% by weight, relative to the total weight of the composition.
  • composition according to the invention also comprises at least one homopolymer of acrylic acid.
  • Such a polymer may be crosslinked or uncrosslinked.
  • the homopolymer of acrylic acid is crosslinked. It may be crosslinked in whole or part, for example with an allyl ether.
  • It may be, for example, a homopolymer of acrylic acid crosslinked with an allyl ether and pentaerythritol, with an allyl ether and sucrose, or with an allyl ether and propylene ether.
  • Such polymers are in particular classified under the name Carbomer in the CTFA dictionary, 10 th edition, 2004. They are among others marketed under the name CARBOPOL by NOVEON.
  • the molecular weight of the acrylic acid homopolymers according to the invention is preferably greater than or equal to 100,000 g / mol. Even more preferably it is greater than or equal to 500 000 g / mol and preferably greater than or equal to 1 000 000 g / mol. It is especially between 1,000,000 g / mol and 10,000,000 g / mol.
  • the composition according to the invention preferably contains at least 0.01% by weight of acrylic acid homopolymer, relative to the total weight of the composition. Preferably, it contains from 0.01 to 10% by weight of such a homopolymer, more preferably from 0.05 to 5% by weight, more preferably from 0.1 to 3% by weight, relative to the total weight. of the composition.
  • the compositions according to the invention may also contain at least one fatty substance.
  • the fatty substances that can be used in the present invention are chosen in particular from vegetable oils, animal oils, mineral oils, natural or synthetic oils, fatty alcohols, waxes and their mixtures.
  • vegetable oil there may be mentioned sweet almond oil, avocado oil, castor oil, olive oil, liquid jojoba wax, sunflower oil, wheat germ oil, sesame oil, peanut oil, grape seed oil, soybean oil, rapeseed oil, safflower oil, coconut oil , corn oil, hazelnut oil, palm oil, apricot kernel oil, calophyllum oil, evening primrose oil, shea butter, rice bran, corn germ oil, passionflower oil and rye oil.
  • mineral oil mention may be made of paraffin oil and liquid petroleum jelly.
  • synthetic oil there may be mentioned squalane, poly ( ⁇ -olefins) such as isododecane or isohexadecane, transesterified vegetable oils and fluorinated oils, fatty esters.
  • fatty esters denotes compounds of formula R 8 COORb in which R a represents the residue of a linear or branched, hydroxylated or unsaturated, saturated or unsaturated higher acid containing from 4 to 29 carbon atoms and Rb represents a chain linear or branched hydrocarbon-based hydrocarbon, saturated or unsaturated, containing from 3 to 30 carbon atoms, the total number of carbon atoms of the ester being greater than 10.
  • R a represents the residue of a linear or branched, hydroxylated or unsaturated, saturated or unsaturated higher acid containing from 4 to 29 carbon atoms
  • Rb represents a chain linear or branched hydrocarbon-based hydrocarbon, saturated or unsaturated, containing from 3 to 30 carbon atoms, the total number of carbon atoms of the ester being greater than 10.
  • Purcellin oil Purcellin oil
  • stearyl octanoate isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, isostearyl neopentanoate or tridecyl neopentanoate.
  • Preferred fatty alcohols include myristyl, cetyl, stearyl, arachidyl, behenyl and erucyl alcohols.
  • a wax within the meaning of the present invention, is a lipophilic compound, solid at room temperature (about 25 ° C.), with a reversible solid / liquid state change, having a melting temperature greater than about 40 ° C. and that can go up to 200 ° C, and having in the solid state an anisotropic crystalline organization.
  • Animal and vegetable waxes comprise, as essential components, esters of carboxylic acids and long-chain alcohols.
  • the size of the crystals of the wax is such that the crystals diffract and / or diffuse the light, conferring on the composition which comprises them a more or less opaque cloudy appearance.
  • animal origin such as beeswax, spermaceti, lanolin wax and lanolin derivatives
  • vegetable waxes such as sunflower wax, rice wax, apple wax, Carnauba wax, Candelilla wax, Ouricury wax, Japan wax, cocoa butter wax or cork fiber wax or sugar cane wax
  • mineral waxes for example paraffin,
  • the fatty substances as described above, when they are present in the composition according to the invention, are preferably present in an amount ranging from 0.1 to 30% by weight, preferably from 1 to 20% by weight. and more preferably from 5 to 15% by weight, based on the total weight of the composition.
  • the composition according to the invention may also comprise at least one surfactant chosen from cationic surfactants, anionic surfactants, nonionic surfactants and amphoteric or zwitterionic surfactants.
  • the composition according to the invention then preferably comprises at least 0.01% by weight of surfactant (s), relative to the total weight of the composition.
  • the composition according to the invention contains from 0.01 to 20% by weight of surfactant (s), more preferably from 0.05 to 4% by weight, relative to the total weight of the composition.
  • anionic surfactants that can be used in the compositions according to the present invention, mention may be made in particular (nonlimiting list) of the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, sodium salts and the like).
  • alkylsulfates alkylethersulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglycerides sulfates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, ⁇ -olefin-sulfonates, paraffin-sulfonates; alkylsulfosuccinates; alkyl ether sulfosuccinates, alkyl amide sulfosuccinates; alkylsulfosuccinamates; alkylsulfoacetates; alkyl ether phosphates, acylsarcosinates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising alkylsulfates, alkylethersulfates, alkylamido
  • anionic surfactants that can still be used, mention may also be made of fatty acid salts such as the oleic, ricinoleic, palmitic and stearic acid salts; coconut oil or hydrogenated coconut oil acids; acyl lactylates whose acyl radical has 8 to 20 carbon atoms.
  • weakly anionic surfactants such as acid alkyl D galactoside uronic and salts thereof, polyoxyalkylenated (C 6 - C 24) ether carboxylic acids, polyoxyalkylenated (C 6 -C2 4) aryl ether carboxylic polyoxyalkylenated, polyoxyalkylenated (C 6 -C 24 ) alkyl ether carboxylic acids and their salts, in particular those containing from 2 to
  • anionic surfactants it is preferred to use, according to the invention, the salts of alkyl sulphates and alkyl ether sulphates and their mixtures.
  • the cationic surfactants that can be used in the compositions of the present invention comprise, for example, primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated salts, quaternary ammonium salts, and mixtures thereof.
  • radicals R 8 to R 11 which may be identical or different, represent a linear or branched aliphatic radical containing from 1 to 30 carbon atoms, or an aromatic radical such as aryl or alkylaryl.
  • the aliphatic radicals may comprise heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens.
  • the aliphatic radicals are for example chosen from alkyl C 1 -30 alkoxy, C 1 -30, polyoxy (C 2 -C 6) alkylamide C 1 -30, (C 1 2-C22) amidoalkyl ( C 2 -C 6) alkyl (Ci2-
  • X is an anion selected from the group of halides, phosphates, acetates, lactates, (C 2 -C 6 ) alkyl sulfates, alkyl- or alkylarylsulfonates.
  • tetraalkylammonium chlorides such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical has from about 12 to 22, are preferred.
  • carbon atoms in particular behenyltrimethylammonium, distearyl dimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides or else palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl (myristylacetate) ammonium chloride sold under the CERAPHYL ® 70 denomination by the company VAN DYK.
  • R 12 represents an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, for example derived from tallow fatty acids
  • R 13 represents a hydrogen atom, a C 1 -C 4 alkyl radical or an alkenyl radical; or alkyl having from 8 to 30 carbon atoms
  • R 14 represents a C 1 -C 4 alkyl radical
  • R 15 represents a hydrogen atom, a C 1 -C 4 alkyl radical
  • X " is an anion selected from the group of halides, phosphates, acetates, lactates, alkyl sulphates, alkyl or alkylaryl sulphonates
  • R 12 and R 13 preferably denote a mixture of alkenyl or alkyl radicals containing from 12 to 21 carbon atoms, for example acid derivatives.
  • fatty tallow R 14 denotes a methyl radical
  • R 15 denotes a hydrogen atom such a product is for example sold under the name
  • R 16 is an aliphatic radical having about 16 to 30 carbon atoms
  • R 17 , R 18 , R 1, R 20 and R 21 which are identical or different, are chosen from a hydrogen atom and an alkyl radical containing from 1 to 4 carbon atoms
  • X is an anion selected from the group of halides, acetates, phosphates, nitrates and methylsulfates.
  • Such diammonium quaternary salts include in particular propane dichloride diammonium;
  • R22 is selected from alkyl C 1 -C 6 hydroxyalkyl or dihydroxyalkyl radicals C 1 -C 6 alkyl;
  • R 23 is chosen from:
  • R 27 hydrocarbon radicals in C 1 -C 22 linear or branched, saturated or unsaturated, - the hydrogen atom
  • R 25 is selected from:
  • R24, R2 6 and R 28 which are identical or different, are chosen from linear or branched, saturated or unsaturated C 7 -C 21 hydrocarbon radicals; r, s and t, identical or different, are integers ranging from 2 to 6; y is an integer from 1 to 10; x and z, which are identical or different, are integers ranging from 0 to 10;
  • X " is a simple or complex anion, organic or inorganic, provided that the sum x + y + z is from 1 to 15, that when x is 0, then R 23 denotes R 27 and that when z is 0, then R 25 denotes R29.
  • the alkyl radicals R 22 may be linear or branched and more particularly linear.
  • R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.
  • the sum x + y + z is from 1 to 10.
  • R 23 is a hydrocarbon radical R 27 , it may be long and have from 12 to 22 carbon atoms, or short and have from 1 to 3 carbon atoms.
  • R 25 is a hydrocarbon radical R 29 , it preferably has 1 to 3 carbon atoms.
  • R 24 , R 26 and R 28 which are identical or different, are chosen from linear or branched, saturated or unsaturated C 11 -C 21 hydrocarbon radicals, and more particularly from C 11 -C 11 alkyl and alkenyl radicals. 21 , linear or branched, saturated or unsaturated.
  • x and z are 0 or 1.
  • y is 1.
  • r, s and t which are identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
  • the anion is preferably a halide (chloride, bromide or iodide) or an alkyl sulphate more particularly methyl sulphate.
  • a halide chloride, bromide or iodide
  • an alkyl sulphate more particularly methyl sulphate.
  • methanesulphonate, phosphate, nitrate, tosylate an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.
  • the anion X - is even more particularly chloride or methylsulfate.
  • the ammonium salts of formula (IV) are used more particularly in which: R 22 denotes a methyl or ethyl radical,
  • z is 0 or 1;
  • r, s and t are equal to 2;
  • R 23 is chosen from:
  • R 25 is chosen from:
  • R 24 , R 26 and R 28 which are identical or different, are chosen from linear or branched, saturated or unsaturated C 13 -C 17 hydrocarbon radicals, and preferably from C 13 -C 17 alkyl and alkenyl radicals; , linear or branched, saturated or unsaturated.
  • hydrocarbon radicals are linear.
  • the compounds of formula (IV) such as the salts (especially chloride or methylsulfate) of diacyloxyethyl-dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, of monoacyloxyethyl-hydroxyethyl-dimethylammonium and mixtures thereof.
  • the acyl radicals preferably have from 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm oil or sunflower oil. When the compound contains more than one acyl radical, the latter may be identical or different.
  • These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine optionally oxyalkylenated on fatty acids or mixtures of fatty acids of plant or animal origin, or by transesterification. of their methyl esters.
  • This esterification is followed by quaternization using an alkylating agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulphate (preferably methyl or ethyl), the methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin.
  • an alkylating agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulphate (preferably methyl or ethyl), the methyl methanesulfonate, methyl para-tolu
  • composition according to the invention may contain, for example, a mixture of quaternary ammonium mono-, di- and triester salts with a majority by weight of diester salts.
  • acyloxyethyl-dihydroxyethyl-methylammonium methylsulfate a mixture of ammonium salts
  • the mixture containing 15 to 30% by weight of acyloxyethyl-dihydroxyethyl-methylammonium methylsulfate, 45 to 60% of diacyloxyethyl-hydroxyethyl-methylammonium methylsulfate and 15 to 30% of triacyloxyethylmethylammonium methylsulfate, the acyl radicals having from 14 to 18 carbon atoms and coming from partially hydrogenated palm oil.
  • ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180.
  • nonionic surfactants that can be used in the compositions of the present invention are well-known compounds per se (see in particular in this regard "Handbook of Surfactants” by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp. - 178). They are chosen in particular from polyethoxylated, polypropoxylated or polyglycerolated alcohols and fatty alcohols, polyethoxylated, polypropoxylated or polyglycerolated alpha-diols, alkyl (Ci).
  • polyethoxylated, polypropoxylated or polyglycerolated phenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids the fatty chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range from 2 to 50 and the number of glycerol groups that can range from 2 to 30.
  • the condensates of ethylene oxide and of propylene oxide on fatty alcohols preferably having from 2 to 30 ethylene oxide units, the polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1, 5 to 4, the esters of fatty acids and of ethoxylated sorbitan having 2 to 30 ethylene oxide units, sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, polyethoxylated vegetable derivatives, N- (C 6- 2 4) glucamine, amine oxides such as oxides of (C 10-14) amines or oxides of N (acyl C 1 14- aminopropylmorpholine.
  • amine derivatives include the products sold under the name Miranol ®, as described in US patents 2,528,378 and US 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxy-glycinate and Amphocarboxypropionate of respective structures (1) and (2):
  • R a represents an alkyl group derived from an R 8 -COOH acid present in the hydrolysed coconut oil, a heptyl, nonyl or undecyl group,
  • Rb represents a beta-hydroxyethyl group, and R 0 represents a carboxymethyl group
  • X ' represents the group -CH 2 CH 2 -COOH or a hydrogen atom
  • Y ' represents -COOH or the group -CH 2 -CHOH-SO 3 H
  • R a ' represents an alkyl group of a R a ' -COOH acid present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially C 17 and its iso form, a C 17 group unsaturated.
  • compositions according to the invention may also comprise at least one silicone or a silicone derivative, in soluble, dispersed or micro-dispersed form.
  • the silicones or silicone derivatives are preferably present in an amount of less than 10% by weight, preferably ranging from 0.01 to 8%, and still more preferably from 0.1 to 5% by weight relative to the total weight of the composition.
  • compositions according to the invention may also contain at least one additional fixing polymer, different from the copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s), to reinforce the holding effect.
  • additional fixing polymer may be anionic, cationic, nonionic or amphoteric and preferably anionic, nonionic or amphoteric.
  • the anionic fixing polymers that can be used in the compositions according to the invention are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acids. and have a number average molecular weight of between about 500 and 5,000,000.
  • the carboxylic groups are provided by unsaturated mono- or di-carboxylic acid monomers, such as those corresponding to the formula:
  • a 1 denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, via a heteroatom such as oxygen or sulfur
  • R 7 denotes a hydrogen atom, a phenyl or benzyl group
  • R 8 denotes a hydrogen atom, a lower alkyl or carboxyl group
  • R 9 denotes a hydrogen atom, a lower alkyl group, a -CH 2 -COOH group, phenyl or benzyl group.
  • a lower alkyl group preferably denotes a group having 1 to 4 carbon atoms and in particular the methyl and ethyl groups.
  • the anionic fixing polymers with preferred carboxylic groups according to the invention are:
  • Copolymers of acrylic acid and of C 1 -C 4 alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and C-alkyl methacrylate may also be mentioned.
  • 1 -C 20 for example lauryl methacrylate, such as that marketed by the company ISP under the name Acrylidone LM ® and methacrylic acid terpolymers / ethyl acrylate / butyl acrylate terpolymers such as the product sold under the name Luvimer ® 100 P by BASF.
  • Copolymers derived from crotonic acid such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid , linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted and crosslinked, or another vinyl ester monomer, allyl or methallylique a carboxylic acid ⁇ - or ⁇ - cyclic.
  • Such polymers are described, inter alia, in French patents Nos . 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798.
  • a commercial product in this class is the resin. 29-30 marketed by the company National Starch.
  • Such polymers are described in particular in US Patents Nos 2,047,398, 2,723,248, January 13 2102, GB Patent No. 839 805.
  • Commercial products include those sold under the Gantrez ® AN or ES by denominations the ISP company.
  • copolymers comprising (i) one or more maleic, citraconic and itaconic anhydride units and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, ⁇ -olefin or acrylic or methacrylic ester groups; acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.
  • the polymers comprising the sulphonic groups are polymers comprising vinylsulphonic, styrene-sulphonic, naphthalenesulphonic or acrylamido-alkylsulphonic units.
  • These polymers may especially be chosen from:
  • polyacrylamidesulfonic acid salts such as those mentioned in US Pat. No. 4,128,631, and more particularly polyacrylamidoethylpropanesulfonic acid.
  • acrylic acid copolymers such as the acrylic acid terpolymers / ethyl acrylate / N-tert-butylacrylamide sold under the name Ultrahold ® STRONG by the company BASF Crotonic acid-derived copolymers such as vinyl acetate terpolymers / tert-butylbenzoate / acid crotonic acid and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters , vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methyl vinyl ether / monoesterified maleic anhydride sold, e.g., under the name GANTREZ ® by the company ISP
  • the anionic fixing polymers mentioned above are chosen from the methyl vinyl ether / monoesterified maleic anhydride sold under the name Gantrez ® ES 425 by the company ISP, the acrylic acid terpolymers / ethyl acrylate / N-tert-butylacrylamide sold under the name Ultrahold ® STRONG by the company BASF, the copolymers of methacrylic acid and of methyl methacrylate sold under the name Eudragit ® L by the company Rohm Pharma, the vinyl acetate / vinyl tert-butylbenzoate / crotonic acid and the terpolymers crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer ® MAEX or MAE by BASF, terpol
  • amphoteric fixing polymers that may be used according to the invention may be chosen from polymers comprising B and C units statistically distributed in the polymer chain where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit derived from an acidic monomer comprising one or more carboxylic or sulphonic groups, or B and C may be groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines;
  • B and C may also designate a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulfonic group connected via a hydrocarbon group, or B and C are part of a chain of an ethylene- ⁇ , ⁇ -dicarboxylic-containing polymer, one of which has been reacted with a polyamine having one or more primary or secondary amine groups.
  • amphoteric fixing polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers:
  • a monomer derived from a vinyl compound carrying a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha-chloro acrylic acid
  • a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide.
  • (2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group; b) with at least one acidic comonomer containing one or more several reactive carboxylic groups, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituted esters of acrylic and methacrylic acids, and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
  • the N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are the compounds whose alkyl groups contain from 2 to 12 carbon atoms, and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
  • the acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.
  • Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.
  • Octylacrylamide / acrylates / butylaminoethyl-methacrylate copolymer such as the products sold under the name or Lovocryl AMPHOMER® ® ® 47 by the company National Starch.
  • R 10 represents a divalent group derived from a saturated dicarboxylic acid, an ethylenically double-bonded mono or dicarboxylic aliphatic acid, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or 'a group derived from the addition of any of said acids with a bis-primary or bis-secondary amine
  • Z denotes a group derived from a bis-primary, mono- or bis-secondary polyalkylene polyamine and preferably represents: a) in the proportions of 60 to 100 mol%, the group
  • polyaminoamides (CHi) 6 -NH- derived from hexamethylenediamine, these polyaminoamides being crosslinked by addition reaction of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or an alkane-sultone or their salts.
  • a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives
  • the saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic and trimethyl-2,4,4-adipic acid, terephthalic acids, double acids and the like.
  • ethylenic bond such as, for example, acrylic, methacrylic, itaconic acids.
  • the alkane sultones used in the acylation are preferably propane or butane sultone, the salts of the acylating agents are preferably the sodium or potassium salts.
  • R 11 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
  • y and z represent an integer of 1 to 3
  • R 12 and R 13 represent a hydrogen atom, a methyl group, ethyl or propyl
  • R 14 and R 15 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R 14 and R 15 does not exceed 10.
  • Polymers comprising such units may also include units derived from non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.
  • non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.
  • R 16 represents a group of formula: R 18 R " ⁇ , 19
  • R 20 represents a hydrogen atom, a CH 3 O, CH 3 CH 2 O, phenyl group
  • R 21 denotes a hydrogen atom or a lower alkyl group such as methyl, ethyl
  • R 22 denotes a hydrogen atom, hydrogen or a C 1 -C 6 lower alkyl group such as methyl, ethyl
  • R 23 denotes a C 1 -C 6 lower alkyl group such as methyl, ethyl or a group of the formula: -R.24-N (R22) 2, R24 representing a -CH2-CH2- group, -CH2-CH2-CH2-, -CH 2 - CH (CH 3) - , R22 having the meanings mentioned above.
  • Amphoteric polymers of the -D-X-D-X type chosen from: a) the polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula:
  • X denotes the symbol E or E ', E or E', which may be the same or different, denotes a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the unsubstituted or substituted backbone.
  • hydroxyl groups and may further comprise oxygen, nitrogen, sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane.
  • E denotes the symbol E or E 'and at least once E';
  • E having the meaning indicated above and E 'is a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl groups and having one or more nitrogen atoms, the nitrogen atom being substituted by an optionally interrupted alkyl chain by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functional groups and betainized by reaction with chloroacetic acid or sodium chloroacetate.
  • (9) (C 1 -C 5 ) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N 5 N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkylaminoalkanol.
  • These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.
  • amphoteric fixing polymers mentioned above that are most particularly preferred according to the invention, mention will be made of those of the family (3) such as the copolymers whose CTFA name is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold. under the names AMPHOMER ® , AMPHOMER ® LV 71 or LOVOCRYL ® 47 by NATIONAL
  • the nonionic fixing polymers that can be used according to the present invention are chosen, for example, from:
  • copolymers of vinyl acetate and of ethylene copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate;
  • copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates, such as the products offered by the company ROHM & HAAS under the ® names Primal AC-261 K and EUDRAGIT ® NE 30 D, by BASF under the name 8845, by Hoechst under the name APPRETAN ® 9212;
  • MOWILITH ® LDM 6070 offered by the company HOECHST, RHODOPAS ® SD 215 and RHODOPAS ® DS 910 products offered by RHODIA CHIMIE;
  • copolymers of styrene, of alkyl methacrylate and of alkyl acrylate
  • the alkyl groups of the nonionic polymers mentioned above preferably have from 1 to 6 carbon atoms.
  • the nonionic setting polymers with vinyllactam motifs can be those described in US Pat. Nos. 3,770,683, 3,929,735, 4,521,504, 5,156,762 and 5,506,315.
  • Homopolymers or copolymers with vinyllactam units comprise units of formula (XI):
  • n is independently 3, 4 or 5.
  • the number-average molecular weight of the polymers with vinyllactam units is generally greater than about 5,000, preferably between about 10,000 and 1,000,000, more preferably between about 10,000 and 100,000.
  • These fixing polymers include polyvinylpyrrolidones such as those marketed under the name Luviskol ® K30 by BASF; polyvinylcaprolactams such as those sold under the name Luviskol ® Plus by BASF; poly (vinylpyrrolidone / vinyl acetate) such as those sold under the name PVPVA® S630L ® by ISP, Luviskol ® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; terpolymers and poly (vinylpyrrolidone / vinyl acetate / vinyl propionate) such as, for example, those marketed under the name Luviskol ® VAP 343 by BASF.
  • polyvinylpyrrolidones such as those marketed under the name Luviskol ® K30 by BASF
  • polyvinylcaprolactams such as those sold under the name Luviskol ® Plus by BASF
  • poly (vinylpyrrolidone / vinyl acetate) such
  • the additional fixing polymers may also be chosen from optionally silicone polyurethanes.
  • fixing polymers of the polyurethane type mention may be made of the Luviset Pur and Luviset Si Pur polymers proposed by BASF.
  • These additional fixing polymers may also be chosen from silicone grafted with a hydrocarbon backbone and silicone or silicone backbone grafts and hydrocarbon grafts such as the products VS 70 and VS 80 proposed by the company 3M. They may also be chosen from polyesters containing sulphonic groups, such as the AQ resins (AQ 55, AQ38, and AQ48) proposed by the company Eastman Chemical.
  • composition according to the invention may then contain at least 0.01% by weight of additional fixing polymer, relative to the total weight of the composition. More preferably, the composition according to the invention contains from 0.01 to 20% by weight of additional fixing polymer, more preferably from 0.05 to 15% by weight, even more preferably from 0.1 to 10% by weight. , relative to the total weight of the composition.
  • the compositions according to the invention may also contain at least one thickener other than the homopolymer of acrylic acid, chosen from natural or synthetic, anionic, amphoteric, zwitterionic, nonionic or cationic, associative or non-associative polymeric thickeners and non-polymeric thickeners. such as for example an electrolyte or a sugar.
  • compositions in accordance with the invention may be packaged in a jar, in a tube, in a pump bottle or in an aerosol device that is usual in cosmetics.
  • the compositions according to the invention may, when they are intended to be packaged in an aerosol-type device, contain at least one propellant, such as a propellant gas.
  • the propellant can then be chosen for example from dimethyl ether, C 3 to C 5 alkanes, halogenated hydrocarbons, and mixtures thereof.
  • compositions according to the invention may further contain at least one additive chosen from pearlescent agents; opacifying agents; plasticizers; solar filters; the perfumes ; dyes; conservatives ; pH stabilizers; acids; the basics ; polyols (for example glycols); mineral charges; glitter, and any other additive conventionally used in the cosmetic field.
  • at least one additive chosen from pearlescent agents; opacifying agents; plasticizers; solar filters; the perfumes ; dyes; conservatives ; pH stabilizers; acids; the basics ; polyols (for example glycols); mineral charges; glitter, and any other additive conventionally used in the cosmetic field.
  • additives are present in the composition according to the invention in an amount ranging from 0 to 50% by weight relative to the total weight of the composition.
  • compositions according to the invention may be in the form of more or less thickened liquids, gels, creams, pastes or foams.
  • compositions according to the invention may advantageously be used as a hair product. It may in particular be used as a styling product, for example as a styling gel.
  • it is used as a non-rinsed styling product, that is to say for shaping and / or maintaining the hairstyle not followed by rinsing.
  • the present invention also relates to a cosmetic hair treatment method, for example a hair care method, or a method of shaping and / or maintaining the hairstyle, which consists in applying to the hair an effective amount of a hair. composition as described above, then to perform a possible rinsing after a possible exposure time.
  • a cosmetic hair treatment method for example a hair care method, or a method of shaping and / or maintaining the hairstyle, which consists in applying to the hair an effective amount of a hair. composition as described above, then to perform a possible rinsing after a possible exposure time.
  • the composition according to the invention is not rinsed.
  • This example illustrates the formulation of a styling gel according to the invention.
  • a styling gel has been prepared from the ingredients indicated in the table below:
  • This composition provides a very good fixation of the hair, both flexible and durable.
  • the fixing polymer film is very friable.
  • this composition has been found to provide the hair with excellent cosmetic properties. In particular, after disentangling, the hair is not dry, and is particularly soft.

Abstract

The invention relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one acrylic acid homopolymer and at least one acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer, the weight ratio between the amount of acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer and the amount of acrylic acid homopolymer being between 0.1 and 10. Said composition is especially used as a hairstyling product.

Description

Composition cosmétique comprenant un homopolymère d'acide acrylique et un copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), ainsi que son utilisation en tant que produit capillaire. Cosmetic composition comprising a homopolymer of acrylic acid and a copolymer of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), and its use as a hair product .
La présente invention est relative à une composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, au moins un homopolymère d'acide acrylique, et au moins un copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s).The present invention relates to a cosmetic composition comprising, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of acrylate hydroxyester (s) or methacrylate (s).
La présente invention concerne également un procédé de traitement cosmétique des cheveux mettant en œuvre la composition précitée, et une utilisation de cette composition cosmétique en tant que produit capillaire, par exemple en tant que produit de coiffage. Les produits de coiffage sont habituellement utilisés pour construire, structurer la coiffure et lui apporter une tenue durable. Les compositions correspondantes comprennent généralement un ou plusieurs polymères filmogènes, dans un milieu cosmétiquement acceptable. Ces polymères permettent la formation d'un film gainant sur les cheveux, assurant ainsi le maintien de la coiffure.The present invention also relates to a cosmetic hair treatment method using the aforementioned composition, and a use of this cosmetic composition as a hair product, for example as a styling product. Hair styling products are usually used to build, structure the hairstyle and give it a lasting hold. The corresponding compositions generally comprise one or more film-forming polymers in a cosmetically acceptable medium. These polymers allow the formation of a sheathing film on the hair, thus ensuring the maintenance of the hairstyle.
Toutefois, les films de polymère fixant ainsi formés présentent l'inconvénient d'être relativement friables, ce qui limite dans le temps la tenue de la coiffure, et engendre la formation sur les cheveux de résidus inesthétiques. Pour diminuer ces problèmes de friabilité, il est connu d'incorporer dans les produits de coiffage à base de polymères filmogènes un agent plastifiant. Ceci permet effectivement d'améliorer la tenue de la coiffure dans le temps et de limiter la formation de résidus au cours de la journée. Cependant, malgré l'ajout d'un tel agent plastifiant, la non friabilité des films de polymères est généralement liée à la concentration en polymère fixant dans le produit de coiffage (ou degré de fixation) : si l'on diminue la concentration en polymère fixant pour diminuer la rigidité de la coiffure, alors le film de polymère devient plus friable et la tenue de la coiffure est moins bonne.However, the fixing polymer films thus formed have the disadvantage of being relatively friable, which limits in time the holding of the hairstyle, and causes the formation on the hair of unsightly residues. To reduce these problems of friability, it is known to incorporate in the styling products based on film-forming polymers a plasticizer. This effectively improves the behavior of the hairstyle over time and limit the formation of residues during the day. However, despite the addition of such a plasticizer, the non-friability of the polymer films is generally related to the fixing polymer concentration in the styling product (or degree of fixation): if the polymer concentration is decreased fixing for reduce the rigidity of the hairstyle, then the polymer film becomes more friable and the behavior of the hairstyle is less good.
Il existe donc un besoin pour des compositions capillaires permettant d'obtenir un maintien durable de la coiffure, et ce quel que soit le degré de fixation.There is therefore a need for hair compositions that make it possible to obtain a lasting hold of the hairstyle, whatever the degree of fixation.
La Demanderesse a maintenant découvert que, de manière surprenante, l'association d'un polymère fixant particulier, du type (méth)acrylate(s) / hydroxyester de (méth)acrylate(s) avec un polymère épaississant à base d'acide acrylique, selon un rapport pondéral spécifique entre les quantités de ces deux polymères, permettait d'obtenir une composition capillaire apportant des propriétés de coiffage améliorées. Notamment, une telle association permet d'obtenir des produits de coiffage procurant une gamme de fixations souples à ultra-fortes, avec un film de polymère extrêmement peu friable, quel que soit le degré de fixation. Il devient ainsi possible de formuler des produits à fixation flexible longue durée.The Applicant has now discovered that, surprisingly, the combination of a particular fixing polymer, of the (meth) acrylate (s) / hydroxyester type of (meth) acrylate (s) with a thickening polymer based on acrylic acid , in a specific weight ratio between the amounts of these two polymers, allowed to obtain a hair composition providing improved styling properties. In particular, such an association makes it possible to obtain hair styling products providing a range of flexible to ultra-strong bindings, with an extremely low-friable polymer film, whatever the degree of fixation. It thus becomes possible to formulate long-lasting flexible fastening products.
La présente invention permet en particulier de préparer des produits de coiffage procurant une durabilité de la coiffure nettement améliorée, y compris dans des produits à fixation souple, c'est-à-dire à faible concentration en polymère fixant.The present invention makes it possible in particular to prepare hair styling products that provide significantly improved hairstyling durability, including in products with flexible fixation, that is to say with a low concentration of fixing polymer.
Par ailleurs, et de manière tout à fait inattendue, les compositions selon l'invention se sont avérées procurer une très nette amélioration des propriétés cosmétiques des cheveux après démêlage : les cheveux sont beaucoup plus doux et moins secs qu'après l'application d'un produit de fixation classique.Moreover, and quite unexpectedly, the compositions according to the invention have been found to provide a very marked improvement in the cosmetic properties of the hair after disentangling: the hair is much softer and less dry than after the application of a conventional fixing product.
La présente invention a donc pour objet une composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, au moins un homopolymère d'acide acrylique, et au moins un copolymère d'acrylate(s) ou de méthacrylate(s)et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), caractérisée en ce que le rapport pondéral entre la quantité de copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) d'une part et la quantité d'homopolymère d'acide acrylique d'autre part est compris entre 0, 1 et 10. Un autre objet de l'invention consiste en un procédé de traitement cosmétique des cheveux mettant en œuvre une composition selon l'invention telle que décrite ci-dessous. L'invention a encore pour objet l'utilisation de la composition selon l'invention pour le traitement cosmétique des cheveux, en particulier pour la mise en forme et/ou le maintien de la coiffure.The subject of the present invention is therefore a cosmetic composition comprising, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), characterized in that the weight ratio between the amount of copolymer of acrylate (s) or methacrylate (s) and of acrylate (s) or methacrylate hydroxyester (s) ) on the one hand and the amount of acrylic acid homopolymer on the other hand is between 0, 1 and 10. Another subject of the invention consists of a cosmetic hair treatment method using a composition according to the invention as described below. The subject of the invention is also the use of the composition according to the invention for the cosmetic treatment of the hair, in particular for shaping and / or maintaining the hairstyle.
D'autres objets, caractéristiques, aspects et avantages de l'invention apparaîtront encore plus clairement à la lecture de la description et de l'exemple qui suivent.Other objects, features, aspects and advantages of the invention will emerge even more clearly on reading the following description and example.
Selon l'invention, la composition cosmétique comprend, dans un milieu cosmétiquement acceptable, au moins un homopolymère d'acide acrylique, et au moins un copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s). Par "milieu cosmétiquement acceptable", on entend un milieu compatible avec les matières kératiniques et en particulier les cheveux.According to the invention, the cosmetic composition comprises, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of acrylate hydroxyester ( s) or methacrylate (s). By "cosmetically acceptable medium" is meant a medium compatible with keratin materials and in particular the hair.
De préférence, le milieu cosmétiquement acceptable comprend de l'eau et/ou au moins un solvant cosmétiquement acceptable choisi parmi les alcools inférieurs en C1-C4, tels que l'éthanol, l'isopropanol, le tertio-butanol ou le n-butanol ; les polyols comme le propylèneglycol ; les éthers de polyols ; les alcanes en C5-C10 ; les cétones en C3 -4 comme l'acétone et la méthyléthylcétone ; les acétates d'alkyle en C1-C4 comme l'acétate de méthyle, l'acétate d'éthyle et l'acétate de butyle ; le diméthoxyéthane, le diéthoxyéthane ; et leurs mélanges.Preferably, the cosmetically acceptable medium comprises water and / or at least one cosmetically acceptable solvent chosen from C 1 -C 4 lower alcohols, such as ethanol, isopropanol, tert-butanol or n-butanol. -butanol; polyols such as propylene glycol; polyol ethers; C 5 -C 10 alkanes; C 3 -4 ketones such as acetone and methyl ethyl ketone; C 1 -C 4 alkyl acetates such as methyl acetate, ethyl acetate and butyl acetate; dimethoxyethane, diethoxyethane; and their mixtures.
La composition selon l'invention comprend au moins un copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), c'est-à-dire un copolymère obtenu par copolymérisation d'au moins deux monomères :The composition according to the invention comprises at least one copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), that is to say a copolymer obtained by copolymerization of at least two monomers:
- au moins un premier monomère choisi parmi l'acide acrylique, l'acide méthacrylique, les acrylates et méthacrylates d'alkyle en C l à C4, et - au moins un second monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en C l à C4.at least one first monomer chosen from acrylic acid, methacrylic acid, C 1 to C 4 alkyl acrylates and methacrylates, and at least one second monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.
De préférence, ledit copolymère est obtenu par copolymérisation d'au moins trois monomères : - au moins un premier monomère choisi parmi l'acide acrylique et l'acide méthacrylique,Preferably, said copolymer is obtained by copolymerization of at least three monomers: at least one first monomer chosen from acrylic acid and methacrylic acid,
- au moins un deuxième monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, etat least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and
- au moins un troisième monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en C l à C4.at least one third monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.
De préférence, ledit deuxième monomère comprend au moins un acrylate ou méthacrylate d'alkyle en Cl ou C2. En d'autres termes, ledit deuxième monomère peut alors être l'acrylate de méthyle, l'acrylate d'éthyle, le méthacrylate de méthyle, le méthacrylate d'éthyle, et les mélanges de ces composés.Preferably, said second monomer comprises at least one C 1 or C 2 alkyl acrylate or methacrylate. In other words, said second monomer can then be methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, and mixtures of these compounds.
De préférence, ledit troisième monomère est choisi parmi l'acrylate d'hydroxyéthyle, le méthacrylate d'hydroxyéthyle, et les mélanges de ces composés.Preferably, said third monomer is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, and mixtures of these compounds.
Selon un mode de réalisation préféré, la composition selon l'invention comprend un mélange d'au moins deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) tels que décrits ci-avant.According to a preferred embodiment, the composition according to the invention comprises a mixture of at least two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) as described above.
Il peut s'agir d'un mélange d'au moins deux copolymères à au moins deux monomères tels que décrits ci-avant, d'un mélange d'au moins deux copolymères à au moins trois monomères tels que décrits ci-avant, ou d'un mélange d'au moins un copolymère à au moins deux monomère et d'au moins un copolymère à au moins trois monomères tels que décrits ci-avant.It may be a mixture of at least two copolymers with at least two monomers as described above, a mixture of at least two copolymers with at least three monomers as described above, or a mixture of at least one copolymer with at least two monomers and at least one copolymer with at least three monomers as described above.
Dans une première variante de ce mode de réalisation préféré, la composition selon l'invention comprend un mélange de deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), chacun des copolymères étant obtenu par copolymérisation d'au moins trois monomères tels que décrits ci-avant, à savoir : - au moins un premier monomère choisi parmi l'acide acrylique et l'acide méthacrylique,In a first variant of this preferred embodiment, the composition according to the invention comprises a mixture of two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s). ), each of the copolymers being obtained by copolymerization of at least three monomers as described above, namely: at least one first monomer chosen from acrylic acid and methacrylic acid,
- au moins un deuxième monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, et - au moins un troisième monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en C l à C4.at least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and at least one third monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.
Dans une deuxième variante de ce mode de réalisation préféré, la composition selon l'invention comprend un mélange de deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), comprenant un premier copolymère obtenu par copolymérisation d'au moins trois monomères tels que décrits ci-avant: au moins un premier monomère choisi parmi l'acide acrylique et l'acide méthacrylique, - au moins un deuxième monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, etIn a second variant of this preferred embodiment, the composition according to the invention comprises a mixture of two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s). ), comprising a first copolymer obtained by copolymerization of at least three monomers as described above: at least one first monomer chosen from acrylic acid and methacrylic acid, - at least one second monomer chosen from acrylates and C1 to C4 alkyl methacrylates, and
- au moins un troisième monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en Cl à C4 ; et un second copolymère obtenu par copolymérisation d'au moins deux monomères : au moins un premier monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, et au moins un second monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en Cl à C4 ; ledit second copolymère ne contenant pas de monomères constitués d'acides carboxyliques insaturés.at least one third monomer chosen from C1 to C4 hydroxyalkyl acrylates and methacrylates; and a second copolymer obtained by copolymerization of at least two monomers: at least one first monomer chosen from C1-C4 alkyl acrylates and methacrylates, and at least one second monomer chosen from C1-hydroxyalkyl acrylates and methacrylates; at C4; said second copolymer does not contain monomers consisting of unsaturated carboxylic acids.
Lorsque la composition selon l'invention comprend un mélange d'au moins deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), les deux copolymères de ce mélange possèdent de préférence des températures de transition vitreuses différentes.When the composition according to the invention comprises a mixture of at least two copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), the two copolymers of this The mixture preferably has different glass transition temperatures.
La température de transition vitreuse (Tg) est mesurée par analyse enthalpique différentielle (ou DSC, Differential Scanning Calorimetry) selon la norme ASTM D3418-97. Un des deux copolymères a de préférence une Tg allant de 35°c à 250°C, plus préférentiellement de 40°C à 150°C et encore plus préférentiellement de 75°C à 100°C. Le second copolymère a de préférence une Tg allant de -20°C à 35°C, plus préférentiellement de 0°C à 35°C et encore plus préférentiellement de 15°C à 30°C.The glass transition temperature (Tg) is measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418-97. One of the two copolymers preferably has a Tg ranging from 35 ° C. to 250 ° C., more preferably from 40 ° C. to 150 ° C. and even more preferentially from 75 ° C. to 100 ° C. The second copolymer preferably has a Tg ranging from -20 ° C to 35 ° C, more preferably from 0 ° C to 35 ° C and even more preferably from 15 ° C to 30 ° C.
L'écart de Tg entre les deux copolymères est de préférence supérieur ou égal à 10°C, plus préférentiellement supérieur ou égal à 20°C et encore plus préférentiellement supérieur ou égal à 30°C.The difference of Tg between the two copolymers is preferably greater than or equal to 10 ° C, more preferably greater than or equal to 20 ° C and even more preferably greater than or equal to 30 ° C.
Le(les) copolymère(s) d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) utilisable(s) dans les compositions selon l'invention peut(peuvent) être un (des) copolymère(s) de type bloc, statistique ou alterné. De préférence, c'est un copolymère statistique.The copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s) usable (s) in the compositions according to the invention can (can) ) be a block copolymer (s), statistical or alternating. Preferably, it is a random copolymer.
Avantageusement, le copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) est un copolymère anionique.Advantageously, the copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) is an anionic copolymer.
Plus avantageusement, il comporte des séquences dures et des séquences molles, c'est-à-dire des séquences avec deux températures de transitions vitreuses (Tg) propres, l'une des Tg étant comprise entre 15 et 35°C, de préférence entre 20 et 30°C, l'autre Tg étant comprise entre 90 et 1 10°C, de préférence entre 95 et 105°C.More preferably, it comprises hard sequences and soft sequences, that is to say sequences with two glass transition temperatures (Tg), one of the Tg being between 15 and 35 ° C, preferably between 20 and 30 ° C, the other Tg being between 90 and 1 10 ° C, preferably between 95 and 105 ° C.
Avantageusement, la séquence dure comprend au moins un monomère choisi parmi le méthacrylate de méthyle, l'acrylate de butyle, le méthacrylate d'hydroxyéthyle , l'acide méthacrylique, et plus avantageusement, la séquence dure comprend tous ces monomères.Advantageously, the hard sequence comprises at least one monomer chosen from methyl methacrylate, butyl acrylate, hydroxyethyl methacrylate and methacrylic acid, and more advantageously, the hard sequence comprises all these monomers.
Avantageusement, la séquence molle comprend au moins un monomère choisi parmi l'acrylate d'éthyle, l'acrylate de butyle, le méthacrylate d'hydroxyéthyle, l'acide méthacrylique et plus avantageusement, la séquence molle comprend tous ces monomères.Advantageously, the soft sequence comprises at least one monomer selected from ethyl acrylate, butyl acrylate, hydroxyethyl methacrylate, methacrylic acid and more preferably, the soft sequence comprises all these monomers.
De préférence, le poids moléculaire de ce copolymère est compris entre 10 000 g/mol et 200 000 g/mol. Encore plus préférentiellement il est compris entre 20 000 g/mol et 100 000 g/mol. Les copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) peuvent se présenter sous des formes très diverses, par exemple sous forme de solutions ou d'émulsions dans l'eau ou dans tout autre solvant. Ils peuvent être synthétisés par toute méthode connue de préparation d'un copolymère à partir de ses différents monomères.Preferably, the molecular weight of this copolymer is between 10,000 g / mol and 200,000 g / mol. Even more preferentially, it is between 20,000 g / mol and 100,000 g / mol. The copolymers of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s) can be in a wide variety of forms, for example in the form of solutions or emulsions in water or any other solvent. They can be synthesized by any known method for preparing a copolymer from its different monomers.
A titre d'exemple de copolymères et mélanges de copolymères utilisables dans les compositions selon l'invention, citons entre autres les produits commercialisés sous la dénomination ACUDYNE par la société ROHM & HAAS, tels que par exemple, et de manière non limitative, les produits proposés sous la dénomination ACUDYNE DHR, ACUDYNE 258, ACUDYNE 180.By way of example of copolymers and copolymer mixtures that may be used in the compositions according to the invention, mention may be made, inter alia, of the products sold under the name Acudyne by the company Rohm & Haas, such as, for example, and in a nonlimiting manner, the products proposed under the name ACUDYNE DHR, ACUDYNE 258, ACUDYNE 180.
La composition selon l'invention contient de préférence au moins 0,01 % en poids de copolymère(s) d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), par rapport au poids total de la composition. De préférence, elle contient de 0,01 à 20 % en poids de copolymère(s) d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), encore plus préférentiellement de 0, 1 à 10% en poids, mieux encore de 0,5 à 8 % en poids, par rapport au poids total de la composition.The composition according to the invention preferably contains at least 0.01% by weight of copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s) , relative to the total weight of the composition. Preferably, it contains from 0.01% to 20% by weight of copolymer (s) of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or methacrylate (s), and even more preferably from 0.1 to 10% by weight, more preferably from 0.5 to 8% by weight, relative to the total weight of the composition.
La composition selon l'invention comprend également au moins un homopolymère d'acide acrylique.The composition according to the invention also comprises at least one homopolymer of acrylic acid.
Un tel polymère peut être réticulé, ou non réticulé.Such a polymer may be crosslinked or uncrosslinked.
De préférence Fhomopolymère d'acide acrylique est réticulé. Il peut être réticulé en tout ou partie, par exemple avec un éther d'allyle.Preferably the homopolymer of acrylic acid is crosslinked. It may be crosslinked in whole or part, for example with an allyl ether.
Il peut s'agir par exemple d'un homopolymère d'acide acrylique réticulé avec un éther d'allyle et de pentaérythritol, avec un éther d'allyle et de sucrose, ou avec un éther d'allyle et de propylène. De tels polymères sont notamment classés sous la dénomination Carbomer dans le dans le dictionnaire CTFA, 10ème édition, 2004. Ils sont entre autres commercialisés sous la dénomination CARBOPOL par la société NOVEON.It may be, for example, a homopolymer of acrylic acid crosslinked with an allyl ether and pentaerythritol, with an allyl ether and sucrose, or with an allyl ether and propylene ether. Such polymers are in particular classified under the name Carbomer in the CTFA dictionary, 10 th edition, 2004. They are among others marketed under the name CARBOPOL by NOVEON.
Le poids moléculaire des homopolymères d'acide acrylique selon l'invention est de préférence supérieur ou égal à 100 000 g/mol. Encore plus préférentiellement il est supérieur ou égal à 500 000 g/mol et de manière préférée supérieur ou égal à 1 000 000 g/mol. Il est tout particulièrement compris entre 1 000 000 g/mol et 10 000 000 g/mol.The molecular weight of the acrylic acid homopolymers according to the invention is preferably greater than or equal to 100,000 g / mol. Even more preferably it is greater than or equal to 500 000 g / mol and preferably greater than or equal to 1 000 000 g / mol. It is especially between 1,000,000 g / mol and 10,000,000 g / mol.
La composition selon l'invention contient de préférence au moins 0,01 % en poids d'homopolymère d'acide acrylique, par rapport au poids total de la composition. De préférence, elle contient de 0,01 à 10 % en poids d'un tel homopolymère, encore plus préférentiellement de 0,05 à 5% en poids, mieux encore de 0, 1 à 3 % en poids, par rapport au poids total de la composition. Le rapport pondéral entre la quantité de copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) d'une part et la quantité d'homopolymère d'acide acrylique d'autre part, est compris entre 0, 1 et 10, et de préférence entre 1 et 8. Les compositions selon l'invention peuvent également contenir au moins un corps gras. Les corps gras utilisables dans la présente invention sont notamment choisis parmi les huiles végétales, les huiles animales, les huiles minérales, les huiles naturelles ou synthétiques, les alcools gras, les cires et leurs mélanges. Comme huile végétale, on peut notamment mentionner l'huile d'amande douce, l'huile d'avocat, l'huile de ricin, l'huile d'olive, la cire liquide de jojoba, l'huile de tournesol, l'huile de germes de blé, l'huile de sésame, l'huile d'arachide, l'huile de pépins de raisin, l'huile de soja, l'huile de colza, l'huile de carthame, l'huile de coprah, l'huile de maïs, l'huile de noisette, l'huile de palme, l'huile de noyau d'abricot, l'huile de calophyllum, l'huile d'onagre, le beurre de karité, l'huile de son de riz, l'huile de germes de maïs, l'huile de passiflore et l'huile de seigle.The composition according to the invention preferably contains at least 0.01% by weight of acrylic acid homopolymer, relative to the total weight of the composition. Preferably, it contains from 0.01 to 10% by weight of such a homopolymer, more preferably from 0.05 to 5% by weight, more preferably from 0.1 to 3% by weight, relative to the total weight. of the composition. The weight ratio between the amount of acrylate (s) or methacrylate (s) copolymer and acrylate (s) or methacrylate hydroxyester (s) on the one hand and the amount of acrylic acid homopolymer on the other hand, is between 0, 1 and 10, and preferably between 1 and 8. The compositions according to the invention may also contain at least one fatty substance. The fatty substances that can be used in the present invention are chosen in particular from vegetable oils, animal oils, mineral oils, natural or synthetic oils, fatty alcohols, waxes and their mixtures. As vegetable oil, there may be mentioned sweet almond oil, avocado oil, castor oil, olive oil, liquid jojoba wax, sunflower oil, wheat germ oil, sesame oil, peanut oil, grape seed oil, soybean oil, rapeseed oil, safflower oil, coconut oil , corn oil, hazelnut oil, palm oil, apricot kernel oil, calophyllum oil, evening primrose oil, shea butter, rice bran, corn germ oil, passionflower oil and rye oil.
Comme huile animale, on peut notamment citer le perhydrosqualène.As animal oil, there may be mentioned perhydrosqualene.
Comme huile minérale, on peut notamment citer l'huile de paraffine et l'huile de vaseline. Comme huile synthétique, on peut notamment citer le squalane, les poly(α-oléfines) comme l'isododécane ou l'isohexadécane, les huiles végétales transestérifiées et les huiles fluorées, les esters gras.As mineral oil, mention may be made of paraffin oil and liquid petroleum jelly. As synthetic oil, there may be mentioned squalane, poly (α-olefins) such as isododecane or isohexadecane, transesterified vegetable oils and fluorinated oils, fatty esters.
Par esters gras, on désigne les composés de formule R8COORb dans laquelle Ra représente le reste d'un acide supérieur linéaire ou ramifié, hydroxylé ou non, saturé ou non, comportant de 4 à 29 atomes de carbone et Rb représente une chaîne hydrocarbonée linéaire ou ramifiée, saturée ou non contenant de 3 à 30 atomes de carbone, le nombre total d'atomes de carbone de l'ester étant supérieur à 10. A titre d'exemples, on peut notamment citer l'huile de PurcellinThe term "fatty esters" denotes compounds of formula R 8 COORb in which R a represents the residue of a linear or branched, hydroxylated or unsaturated, saturated or unsaturated higher acid containing from 4 to 29 carbon atoms and Rb represents a chain linear or branched hydrocarbon-based hydrocarbon, saturated or unsaturated, containing from 3 to 30 carbon atoms, the total number of carbon atoms of the ester being greater than 10. By way of examples, mention may especially be made of Purcellin oil
(octanoate de stéaryle), le myristate d'isopropyle, le palmitate d'isopropyle, le stéarate de butyle, le laurate d'hexyle, l'isononanoate d'isononyle, le palmitate de 2-éthylhexyle, le laurate de 2-hexyldécyle, le palmitate de 2-octyldécyle, le myristate de 2-octyldodécyle, le néopentanoate d'isostéaryle ou le néopentanoate de tridécyle.(stearyl octanoate), isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, isostearyl neopentanoate or tridecyl neopentanoate.
Les alcools gras préférés comprennent les alcools myristylique, cétylique, stéarylique, arachidylique, béhénylique et érucylique.Preferred fatty alcohols include myristyl, cetyl, stearyl, arachidyl, behenyl and erucyl alcohols.
Une cire, au sens de la présente invention, est un composé lipophile, solide à température ambiante (environ 25 °C), à changement d'état solide/liquide réversible, ayant une température de fusion supérieure à environ 40°C et pouvant aller jusqu'à 200°C, et présentant à l'état solide une organisation cristalline anisotrope. Les cires animales et végétales comprennent comme constituants essentiels des esters d'acides carboxyliques et d'alcools à longues chaînes. D'une manière générale, la taille des cristaux de la cire est telle que les cristaux diffractent et/ou diffusent la lumière, conférant à la composition qui les comprend un aspect trouble plus ou moins opaque. En portant la cire à sa température de fusion, il est possible de la rendre miscible aux huiles et de former un mélange homogène microscopiquement, mais en ramenant la température du mélange à la température ambiante, on obtient une recristallisation de la cire dans les huiles du mélange, détectable microscopiquement et macroscopiquement (opalescence). A titre de cires utilisables dans la présente invention, on peut citer les cires d'origine animale telles que la cire d'abeille, le spermaceti, la cire de lanoline et les dérivés de lanoline ; les cires végétales telles que les cires de tournesol, de riz, de pomme, la cire de Carnauba, de Candellila, d'Ouricury, du Japon, le beurre de cacao ou les cires de fibres de liège ou de canne à sucre ; les cires minérales, par exemple, de paraffine, de vaseline, de lignite ou les cires microcristallines, la cérésine ou l'ozokérite ; les cires synthétiques telles que les cires de polyéthylènes, les cires de Fischer-Tropsch, et leurs mélanges.A wax, within the meaning of the present invention, is a lipophilic compound, solid at room temperature (about 25 ° C.), with a reversible solid / liquid state change, having a melting temperature greater than about 40 ° C. and that can go up to 200 ° C, and having in the solid state an anisotropic crystalline organization. Animal and vegetable waxes comprise, as essential components, esters of carboxylic acids and long-chain alcohols. In general, the size of the crystals of the wax is such that the crystals diffract and / or diffuse the light, conferring on the composition which comprises them a more or less opaque cloudy appearance. By bringing the wax to its melting temperature, it is possible to render it miscible with oils and to form a homogeneous mixture microscopically, but by bringing the temperature of the mixture to room temperature, a recrystallization of the wax in the oils of the mixture, detectable microscopically and macroscopically (opalescence). As waxes that can be used in the present invention, mention may be made of waxes of animal origin, such as beeswax, spermaceti, lanolin wax and lanolin derivatives; vegetable waxes such as sunflower wax, rice wax, apple wax, Carnauba wax, Candelilla wax, Ouricury wax, Japan wax, cocoa butter wax or cork fiber wax or sugar cane wax; mineral waxes, for example paraffin, petrolatum, lignite or microcrystalline waxes, ceresin or ozokerite; synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes, and mixtures thereof.
Les corps gras tels que décrits ci-dessus, lorsqu'ils sont présents dans la composition selon l'invention, sont de préférence présents en une quantité allant de 0, 1 à 30 % en poids, de préférence de 1 à 20 % en poids, et mieux encore de 5 à 15% en poids, par rapport au poids total de la composition.The fatty substances as described above, when they are present in the composition according to the invention, are preferably present in an amount ranging from 0.1 to 30% by weight, preferably from 1 to 20% by weight. and more preferably from 5 to 15% by weight, based on the total weight of the composition.
La composition selon l'invention peut également comprendre au moins un tensioactif, choisi parmi les tensioactifs cationiques, les tensioactifs anioniques, les tensioactifs non ioniques, les tensioactifs amphotères ou zwittérioniques. La composition selon l'invention comprend alors de préférence au moins 0,01 % en poids de tensioactif(s), par rapport au poids total de la composition. De préférence, la composition selon l'invention contient de 0,01 à 20 % en poids de tensioactif(s), de manière plus préférée de 0,05 à 4 % en poids, par rapport au poids total de la composition.The composition according to the invention may also comprise at least one surfactant chosen from cationic surfactants, anionic surfactants, nonionic surfactants and amphoteric or zwitterionic surfactants. The composition according to the invention then preferably comprises at least 0.01% by weight of surfactant (s), relative to the total weight of the composition. Preferably, the composition according to the invention contains from 0.01 to 20% by weight of surfactant (s), more preferably from 0.05 to 4% by weight, relative to the total weight of the composition.
A titre d'exemple de tensioactifs anioniques utilisables dans les compositions selon la présente invention, on peut citer notamment (liste non limitative) les sels (en particulier sels alcalins, notamment de sodium, sels d'ammonium, sels d'aminés, sels d'aminoalcools ou sels d'alcalinoterreux (de magnésium)) des composés suivants : les alkylsulfates, les alkyléthersulfates, alkylamidoéthersulfates, alkylarylpolyéthersulfates, les monoglycérides sulfates ; les alkylsulfonates, les alkylphosphates, les alkylamidesulfonates, alkylarylsulfonates, les α-oléfine-sulfonates, lesparaffine-sulfonates ; les alkylsulfosuccinates ; les alkyléthersulfosuccinates, les alkylamidesulfosuccinates ; les alkylsulfosuccinamates ; les alkylsulfoacétates ; les alkylétherphosphates, les acylsarcosinates ; les acyliséthionates et les N-acyltaurates, le radical alkyle ou acyle de tous ces différents composés comportant de préférence de 12 à 20 atomes de carbone, et le radical aryle désignant de préférence un groupement phényle ou benzyle.By way of example of anionic surfactants that can be used in the compositions according to the present invention, mention may be made in particular (nonlimiting list) of the salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, sodium salts and the like). aminoalcohols or alkaline earth (magnesium) salts) of the following compounds: alkylsulfates, alkylethersulfates, alkylamidoethersulfates, alkylarylpolyethersulfates, monoglycerides sulfates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; alkylsulfosuccinates; alkyl ether sulfosuccinates, alkyl amide sulfosuccinates; alkylsulfosuccinamates; alkylsulfoacetates; alkyl ether phosphates, acylsarcosinates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group.
Parmi les tensioactifs anioniques encore utilisables, on peut également citer les sels d'acides gras tels que les sels acides oléique, ricinoléique, palmitique, stéarique ; les acides d'huile de coprah ou d'huile de coprah hydrogénée ; les acyl-lactylates dont le radical acyle comporte 8 à 20 atomes de carbone.Among the anionic surfactants that can still be used, mention may also be made of fatty acid salts such as the oleic, ricinoleic, palmitic and stearic acid salts; coconut oil or hydrogenated coconut oil acids; acyl lactylates whose acyl radical has 8 to 20 carbon atoms.
On peut également utiliser des tensioactifs faiblement anioniques, comme les acides d'alkyl D galactoside uroniques et leurs sels ainsi que les acides alkyl (C6 - C24) éther carboxyliques polyoxyalkylénés, les acides alkyl (C6-C24)aryl éther carboxyliques polyoxyalkylénés, les acides alkyl (C6-C24) amino éther carboxyliques polyoxyalkylénés et leurs sels, en particulier ceux comportant de 2 àIt is also possible to use weakly anionic surfactants, such as acid alkyl D galactoside uronic and salts thereof, polyoxyalkylenated (C 6 - C 24) ether carboxylic acids, polyoxyalkylenated (C 6 -C2 4) aryl ether carboxylic polyoxyalkylenated, polyoxyalkylenated (C 6 -C 24 ) alkyl ether carboxylic acids and their salts, in particular those containing from 2 to
50 groupements oxyde d'éthylène et leurs mélanges. Parmi les tensioactifs anioniques, on préfère utiliser selon l'invention les sels d'alkylsulfates et d'alkyléthersulfates et leurs mélanges.50 ethylene oxide groups and mixtures thereof. Among the anionic surfactants, it is preferred to use, according to the invention, the salts of alkyl sulphates and alkyl ether sulphates and their mixtures.
Les tensioactifs cationiques utilisables dans les compositions de la présente invention comprennent par exemple les sels d'aminés grasses primaires, secondaires ou tertiaires, éventuellement polyoxyalkylénées, les sels d'ammonium quaternaire, et leurs mélanges.The cationic surfactants that can be used in the compositions of the present invention comprise, for example, primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated salts, quaternary ammonium salts, and mixtures thereof.
A titre de sels d'ammonium quaternaire, on peut notamment citer, par exemple : - ceux répondant à la formule générale (I) suivante :
Figure imgf000013_0001
As quaternary ammonium salts, mention may be made, for example: - those corresponding to the following general formula (I):
Figure imgf000013_0001
dans laquelle les radicaux R8 à R11, qui peuvent être identiques ou différents, représentent un radical aliphatique, linéaire ou ramifié, comportant de 1 à 30 atomes de carbone, ou un radical aromatique tel que aryle ou alkylaryle. Les radicaux aliphatiques peuvent comporter des hétéroatomes tels que notamment l'oxygène, l'azote, le soufre et les halogènes. Les radicaux aliphatiques sont par exemple choisis parmi les radicaux alkyle en C1 -30, alcoxy en C1 -30, polyoxyalkylène (C2-C6), alkylamide en C1 -30, alkyl(C12-C22)amidoalkyle(C2-C6), alkyl(Ci2-in which the radicals R 8 to R 11 , which may be identical or different, represent a linear or branched aliphatic radical containing from 1 to 30 carbon atoms, or an aromatic radical such as aryl or alkylaryl. The aliphatic radicals may comprise heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens. The aliphatic radicals are for example chosen from alkyl C 1 -30 alkoxy, C 1 -30, polyoxy (C 2 -C 6) alkylamide C 1 -30, (C 1 2-C22) amidoalkyl ( C 2 -C 6) alkyl (Ci2-
C22)acétate, et hydroxyalkyle en C1 -30 ; X est un anion choisi dans le groupe des halogénures, phosphates, acétates, lactates, alkyl(C2- C6)sulfates, alkyl- ou alkylaryl-sulfonates.C22) acetate, and hydroxyalkyl C 1 -30 ; X is an anion selected from the group of halides, phosphates, acetates, lactates, (C 2 -C 6 ) alkyl sulfates, alkyl- or alkylarylsulfonates.
Parmi les sels d'ammonium quaternaire de formule (I), on préfère d'une part, les chlorures de tétraalkylammonium comme, par exemple, les chlorures de dialkyldiméthylammonium ou d'alkyltrimé- thylammonium dans lesquels le radical alkyle comporte environ de 12 à 22 atomes de carbone, en particulier les chlorures de béhényltriméthyl- ammonium, de distéaryldiméthylammonium, de cétyltriméthylammo- nium, de benzyldiméthylstéarylammonium ou encore, d'autre part, le chlorure de palmitylamidopropyltriméthylammonium ou le chlorure de stéaramidopropyldiméthyl-(myristyl acétate)-ammonium commercialisé sous la dénomination CERAPHYL® 70 par la société VAN DYK.Of the quaternary ammonium salts of formula (I), tetraalkylammonium chlorides, such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical has from about 12 to 22, are preferred. carbon atoms, in particular behenyltrimethylammonium, distearyl dimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides or else palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl (myristylacetate) ammonium chloride sold under the CERAPHYL ® 70 denomination by the company VAN DYK.
- les sels d'ammonium quaternaire de Fimidazoline, comme par exemple ceux de formule (II) suivante :the quaternary ammonium salts of imidazoline, for example those of formula (II) below:
Figure imgf000013_0002
dans laquelle R12 représente un radical alcényle ou alkyle comportant de 8 à 30 atomes de carbone, par exemple dérivés des acides gras du suif, R13 représente un atome d'hydrogène, un radical alkyle en C1-C4 ou un radical alcényle ou alkyle comportant de 8 à 30 atomes de carbone, R14 représente un radical alkyle en C1-C4, R15 représente un atome d'hydrogène, un radical alkyle en C1-C4, X" est un anion choisi dans le groupe des halogénures, phosphates, acétates, lactates, alkylsulfates, alkyl- ou alkylaryl-sulfonates. De préférence, R12 et R13 désignent un mélange de radicaux alcényle ou alkyle comportant de 12 à 21 atomes de carbone, par exemple dérivés des acides gras du suif, R14 désigne un radical méthyle, R15 désigne un atome d'hydrogène. Un tel produit est par exemple commercialisé sous la dénomination REWOQUAT® W 75 par la société REWO ;
Figure imgf000013_0002
in which R 12 represents an alkenyl or alkyl radical containing from 8 to 30 carbon atoms, for example derived from tallow fatty acids, R 13 represents a hydrogen atom, a C 1 -C 4 alkyl radical or an alkenyl radical; or alkyl having from 8 to 30 carbon atoms, R 14 represents a C 1 -C 4 alkyl radical, R 15 represents a hydrogen atom, a C 1 -C 4 alkyl radical, X " is an anion selected from the group of halides, phosphates, acetates, lactates, alkyl sulphates, alkyl or alkylaryl sulphonates, R 12 and R 13 preferably denote a mixture of alkenyl or alkyl radicals containing from 12 to 21 carbon atoms, for example acid derivatives. . fatty tallow, R 14 denotes a methyl radical, R 15 denotes a hydrogen atom such a product is for example sold under the name Rewoquat ® W 75 by Rewo;
- les sels de diammonium quaternaire de formule (III) :the quaternary diammonium salts of formula (III):
R17 R19 R 17 R 19
R16 -N-(CH2)3-N-R21 2X- (III)R 16 -N- (CH 2 ) 3 -NR 21 2X- (III)
R 18 R 20R 18 R 20
dans laquelle R16 désigne un radical aliphatique comportant environ de 16 à 30 atomes de carbone ; R17, R18, R1^ R20 et R21, identiques ou différents sont choisis parmi un atome d'hydrogène et un radical alkyle comportant de 1 à 4 atomes de carbone ; et X est un anion choisi dans le groupe des halogénures, acétates, phosphates, nitrates et méthylsulfates.wherein R 16 is an aliphatic radical having about 16 to 30 carbon atoms; R 17 , R 18 , R 1, R 20 and R 21 , which are identical or different, are chosen from a hydrogen atom and an alkyl radical containing from 1 to 4 carbon atoms; and X is an anion selected from the group of halides, acetates, phosphates, nitrates and methylsulfates.
De tels sels de diammonium quaternaire comprennent notamment le dichlorure de propanesuif diammonium ;Such diammonium quaternary salts include in particular propane dichloride diammonium;
- les sels d'ammonium quaternaire contenant au moins une fonction ester, tels que ceux de formule (IV) suivante :
Figure imgf000015_0001
the quaternary ammonium salts containing at least one ester function, such as those of formula (IV) below:
Figure imgf000015_0001
dans laquelle :in which :
R22 est choisi parmi les radicaux alkyles en C1-C6 et les radicaux hydroxyalkyles ou dihydroxyalkyles en C1 -C6 ;R22 is selected from alkyl C 1 -C 6 hydroxyalkyl or dihydroxyalkyl radicals C 1 -C 6 alkyl;
R23 est choisi parmi :R 23 is chosen from:
OO
IIII
- le radical R26 — C —the radical R 26 - C -
- les radicaux R27 hydrocarbonés en C1-C22, linéaires ou ramifiés, saturés ou insaturés, - l'atome d'hydrogène,- R 27 hydrocarbon radicals in C 1 -C 22 linear or branched, saturated or unsaturated, - the hydrogen atom,
R25 est choisi parmi :R 25 is selected from:
OO
IIII
- le radical R28 — C —the radical R 28 - C -
- les radicaux R29 hydrocarbonés en C1-C6, linéaires ou ramifiés, saturés ou insaturés, - l'atome d'hydrogène,- the radicals R2 9 hydrocarbon C 1 -C 6 linear or branched, saturated or unsaturated, - the hydrogen atom,
R24, R26 et R28, identiques ou différents, sont choisis parmi les radicaux hydrocarbonés en C7-C21, linéaires ou ramifiés, saturés ou insaturés ; r, s et t, identiques ou différents, sont des entiers valant de 2 à 6 ; y est un entier valant de 1 à 10 ; x et z, identiques ou différents, sont des entiers valant de 0 à 10 ;R24, R2 6 and R 28 , which are identical or different, are chosen from linear or branched, saturated or unsaturated C 7 -C 21 hydrocarbon radicals; r, s and t, identical or different, are integers ranging from 2 to 6; y is an integer from 1 to 10; x and z, which are identical or different, are integers ranging from 0 to 10;
X" est un anion simple ou complexe, organique ou inorganique ; sous réserve que la somme x + y + z vaut de 1 à 15, que lorsque x vaut 0 alors R23 désigne R27 et que lorsque z vaut 0 alors R25 désigne R29.X " is a simple or complex anion, organic or inorganic, provided that the sum x + y + z is from 1 to 15, that when x is 0, then R 23 denotes R 27 and that when z is 0, then R 25 denotes R29.
Les radicaux alkyles R22 peuvent être linéaires ou ramifiés et plus particulièrement linéaires.The alkyl radicals R 22 may be linear or branched and more particularly linear.
De préférence R22 désigne un radical méthyle, éthyle, hydroxyéthyle ou dihydroxypropyle, et plus particulièrement un radical méthyle ou éthyle. Avantageusement, la somme x + y + z vaut de 1 à 10.Preferably R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical, and more particularly a methyl or ethyl radical. Advantageously, the sum x + y + z is from 1 to 10.
Lorsque R23 est un radical R27 hydrocarboné, il peut être long et avoir de 12 à 22 atomes de carbone, ou court et avoir de 1 à 3 atomes de carbone. Lorsque R25 est un radical R29 hydrocarboné, il a de préférence 1 à 3 atomes de carbone.When R 23 is a hydrocarbon radical R 27 , it may be long and have from 12 to 22 carbon atoms, or short and have from 1 to 3 carbon atoms. When R 25 is a hydrocarbon radical R 29 , it preferably has 1 to 3 carbon atoms.
Avantageusement, R24, R26 et R28, identiques ou différents, sont choisis parmi les radicaux hydrocarbonés en C11-C21, linéaires ou ramifiés, saturés ou insaturés, et plus particulièrement parmi les radicaux alkyle et alcényle en C11-C21, linéaires ou ramifiés, saturés ou insaturés.Advantageously, R 24 , R 26 and R 28 , which are identical or different, are chosen from linear or branched, saturated or unsaturated C 11 -C 21 hydrocarbon radicals, and more particularly from C 11 -C 11 alkyl and alkenyl radicals. 21 , linear or branched, saturated or unsaturated.
De préférence, x et z, identiques ou différents, valent 0 ou 1.Preferably, x and z, identical or different, are 0 or 1.
Avantageusement, y est égal à 1.Advantageously, y is 1.
De préférence, r, s et t, identiques ou différents, valent 2 ou 3, et encore plus particulièrement sont égaux à 2.Preferably, r, s and t, which are identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
L'anion est de préférence un halogénure (chlorure, bromure ou iodure) ou un alkylsulfate plus particulièrement méthylsulfate. On peut cependant utiliser le méthanesulfonate, le phosphate, le nitrate, le tosylate, un anion dérivé d'acide organique tel que l'acétate ou le lactate ou tout autre anion compatible avec l'ammonium à fonction ester.The anion is preferably a halide (chloride, bromide or iodide) or an alkyl sulphate more particularly methyl sulphate. However, it is possible to use methanesulphonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.
L'anion X" est encore plus particulièrement le chlorure ou le méthylsulfate.The anion X - is even more particularly chloride or methylsulfate.
On utilise plus particulièrement dans la composition selon l'invention, les sels d'ammonium de formule (IV) dans laquelle : - R22 désigne un radical méthyle ou éthyle,In the composition according to the invention, the ammonium salts of formula (IV) are used more particularly in which: R 22 denotes a methyl or ethyl radical,
- x et y sont égaux à 1 ;- x and y are equal to 1;
- z est égal à 0 ou 1 ;z is 0 or 1;
- r, s et t sont égaux à 2 ;r, s and t are equal to 2;
- R23 est choisi parmi :R 23 is chosen from:
OO
IIII
- le radical R76 — C — 26 the radical R 76 - C - 26
- les radicaux méthyle, éthyle ou hydrocarbonés en C14-C22,methyl, ethyl or C 14 -C 22 hydrocarbon radicals,
- l'atome d'hydrogène ; - R25 est choisi parmi :- the hydrogen atom; R 25 is chosen from:
OO
- le radical R28 — C —the radical R 28 - C -
- l'atome d'hydrogène ;- the hydrogen atom;
- R24, R26 et R28, identiques ou différents, sont choisis parmi les radicaux hydrocarbonés en C13-C17, linéaires ou ramifiés, saturés ou insaturés, et de préférence parmi les radicaux alkyles et alcényles en C13-C17, linéaires ou ramifiés, saturés ou insaturés.R 24 , R 26 and R 28 , which are identical or different, are chosen from linear or branched, saturated or unsaturated C 13 -C 17 hydrocarbon radicals, and preferably from C 13 -C 17 alkyl and alkenyl radicals; , linear or branched, saturated or unsaturated.
Avantageusement, les radicaux hydrocarbonés sont linéaires.Advantageously, the hydrocarbon radicals are linear.
On peut citer par exemple les composés de formule (IV) tels que les sels (chlorure ou méthylsulfate notamment) de diacyloxyéthyl-dimé- thylammonium, de diacyloxyéthyl-hydroxyéthyl-méthylammonium, de monoacyloxyéthyl-dihydroxyéthyl-méthylammonium, de triacyloxy- éthyl-méthylammonium, de monoacyloxyéthyl-hydroxyéthyl-diméthyl- ammonium et leurs mélanges. Les radicaux acyles ont de préférence 14 à 18 atomes de carbone et proviennent plus particulièrement d'une huile végétale comme l'huile de palme ou de tournesol. Lorsque le composé contient plusieurs radicaux acyles, ces derniers peuvent être identiques ou différents.There may be mentioned, for example, the compounds of formula (IV) such as the salts (especially chloride or methylsulfate) of diacyloxyethyl-dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, of monoacyloxyethyl-hydroxyethyl-dimethylammonium and mixtures thereof. The acyl radicals preferably have from 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm oil or sunflower oil. When the compound contains more than one acyl radical, the latter may be identical or different.
Ces produits sont obtenus, par exemple, par estérification directe de la triéthanolamine, de la triisopropanolamine, d'alkyldiéthanolamine ou d'alkyldiisopropanolamine éventuellement oxyalkylénées sur des acides gras ou sur des mélanges d'acides gras d'origine végétale ou animale, ou par transestérification de leurs esters méthyliques. Cette estérification est suivie d'une quaternisation à l'aide d'un agent d'alkyla- tion tel qu'un halogénure d'alkyle (méthyle ou éthyle de préférence), un sulfate de dialkyle (méthyle ou éthyle de préférence), le méthane- sulfonate de méthyle, le para-toluènesulfonate de méthyle, la chlorhydrine du glycol ou du glycérol.These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldiisopropanolamine optionally oxyalkylenated on fatty acids or mixtures of fatty acids of plant or animal origin, or by transesterification. of their methyl esters. This esterification is followed by quaternization using an alkylating agent such as an alkyl halide (preferably methyl or ethyl), a dialkyl sulphate (preferably methyl or ethyl), the methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin.
De tels composés sont par exemple commercialisés sous les dénominations DEHYQUART® par la société HENKEL, STEPANQUAT® par la société STEPAN, NOXAMIUM® par la société CECA, REWOQUAT® WE 18 par la société REWO-WITCO. La composition selon l'invention peut contenir par exemple un mélange de sels de mono-, di- et triester d'ammonium quaternaire avec une majorité en poids de sels de diester.Such compounds are for example marketed under the names DEHYQUART ® by the company Henkel, Stepanquat® ® by the company Stepan, Noxamium ® by CECA Rewoquat ® WE 18 by Rewo-Witco. The composition according to the invention may contain, for example, a mixture of quaternary ammonium mono-, di- and triester salts with a majority by weight of diester salts.
Comme mélange de sels d'ammonium, on peut utiliser par exemple le mélange contenant 15 à 30 % en poids de méthylsulfate d'acyloxyéthyl-dihydroxyéthyl-méthylammonium, 45 à 60% de méthylsulfate de diacyloxyéthyl-hydroxyéthyl-méthylammonium et 15 à 30% de méthylsulfate de triacyloxyéthyl-méthylammonium, les radicaux acyles ayant de 14 à 18 atomes de carbone et provenant d'huile de palme éventuellement partiellement hydrogénée.As a mixture of ammonium salts, it is possible to use, for example, the mixture containing 15 to 30% by weight of acyloxyethyl-dihydroxyethyl-methylammonium methylsulfate, 45 to 60% of diacyloxyethyl-hydroxyethyl-methylammonium methylsulfate and 15 to 30% of triacyloxyethylmethylammonium methylsulfate, the acyl radicals having from 14 to 18 carbon atoms and coming from partially hydrogenated palm oil.
On peut aussi utiliser les sels d'ammonium contenant au moins une fonction ester décrits dans les brevets US-A-4874554 et US-A- 4137180.It is also possible to use the ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180.
Les tensioactifs non-ioniques utilisables dans les compositions de la présente invention sont des composés bien connus en soi (voir notamment à cet égard "Handbook of Surfactants" par M. R. PORTER, éditions Blackie & Son (Glasgow and London), 1991 , pp 1 16- 178). Ils sont choisis notamment parmi les alcools et alcools gras polyéthoxylés, polypropoxylés ou polyglycérolés, les alpha-diols polyéthoxylés, polypropoxylés ou polyglycérolés, les alkyl(Ci_The nonionic surfactants that can be used in the compositions of the present invention are well-known compounds per se (see in particular in this regard "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp. - 178). They are chosen in particular from polyethoxylated, polypropoxylated or polyglycerolated alcohols and fatty alcohols, polyethoxylated, polypropoxylated or polyglycerolated alpha-diols, alkyl (Ci
2o)phénols polyéthoxylés, polypropoxylés ou polyglycérolés ou les acides gras polyéthoxylés, polypropoxylés ou polyglycérolés, la chaîne grasse comportant, par exemple, de 8 à 18 atomes de carbone, le nombre de groupements oxyde d'éthylène ou oxyde de propylène pouvant aller notamment de 2 à 50 et le nombre de groupements glycérol pouvant aller notamment de 2 à 30.2o) polyethoxylated, polypropoxylated or polyglycerolated phenols or polyethoxylated, polypropoxylated or polyglycerolated fatty acids, the fatty chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups being able to range from 2 to 50 and the number of glycerol groups that can range from 2 to 30.
On peut également citer les condensats d'oxyde d'éthylène et d'oxyde de propylène sur des alcools gras ; les amides gras polyéthoxylés ayant de préférence de 2 à 30 motifs d'oxyde d'éthylène, les amides gras polyglycérolés comportant en moyenne de 1 à 5 groupements glycérol et en particulier de 1 ,5 à 4, les esters d'acides gras et de sorbitane éthoxylés ayant de 2 à 30 motifs d'oxyde d'éthylène, les esters d'acides gras du saccharose, les esters d'acides gras et de polyéthylèneglycol, les alkylpolyglycosides, les huiles végétales polyéthoxylées, les dérivés de N-(alkyl en C6-24)glucamine, les oxydes d'aminés tels que les oxydes d'(alkyl en C10-14)amines ou les oxydes de N-(acyl en C1o_14)-aminopropylmorpholine.It is also possible to mention the condensates of ethylene oxide and of propylene oxide on fatty alcohols; the polyethoxylated fatty amides preferably having from 2 to 30 ethylene oxide units, the polyglycerolated fatty amides comprising on average from 1 to 5 glycerol groups and in particular from 1, 5 to 4, the esters of fatty acids and of ethoxylated sorbitan having 2 to 30 ethylene oxide units, sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, polyethoxylated vegetable derivatives, N- (C 6- 2 4) glucamine, amine oxides such as oxides of (C 10-14) amines or oxides of N (acyl C 1 14- aminopropylmorpholine.
Les tensioactifs amphotères ou zwitttérioniques utilisables dans les compositions de la présente invention comprennent par exemple les dérivés d'aminés aliphatiques secondaires ou tertiaires, dans lesquels le groupe aliphatique est une chaîne linéaire ou ramifiée comportant deThe amphoteric or zwitterionic surfactants that can be used in the compositions of the present invention comprise, for example, secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain comprising
8 à 22 atomes de carbone et contenant au moins un groupe anionique tel que, par exemple, un groupe carboxylate, sulfonate, sulfate, phosphate ou phosphonate. On peut citer également les alkyl(C8_8 to 22 carbon atoms and containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may also be made of alkyl (C 8 _
2o)bétaïnes, les sulfobétaïnes, les (alkyl en C8-20)amido(alkyl en C6- 2o) alkylbetaines, sulphobetaines, (C 8 2 0) amido (C 6-
8)bétaïnes ou les (alkyl en C8_20)amido(alkyl en C6_8)sulfobétaïnes. 8) betaines or (C 8 0 _2) amido (C 6 _ 8) sulphobetaines.
Parmi les dérivés d'aminés, on peut citer les produits commercialisés sous la dénomination MIRANOL®, tels que décrits dans les brevets US 2 528 378 et US 2 781 354 et classés dans le dictionnaire CTFA, 3ème édition, 1982, sous les dénominations Amphocarboxy-glycinate et Amphocarboxypropionate de structures respectives (1 ) et (2) :Among the amine derivatives include the products sold under the name Miranol ®, as described in US patents 2,528,378 and US 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxy-glycinate and Amphocarboxypropionate of respective structures (1) and (2):
Ra-CONHCH2CH2-N(Rb)(Rc)(CH2COO") (1 ) dans laquelle :Ra-CONHCH 2 CH 2 -N (Rb) (Rc) (CH 2 COO ") (1) wherein:
Ra représente un groupe alkyle dérivé d'un acide R8-COOH présent dans l'huile de coprah hydrolysée, un groupe heptyle, nonyle ou undécyle,R a represents an alkyl group derived from an R 8 -COOH acid present in the hydrolysed coconut oil, a heptyl, nonyl or undecyl group,
Rb représente un groupe bêta-hydroxyéthyle, et R0 représente un groupe carboxyméthyle ; etRb represents a beta-hydroxyethyl group, and R 0 represents a carboxymethyl group; and
Ra'-CONHCH2CH2-N(B)(B') (2) dans laquelle : B représente -CH2CH2OX', B' représente -(CH2)Z-Y', avec z = 1 ou 2,R a '-CONHCH 2 CH 2 -N (B) (B') (2) wherein: B represents -CH 2 CH 2 OX ', B' represents - (CH 2 ) Z -Y ', with z = 1 or 2,
X' représente le groupe -CH2CH2-COOH ou un atome d'hydrogène,X 'represents the group -CH 2 CH 2 -COOH or a hydrogen atom,
Y' représente -COOH ou le groupe -CH2-CHOH-SO3H, Ra' représente un groupe alkyle d'un acide Ra'-COOH présent dans l'huile de coprah ou dans l'huile de lin hydrolysée, un groupe alkyle, notamment en C17 et sa forme iso, un groupe en C17 insaturé.Y 'represents -COOH or the group -CH 2 -CHOH-SO 3 H, R a 'represents an alkyl group of a R a ' -COOH acid present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially C 17 and its iso form, a C 17 group unsaturated.
Ces composés sont classés dans le dictionnaire CTFA, 5ème édition, 1993, sous les dénominations cocoamphodiacétate de disodium, lauroamphodiacétate de disodium, caprylamphodiacétate de disodium, capryloamphodiacétate de disodium, cocoamphodipropionate de disodium, lauroamphodipropionate de disodium, caprylamphodipropionate de disodium, capryloamphodipropionate de disodium, acide lauroamphodipropionique, acide cocoamphodipropionique.These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate caprylamphodiacetate disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate disodium capryloamphodipropionate, disodium lauroamphodipropionic acid, cocoamphodipropionic acid.
A titre d'exemple, on peut citer le cocoamphodiacétate commercialisé par la société RHODIA sous la dénomination commerciale MIRANOL® C2M concentré. Les compositions selon l'invention peuvent également comprendre en outre au moins une silicone ou un dérivé de silicone, sous forme soluble, dispersée ou micro-dispersée. Les silicones ou dérivés de silicones sont de préférence présents en une quantité inférieure à 10 % en poids, de préférence allant de 0,01 à 8%, et encore plus préférentiellement de 0, 1 à 5% en poids par rapport au poids total de la composition.Examples include the cocoamphodiacetate sold by Rhodia under the trade name Miranol ® C2M concentrate. The compositions according to the invention may also comprise at least one silicone or a silicone derivative, in soluble, dispersed or micro-dispersed form. The silicones or silicone derivatives are preferably present in an amount of less than 10% by weight, preferably ranging from 0.01 to 8%, and still more preferably from 0.1 to 5% by weight relative to the total weight of the composition.
A titre d'exemple, on peut notamment citer les huiles siliconées, telles que par exemple les polydiméthylsiloxanes linéaires ou cycliques. Les compositions selon l'invention peuvent également contenir au moins un polymère fixant additionnel, différent du copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), pour renforcer l'effet de maintien. Un tel polymère fixant additionnel peut être de nature anionique, cationique, non ionique ou amphotère et de préférence anionique, non ionique ou amphotère.By way of example, mention may be made especially of silicone oils, such as, for example, linear or cyclic polydimethylsiloxanes. The compositions according to the invention may also contain at least one additional fixing polymer, different from the copolymer of acrylate (s) or of methacrylate (s) and of hydroxyester of acrylate (s) or of methacrylate (s), to reinforce the holding effect. Such an additional fixing polymer may be anionic, cationic, nonionic or amphoteric and preferably anionic, nonionic or amphoteric.
Les polymères fixants anioniques utilisables dans les compositions selon l'invention sont des polymères comportant des groupements dérivés d'acide carboxylique, sulfonique ou phosphorique et ont une masse moléculaire moyenne en nombre comprise entre environ 500 et 5 000 000.The anionic fixing polymers that can be used in the compositions according to the invention are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acids. and have a number average molecular weight of between about 500 and 5,000,000.
Les groupements carboxyliques sont apportés par des monomères mono ou diacides carboxyliques insaturés tels que ceux répondant à la formule :The carboxylic groups are provided by unsaturated mono- or di-carboxylic acid monomers, such as those corresponding to the formula:
Figure imgf000021_0001
dans laquelle n est un nombre entier de 0 à 10, A1 désigne un groupement méthylène, éventuellement relié à l'atome de carbone du groupement insaturé ou au groupement méthylène voisin lorsque n est supérieur à 1 , par l'intermédiaire d'un hétéroatome tel qu'oxygène ou soufre, R7 désigne un atome d'hydrogène, un groupement phényle ou benzyle, R8 désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, R9 désigne un atome d'hydrogène, un groupement alkyle inférieur, un groupement -CH2-COOH, phényle ou benzyle.
Figure imgf000021_0001
in which n is an integer from 0 to 10, A 1 denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, via a heteroatom such as oxygen or sulfur, R 7 denotes a hydrogen atom, a phenyl or benzyl group, R 8 denotes a hydrogen atom, a lower alkyl or carboxyl group, R 9 denotes a hydrogen atom, a lower alkyl group, a -CH 2 -COOH group, phenyl or benzyl group.
Dans la formule précitée, un groupement alkyle inférieur désigne de préférence un groupement ayant 1 à 4 atomes de carbone et en particulier, les groupements méthyle et éthyle. Les polymères fixants anioniques à groupements carboxyliques préférés selon l'invention sont :In the abovementioned formula, a lower alkyl group preferably denotes a group having 1 to 4 carbon atoms and in particular the methyl and ethyl groups. The anionic fixing polymers with preferred carboxylic groups according to the invention are:
A) Les copolymères d'acide acrylique et d'acrylamide ;A) copolymers of acrylic acid and acrylamide;
B) Les copolymères d'acide acrylique ou méthacrylique avec un monomère monoéthylénique choisi parmi l'éthylène, le styrène, les esters vinyliques, les esters d'acide acrylique ou méthacrylique, éventuellement greffés sur un polyalkylène-glycol tel que le polyéthylène-glycol, et éventuellement réticulés. De tels polymères sont décrits en particulier dans le brevet français n° 1 222 944 et la demande allemande n° 2 330 956, les copolymères de ce type comportant dans leur chaîne un motif acrylamide éventuellement N- alkylé et/ou hydroxyalkylé tels que décrits notamment dans les demandes de brevets luxembourgeois nos 75370 et 75371. On peut également citer les copolymères d'acide acrylique et de méthacrylate d'alkyle en C1-C4 et les terpolymères de vinylpyrrolidone, d'acide acrylique et de méthacrylate d'alkyle en C1-C20, par exemple, de lauryle, tels que celui commercialisé par la société ISP sous la dénomination ACRYLIDONE® LM et les terpolymères acide méthacrylique/acrylate d'éthyle/acrylate de tertiobutyle tels que le produit commercialisé sous la dénomination LUVIMER® 100 P par la société BASF. C) Les copolymères dérivés d'acide crotonique, tels que ceux comportant dans leur chaîne des motifs acétate ou propionate de vinyle, et éventuellement d'autres monomères tels que les esters allylique ou méthallylique, éther vinylique ou ester vinylique d'un acide carboxylique saturé, linéaire ou ramifié, à longue chaîne hydrocarbonée, comme ceux comportant au moins 5 atomes de carbone, ces polymères pouvant éventuellement être greffés et réticulés, ou encore un autre monomère ester vinylique, allylique ou méthallylique d'un acide carboxylique α- ou β-cyclique. De tels polymères sont décrits entre autres dans les brevets français nos 1 222 944, 1 580 545, 2 265 782, 2 265 781 , 1 564 1 10 et 2 439 798. Un produit commercial entrant dans cette classe est la résine 28-29-30 commercialisée par la société National Starch.B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer chosen from ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. Such polymers are described in particular in French Patent No. 1,222,944 and German Application No. 2,330,956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and / or hydroxyalkylated such as described in particular in the patent applications Nos . 75370 and 75371. Copolymers of acrylic acid and of C 1 -C 4 alkyl methacrylate and terpolymers of vinylpyrrolidone, acrylic acid and C-alkyl methacrylate may also be mentioned. 1 -C 20, for example lauryl methacrylate, such as that marketed by the company ISP under the name Acrylidone LM ® and methacrylic acid terpolymers / ethyl acrylate / butyl acrylate terpolymers such as the product sold under the name Luvimer ® 100 P by BASF. C) Copolymers derived from crotonic acid, such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid , linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted and crosslinked, or another vinyl ester monomer, allyl or methallylique a carboxylic acid α- or β- cyclic. Such polymers are described, inter alia, in French patents Nos . 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. A commercial product in this class is the resin. 29-30 marketed by the company National Starch.
D) Les copolymères dérivés d'acides ou d'anhydrides carboxyliques monoinsaturés en C4-C8 choisis parmi : - les copolymères comprenant (i) un ou plusieurs acides ou anhydrides maléique, fumarique, itaconique et (ii) au moins un monomère choisi parmi les esters vinyliques, les éthers vinyliques, les halogénures vinyliques, les dérivés phénylvinyliques, l'acide acrylique et ses esters, les fonctions anhydrides de ces copolymères étant éventuellement monoestérifiées ou monoamidifiées. De tels polymères sont décrits en particulier dans les brevets US nos 2 047 398, 2 723 248, 2 102 1 13, le brevet GB n° 839 805. Des produits commerciaux sont notamment ceux vendus sous les dénominations GANTREZ® AN ou ES par la société ISP. - les copolymères comprenant (i) un ou plusieurs motifs anhydrides maléique, citraconique, itaconique et (ii) un ou plusieurs monomères choisis parmi les esters allyliques ou méthallyliques comportant éventuellement un ou plusieurs groupements acrylamide, méthacrylamide, α-oléfine, esters acryliques ou méthacryliques, acides acrylique ou méthacrylique ou vinylpyrrolidone dans leur chaîne, les fonctions anhydrides de ces copolymères étant éventuellement monoestérifiées ou monoamidifiées.D) Copolymers derived from C 4 -C 8 monounsaturated carboxylic acids or anhydrides chosen from: copolymers comprising (i) one or more maleic, fumaric, itaconic acids and anhydrides and (ii) at least one monomer chosen among the vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. Such polymers are described in particular in US Patents Nos 2,047,398, 2,723,248, January 13 2102, GB Patent No. 839 805. Commercial products include those sold under the Gantrez ® AN or ES by denominations the ISP company. copolymers comprising (i) one or more maleic, citraconic and itaconic anhydride units and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, α-olefin or acrylic or methacrylic ester groups; acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.
Ces polymères sont par exemple décrits dans les brevets français nos 2 350 384 et 2 357 241 de la demanderesse.These polymers are for example described in French Patent Nos . 2,350,384 and 2,357,241 of the Applicant.
E) Les polyacrylamides comportant des groupements carboxylates.E) Polyacrylamides having carboxylate groups.
Les polymères comprenant les groupements sulfoniques sont des polymères comportant des motifs vinylsulfonique, styrène- sulfonique, naphtalène-sulfonique ou acrylamido-alkylsulfonique.The polymers comprising the sulphonic groups are polymers comprising vinylsulphonic, styrene-sulphonic, naphthalenesulphonic or acrylamido-alkylsulphonic units.
Ces polymères peuvent être notamment choisis parmi :These polymers may especially be chosen from:
- les sels de l'acide polyvinylsulfonique ayant une masse moléculaire comprise entre environ 1 000 et 100 000, ainsi que les copolymères avec un comonomère insaturé tel que les acides acrylique ou méthacrylique et leurs esters, ainsi que Facrylamide ou ses dérivés, les éthers vinyliques et la vinylpyrrolidone.salts of polyvinylsulphonic acid having a molecular mass of between about 1,000 and 100,000, as well as copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters, as well as acrylamide or its derivatives, vinyl ethers; and vinylpyrrolidone.
- les sels de l'acide polystyrène-sulfonique tels que les sels de sodium vendus par exemple sous la dénomination Flexan® 130 par National Starch. Ces composés sont décrits dans le brevet FR 2 198 719.- salts of polystyrene sulfonic acid such as the sodium salts are sold under the name Flexan ® 130 by National Starch. These compounds are described in patent FR 2 198 719.
- les sels d'acides polyacrylamide-sulfoniques tels que ceux mentionnés dans le brevet US 4 128 631 , et plus particulièrement l'acide polyacrylamidoéthylpropane- sulfonique.polyacrylamidesulfonic acid salts such as those mentioned in US Pat. No. 4,128,631, and more particularly polyacrylamidoethylpropanesulfonic acid.
Selon l'invention, parmi les polymères fixants anioniques cités ci-dessus, on préférera les copolymères d'acide acrylique tels que les terpolymères acide acrylique/acrylate d'éthyle/N-tertiobutylacrylamide vendus notamment sous la dénomination ULTRAHOLD® STRONG par la société BASF, les copolymères dérivés d'acide crotonique tels que les terpolymères acétate de vinyle/tertio-butylbenzoate de vinyle/acide crotonique et les terpolymères acide crotonique/acétate de vinyle/ néododécanoate de vinyle vendus notamment sous la dénomination Résine 28-29-30 par la société NATIONAL STARCH, les polymères dérivés d'acides ou d'anhydrides maléique, fumarique, itaconique avec des esters vinyliques, des éthers vinyliques, des halogénures vinyliques, des dérivés phénylvinyliques, l'acide acrylique et ses esters tels que les copolymères méthylvinyléther/anhydride maléique monoestérifié vendus, par exemple, sous la dénomination GANTREZ® par la société ISP, les copolymères d'acide méthacrylique et de méthacrylate de méthyle vendus sous la dénomination EUDRAGIT® L par la société ROHM PHARMA, les copolymères d'acide méthacrylique et d'acrylate d'éthyle vendus sous la dénomination LUVIMER® MAEX ou MAE par la société BASF et les copolymères acétate de vinyle/acide crotonique et les copolymères acétate de vinyle/acide crotonique greffés par du polyéthylèneglycol vendus sous la dénomination ARISTOFLEX® A par la société BASF.According to the invention, among the anionic fixing polymers mentioned above, are preferred acrylic acid copolymers such as the acrylic acid terpolymers / ethyl acrylate / N-tert-butylacrylamide sold under the name Ultrahold ® STRONG by the company BASF Crotonic acid-derived copolymers such as vinyl acetate terpolymers / tert-butylbenzoate / acid crotonic acid and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters , vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters such as the methyl vinyl ether / monoesterified maleic anhydride sold, e.g., under the name GANTREZ ® by the company ISP, copolymers of methacrylic acid and methyl methacrylate sold under the name Eudragit ® L by the company Rohm Pharma, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer ® MAEX or MAE by the company BASF and the vinyl acetate copolymers / crotonic acid and vinyl acetate / crotonic acid copolymers grafted with polyethylenegly neck sold under the name ARISTOFLEX ® A by the company BASF.
Les polymères fixants anioniques cités ci-dessus, les plus particulièrement préférés sont choisis parmi les copolymères méthylvinyléther/anhydride maléique monoestérifiés vendus sous la dénomination GANTREZ® ES 425 par la société ISP, les terpolymères acide acrylique/acrylate d'éthyle/N-tertiobutylacrylamide vendus sous la dénomination ULTRAHOLD® STRONG par la société BASF, les copolymères d'acide méthacrylique et de méthacrylate de méthyle vendus sous la dénomination EUDRAGIT® L par la société ROHM PHARMA, les terpolymères acétate de vinyle/tertio-butylbenzoate de vinyle/acide crotonique et les terpolymères acide crotonique/acétate de vinyle/ néododécanoate de vinyle vendus sous la dénomination Résine 28-29-30 par la société NATIONAL STARCH, les copolymères d'acide méthacrylique et d'acrylate d'éthyle vendus sous la dénomination LUVIMER® MAEX OU MAE par la société BASF, les terpolymères vinylpyrrolidone/acide acrylique/méthacrylate de lauryle vendus sous la dénomination ACRYLIDONE® LM par la société ISP.The anionic fixing polymers mentioned above, most particularly preferred are chosen from the methyl vinyl ether / monoesterified maleic anhydride sold under the name Gantrez ® ES 425 by the company ISP, the acrylic acid terpolymers / ethyl acrylate / N-tert-butylacrylamide sold under the name Ultrahold ® STRONG by the company BASF, the copolymers of methacrylic acid and of methyl methacrylate sold under the name Eudragit ® L by the company Rohm Pharma, the vinyl acetate / vinyl tert-butylbenzoate / crotonic acid and the terpolymers crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and of ethyl acrylate sold under the name Luvimer ® MAEX or MAE by BASF, terpolymers vinylpyrrolidone / acrylic acid / methacrylate lauryl sold under the name ACRYLIDONE ® LM by ISP.
Les polymères fixants amphotères utilisables conformément à l'invention peuvent être choisis parmi les polymères comportant des motifs B et C répartis statistiquement dans la chaîne polymère où B désigne un motif dérivant d'un monomère comportant au moins un atome d'azote basique et C désigne un motif dérivant d'un monomère acide comportant un ou plusieurs groupements carboxyliques ou sulfoniques, ou bien B et C peuvent désigner des groupements dérivant de monomères zwittérioniques de carboxybétaïnes ou de sulfobétaïnes;The amphoteric fixing polymers that may be used according to the invention may be chosen from polymers comprising B and C units statistically distributed in the polymer chain where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit derived from an acidic monomer comprising one or more carboxylic or sulphonic groups, or B and C may be groups derived from zwitterionic monomers of carboxybetaines or sulfobetaines;
B et C peuvent également désigner une chaîne polymère cationique comportant des groupements aminé primaire, secondaire, tertiaire ou quaternaire, dans laquelle au moins l'un des groupements aminé porte un groupement carboxylique ou sulfonique relié par l'intermédiaire d'un groupe hydrocarboné, ou bien B et C font partie d'une chaîne d'un polymère à motif éthylène-α,β-dicarboxylique dont l'un des groupements carboxyliques a été amené à réagir avec une polyamine comportant un ou plusieurs groupements aminé primaire ou secondaire.B and C may also designate a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulfonic group connected via a hydrocarbon group, or B and C are part of a chain of an ethylene-α, β-dicarboxylic-containing polymer, one of which has been reacted with a polyamine having one or more primary or secondary amine groups.
Les polymères fixants amphotères répondant à la définition donnée ci-dessus plus particulièrement préférés sont choisis parmi les polymères suivants :The amphoteric fixing polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers:
(1 ) les polymères résultant de la copolymérisation d'un monomère dérivé d'un composé vinylique portant un groupement carboxylique tel que plus particulièrement l'acide acrylique, l'acide méthacrylique, l'acide maléïque, l'acide alpha-chloracrylique, et d'un monomère basique dérivé d'un composé vinylique substitué contenant au moins un atome basique, tel que plus particulièrement les dialkyl- aminoalkylméthacrylate et acrylate, les dialkylaminoalkyl- méthacrylamide et acrylamide. De tels composés sont décrits dans le brevet américain n° 3 836 537.(1) polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, alpha-chloro acrylic acid, and of a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as more particularly dialkylaminoalkylmethacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537.
(2) les polymères comportant des motifs dérivant : a) d'au moins un monomère choisi parmi les acrylamides ou les méthacrylamides substitués sur l'atome d'azote par un groupe alkyle, b) d'au moins un comonomère acide contenant un ou plusieurs groupements carboxyliques réactifs, et c) d'au moins un comonomère basique tel que des esters à substituants aminé primaire, secondaire, tertiaire et quaternaire des acides acrylique et méthacrylique, et le produit de quaternisation du méthacrylate de diméthylaminoéthyle avec le sulfate de diméthyle ou diéthyle.(2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen atom with an alkyl group; b) with at least one acidic comonomer containing one or more several reactive carboxylic groups, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituted esters of acrylic and methacrylic acids, and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
Les acrylamides ou méthacrylamides N-substitués plus particulièrement préférés selon l'invention sont les composés dont les groupes alkyle comportent de 2 à 12 atomes de carbone, et plus particulièrement le N-éthylacrylamide, le N-tertiobutylacrylamide, le N-tertiooctylacrylamide, le N-octylacrylamide, le N-décylacrylamide, le N-dodécylacrylamide ainsi que les méthacrylamides correspondants.The N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are the compounds whose alkyl groups contain from 2 to 12 carbon atoms, and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
Les comonomères acides sont choisis plus particulièrement parmi les acides acrylique, méthacrylique, crotonique, itaconique, maléïque, fumarique ainsi que les monoesters d'alkyle ayant 1 à 4 atomes de carbone des acides ou des anhydrides maléïque ou fumarique.The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.
Les comonomères basiques préférés sont des méthacrylates d'aminoéthyle, de butylaminoéthyle, de N,N'-diméthylaminoéthyle, de N-tertio-butylaminoéthyle. On utilise particulièrement les copolymères dont la dénomination CTFA (4ème Ed., 1991 ) estPreferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. The copolymers whose CTFA name (4th Ed., 1991) is
Octylacrylamide/acrylates/butylaminoethyl-methacrylate copolymer, tels que les produits vendus sous la dénomination AMPHOMER® ou LOVOCRYL® 47 par la société NATIONAL STARCH. (3) les polyaminoamides réticulés et acylés partiellement ou totalement dérivant de poyaminoamides de formule générale :Octylacrylamide / acrylates / butylaminoethyl-methacrylate copolymer such as the products sold under the name or Lovocryl AMPHOMER® ® ® 47 by the company National Starch. (3) polyamino amides crosslinked and acylated partially or totally derived from poyaminoamides of general formula:
dans laquelle R10 représente un groupe divalent dérivé d'un acide dicarboxylique saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atome de carbone de ces acides ou d'un groupe dérivant de l'addition de l'un quelconque desdits acides avec une aminé bis-primaire ou bis-secondaire, et Z désigne un groupe dérivant d'une polyalkylène-polyamine bis-primaire, mono- ou bis-secondaire et de préférence représente : a) dans les proportions de 60 à 100 % en moles, le groupewherein R 10 represents a divalent group derived from a saturated dicarboxylic acid, an ethylenically double-bonded mono or dicarboxylic aliphatic acid, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or 'a group derived from the addition of any of said acids with a bis-primary or bis-secondary amine, and Z denotes a group derived from a bis-primary, mono- or bis-secondary polyalkylene polyamine and preferably represents: a) in the proportions of 60 to 100 mol%, the group
— NH ^(CH2,,- NH3^ m) où x=2 et p=2 ou 3, ou bien x=3 et p=2 ce groupe dérivant de la diéthylène-triamine, de la triéthylène- tétraamine ou de la dipropylène-triamine; b) dans les proportions de 0 à 40 % en moles, le groupe (Vllbis) ci-dessus, dans lequel x=2 et p=l et qui dérive de l'éthylène- diamine, ou le groupe dérivant de la pipérazine :- ^ NH (CH 2 ,, - NH 3 ^ m) where x = 2 and p = 2 or 3, or alternatively x = 3 and p = 2 this group derived from diethylene triamine, triethylene tetraamine of or dipropylene triamine; b) in the proportions of 0 to 40 mol%, the group (VIIa) above, in which x = 2 and p = 1 and which is derived from ethylenediamine, or the group derived from piperazine:
Figure imgf000027_0001
c) dans les proportions de 0 à 20 % en moles, le groupe -NH-
Figure imgf000027_0001
c) in the proportions of 0 to 20 mol%, the group -NH-
(CHi)6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamides étant réticulés par réaction d'addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis-insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par groupement aminé du polyaminoamide, et acylés par action d'acide acrylique, d'acide chloracétique ou d'une alcane-sultone ou de leurs sels.(CHi) 6 -NH- derived from hexamethylenediamine, these polyaminoamides being crosslinked by addition reaction of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, by means of 0.025 to 0.35 mole of crosslinking agent per amine group of the polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or an alkane-sultone or their salts.
Les acides carboxyliques saturés sont choisis de préférence parmi les acides ayant 6 à 10 atomes de carbone tels que les acides adipique, triméthyl-2,2,4-adipique et triméthyl-2,4,4-adipique, téréphtalique, les acides à double liaison éthylénique comme, par exemple, les acides acrylique, méthacrylique, itaconique.The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic and trimethyl-2,4,4-adipic acid, terephthalic acids, double acids and the like. ethylenic bond such as, for example, acrylic, methacrylic, itaconic acids.
Les alcane-sultones utilisées dans l'acylation sont de préférence la propane- ou la butane-sultone, les sels des agents d'acylation sont de préférence les sels de sodium ou de potassium.The alkane sultones used in the acylation are preferably propane or butane sultone, the salts of the acylating agents are preferably the sodium or potassium salts.
(4) les polymères comportant des motifs zwittérioniques de formule :
Figure imgf000028_0001
dans laquelle R11 désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent un nombre entier de 1 à 3, R12 et R13 représentent un atome d'hydrogène, un groupe méthyle, éthyle ou propyle, R14 et R15 représentent un atome d'hydrogène ou un groupe alkyle de telle façon que la somme des atomes de carbone dans R14 et R15 ne dépasse pas 10.(4) polymers having zwitterionic units of formula:
Figure imgf000028_0001
in which R 11 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, R 12 and R 13 represent a hydrogen atom, a methyl group, ethyl or propyl, R 14 and R 15 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R 14 and R 15 does not exceed 10.
Les polymères comprenant de telles unités peuvent également comporter des motifs dérivés de monomères non zwittérioniques tels que l'acrylate ou le méthacrylate de diméthyl- ou diéthylaminoéthyle ou des acrylates ou méthacrylates d'alkyle, des acrylamides ou méthacrylamides, ou l'acétate de vinyle.Polymers comprising such units may also include units derived from non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.
A titre d'exemple, on peut citer les copolymères méthacrylate de méthyle/diméthyl-carboxyméthyammonio-éthylméthacrylate de méthyle.By way of example, mention may be made of methyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate copolymers.
(5) les polymères dérivés du chitosane comportant des motifs monomères répondant aux formules suivantes :(5) polymers derived from chitosan having monomeric units corresponding to the following formulas:
Figure imgf000028_0002
le motif (D) étant présent dans des proportions comprises entre O et 30%, le motif (E) dans des proportions comprises entre 5 et 50% et le motif (F) dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (F), R16 représente un groupe de formule : R 18 R "Λ,19
Figure imgf000028_0002
the unit (D) being present in proportions of between 0 and 30%, the unit (E) in proportions of between 5 and 50% and the unit (F) in proportions of between 30 and 90%, it being understood that in this unit (F), R 16 represents a group of formula: R 18 R "Λ, 19
X17 C-(O)-C X 17 C- (O) -C
dans laquelle si q=0, R17, R18 et Rig, identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoalcoylamine ou un reste dialcoylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes aminé, hydroxyle, carboxyle, alcoylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des groupes R17, R18 et R^ étant dans ce cas un atome d'hydrogène ; ou si q=l , R17, R18 et R^ représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.in which if q = 0, R 17 , R 18 and R 1, identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted with one or more amino, hydroxyl, carboxyl, alkylthio, sulphonic groups, an alkylthio radical whose alkyl group carries an amino residue, at least one of R 17 , R 18 and R groups. being in this case a hydrogen atom; or if q = 1, R 17 , R 18 and R 4 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
(6) Les polymères répondant à la formule générale (IX) sont, par exemple, décrits dans le brevet français 1 400 366 :(6) The polymers corresponding to the general formula (IX) are, for example, described in French Patent 1,400,366:
Figure imgf000029_0001
dans laquelle R20 représente un atome d'hydrogène, un groupe CH3O, CH3CH2O, phényle, R21 désigne un atome d'hydrogène ou un groupe alkyle inférieur tel que méthyle, éthyle, R22 désigne un atome d'hydrogène ou un groupe alkyle inférieur en C1-C6 tel que méthyle, éthyle, R23 désigne un groupe alkyle inférieur en C1-C6 tel que méthyle, éthyle ou un groupe répondant à la formule : -R.24-N(R22)2, R24 représentant un groupement -CH2-CH2- , -CH2-CH2-CH2-, -CH2- CH(CH3)-, R22 ayant les significations mentionnées ci-dessus.
Figure imgf000029_0001
in which R 20 represents a hydrogen atom, a CH 3 O, CH 3 CH 2 O, phenyl group, R 21 denotes a hydrogen atom or a lower alkyl group such as methyl, ethyl, R 22 denotes a hydrogen atom, hydrogen or a C 1 -C 6 lower alkyl group such as methyl, ethyl, R 23 denotes a C 1 -C 6 lower alkyl group such as methyl, ethyl or a group of the formula: -R.24-N (R22) 2, R24 representing a -CH2-CH2- group, -CH2-CH2-CH2-, -CH 2 - CH (CH 3) - , R22 having the meanings mentioned above.
(7) Les polymères dérivés de la N-carboxyalkylation du chitosane comme le N-carboxyméthyl-chitosane ou le N-carboxybutyl- chitosane.(7) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl-chitosan or N-carboxybutylchitosan.
(8) Les polymères amphotères du type -D-X-D-X choisis parmi: a) les polymères obtenus par action de l'acide chloracétique ou le chloracétate de sodium sur les composés comportant au moins un motif de formule :(8) Amphoteric polymers of the -D-X-D-X type chosen from: a) the polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula:
-D-X-D-X-D- (X) où D désigne un groupe-D-X-D-X-D- (X) where D denotes a group
Figure imgf000030_0001
et X désigne le symbole E ou E', E ou E' identiques ou différents désignent un groupe bivalent qui est un groupe alkylène à chaîne droite ou ramifiée, comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle et pouvant comporter en outre des atomes d'oxygène, d'azote, de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques ; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkylamine, alcénylamine, des groupements hydroxyle, benzylamine, oxyde d'aminé, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne. b) Les polymères de formule :
Figure imgf000030_0001
and X denotes the symbol E or E ', E or E', which may be the same or different, denotes a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the unsubstituted or substituted backbone. hydroxyl groups and may further comprise oxygen, nitrogen, sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane. b) polymers of formula:
-D-X-D-X- (X') où D désigne un groupe-D-X-D-X- (X ') where D denotes a group
Figure imgf000030_0002
et X désigne le symbole E ou E' et au moins une fois E' ; E ayant la signification indiquée ci-dessus et E' est un groupe bivalent qui est un groupe alkylène à chaîne droite ou ramifiée, ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs groupes hydroxyle et comportant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude.
Figure imgf000030_0002
and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a divalent group which is a straight or branched chain alkylene group having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl groups and having one or more nitrogen atoms, the nitrogen atom being substituted by an optionally interrupted alkyl chain by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functional groups and betainized by reaction with chloroacetic acid or sodium chloroacetate.
(9) les copolymères alkyl(C1-C5)vinyléther/anhydride maléique modifiés partiellement par semiamidification avec une N5N- dialkylaminoalkylamine telle que la N,N-diméthylaminopropylamine ou par semiestérification avec un N,N-dialkylaminoalcanol. Ces copolymères peuvent également comporter d'autres comonomères vinyliques tels que le vinylcaprolactame. Parmi les polymères fixants amphotères cités ci-dessus les plus particulièrement préférés selon l'invention, on citera ceux de la famille (3) tels que les copolymères dont la dénomination CTFA est Octylacrylamide/acrylates/butylamino-ethylmethacrylate copolymer, tels que les produits vendus sous les dénominations AMPHOMER®, AMPHOMER® LV 71 ou LOVOCRYL® 47 par la société NATIONAL(9) (C 1 -C 5 ) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N 5 N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkylaminoalkanol. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam. Among the amphoteric fixing polymers mentioned above that are most particularly preferred according to the invention, mention will be made of those of the family (3) such as the copolymers whose CTFA name is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold. under the names AMPHOMER ® , AMPHOMER ® LV 71 or LOVOCRYL ® 47 by NATIONAL
STARCH et ceux de la famille (4) tels que les copolymères méthacrylate de méthyle/diméthyl-carboxyméthylammonio- éthylméthacrylate de méthyle.STARCH and those of the family (4) such as methyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate copolymers.
Les polymères fixants non ioniques utilisables selon la présente invention sont choisis, par exemple, parmi :The nonionic fixing polymers that can be used according to the present invention are chosen, for example, from:
- les polyalkyloxazolines ;polyalkyloxazolines;
- les homopolymères d'acétate de vinyle ;homopolymers of vinyl acetate;
- les copolymères d'acétate de vinyle et d'ester acrylique ;copolymers of vinyl acetate and of acrylic ester;
- les copolymères d'acétate de vinyle et d'éthylène ; - les copolymères d'acétate de vinyle et d'ester maléïque, par exemple, de maléate de dibutyle ;copolymers of vinyl acetate and of ethylene; copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate;
- les copolymères d'esters acryliques tels que, par exemple, les copolymères d'acrylates d'alkyle et de méthacrylates d'alkyle tels que les produits proposés par la société ROHM & HAAS sous les dénominations PRIMAL® AC-261 K et EUDRAGIT® NE 30 D, par la société BASF sous la dénomination 8845, par la société HOECHST sous la dénomination APPRETAN® N9212 ;copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates, such as the products offered by the company ROHM & HAAS under the ® names Primal AC-261 K and EUDRAGIT ® NE 30 D, by BASF under the name 8845, by Hoechst under the name APPRETAN ® 9212;
- les copolymères d'acrylonitrile et d'un monomère non ionique choisis, par exemple, parmi le butadiène et les (méth)acrylates d'alkyle ; on peut citer les produits proposés sous la dénomination CJ 0601 B par la société ROHM & HAAS ;copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of the products sold under the name CJ 0601 B by the company Rohm &Haas;
- les homopolymères de styrène ;homopolymers of styrene;
- les copolymères de styrène et de (méth)acrylate d'alkyle tels que les produits MOWILITH® LDM 691 1 , MOWILITH® DM 61 1 et- copolymers of styrene and of alkyl (meth) acrylate such as Mowilith LDM products ® 691 1 Mowilith ® DM 61 1 and
MOWILITH® LDM 6070 proposés par la société HOECHST, les produits RHODOPAS® SD 215 et RHODOPAS® DS 910 proposés par la société RHODIA CHIMIE;MOWILITH ® LDM 6070 offered by the company HOECHST, RHODOPAS ® SD 215 and RHODOPAS ® DS 910 products offered by RHODIA CHIMIE;
- les copolymères de styrène, de méthacrylate d'alkyle et d'acrylate d'alkyle ;copolymers of styrene, of alkyl methacrylate and of alkyl acrylate;
- les copolymères de styrène et de butadiène ;copolymers of styrene and butadiene;
- les copolymères de styrène, de butadiène et de vinylpyridine ;copolymers of styrene, butadiene and vinylpyridine;
- les copolymères d'acrylate d'alkyle et d'uréthanne ;copolymers of alkyl acrylate and urethane;
- les polyamides, - les homopolymères et copolymères de vinyllactame.polyamides, homopolymers and copolymers of vinyllactam.
Les groupes alkyle des polymères non ioniques mentionnés ci- dessus ont, de préférence, de 1 à 6 atomes de carbone.The alkyl groups of the nonionic polymers mentioned above preferably have from 1 to 6 carbon atoms.
Selon la présente invention, les polymères fixants non-ioniques à motifs vinyllactames peuvent être ceux décrits dans les brevets US 3 770 683, US 3 929 735, US 4 521 504, US 5 158 762, US 5 506 315 et dans les demandes de brevet WO 94/121 148, WO 96/06592 et WO 96/10593. Ils peuvent se présenter sous forme pulvérulente ou sous forme de solution ou de suspension.According to the present invention, the nonionic setting polymers with vinyllactam motifs can be those described in US Pat. Nos. 3,770,683, 3,929,735, 4,521,504, 5,156,762 and 5,506,315. WO 94/12148, WO 96/06592 and WO 96/10593. They can be in powder form or in the form of solution or suspension.
Les homopolymères ou copolymères à motifs vinyllactame comprennent des motifs de formule (XI):Homopolymers or copolymers with vinyllactam units comprise units of formula (XI):
— CH2-CH —- CH 2 -CH -
N C— V(CH2)n NC- V (CH 2 ) n
° (XI) dans laquelle n est indépendamment 3, 4 ou 5.° (XI) wherein n is independently 3, 4 or 5.
La masse moléculaire en nombre des polymères à motifs vinyllactames est généralement supérieure à environ 5 000, de préférence comprise entre 10 000 et 1 000 000 environ, plus préférentiellement comprise entre 10 000 et 100 000 environ.The number-average molecular weight of the polymers with vinyllactam units is generally greater than about 5,000, preferably between about 10,000 and 1,000,000, more preferably between about 10,000 and 100,000.
Parmi ces polymères fixants, on peut citer les polyvinylpyrrolidones telles que celles commercialisées sous la dénomination Luviskol® K30 par la société BASF ; les polyvinylcaprolactames tels que ceux commercialisés sous la dénomination Luviskol® PLUS par la société BASF ; les copolymères poly(vinylpyrrolidone/acétate de vinyle) tels que ceux commercialisés sous la dénomination PVPVA® S630L par la société ISP, Luviskol® VA 73, VA 64, VA 55, VA 37 et VA 28 par la société BASF ; et les terpolymères poly(vinylpyrrolidone/acétate de vinyle/propionate de vinyle) tels que, par exemple, ceux commercialisés sous la dénomination Luviskol® VAP 343 par la société BASF.These fixing polymers include polyvinylpyrrolidones such as those marketed under the name Luviskol ® K30 by BASF; polyvinylcaprolactams such as those sold under the name Luviskol ® Plus by BASF; poly (vinylpyrrolidone / vinyl acetate) such as those sold under the name PVPVA® S630L ® by ISP, Luviskol ® VA 73, VA 64, VA 55, VA 37 and VA 28 by the company BASF; terpolymers and poly (vinylpyrrolidone / vinyl acetate / vinyl propionate) such as, for example, those marketed under the name Luviskol ® VAP 343 by BASF.
Les polymères fixants additionnels peuvent être également choisis parmi les polyuréthanes éventuellement siliconés. A titre de polymères fixants de type polyuréthanes, on peut citer les polymères Luviset Pur et Luviset Si Pur proposés par la société BASF.The additional fixing polymers may also be chosen from optionally silicone polyurethanes. As fixing polymers of the polyurethane type, mention may be made of the Luviset Pur and Luviset Si Pur polymers proposed by BASF.
Ces polymères fixants additionnels peuvent être aussi choisis parmi les siliconés greffées à squelette hydrocarboné et greffons siliconés ou à squelette siliconé et greffons hydrocarbonés tels que les produits VS 70 et VS 80 proposés par la société 3M. Ils peuvent être aussi choisis parmi les polyesters à groupements sulfoniques tels que les résines AQ (AQ 55, AQ38, et AQ48) proposées par la société EASTMAN CHEMICAL.These additional fixing polymers may also be chosen from silicone grafted with a hydrocarbon backbone and silicone or silicone backbone grafts and hydrocarbon grafts such as the products VS 70 and VS 80 proposed by the company 3M. They may also be chosen from polyesters containing sulphonic groups, such as the AQ resins (AQ 55, AQ38, and AQ48) proposed by the company Eastman Chemical.
La composition selon l'invention peut alors contenir au moins 0,01 % en poids de polymère fixant additionnel, par rapport au poids total de la composition. De manière plus préférée, la composition selon l'invention contient de 0,01 à 20% en poids de polymère fixant additionnel, mieux encore de 0,05 à 15% en poids, encore plus préférentiellement de 0, 1 à 10% en poids, par rapport au poids total de la composition. Les compositions selon l'invention peuvent également contenir au moins un épaississant autre que Fhomopolymère d'acide acrylique, choisi parmi les épaississants polymériques naturels ou synthétiques, anioniques, amphotères, zwittérioniques, non ioniques ou cationiques, associatifs ou non, et les épaississants non polymériques tels que par exemple un électrolyte ou un sucre.The composition according to the invention may then contain at least 0.01% by weight of additional fixing polymer, relative to the total weight of the composition. More preferably, the composition according to the invention contains from 0.01 to 20% by weight of additional fixing polymer, more preferably from 0.05 to 15% by weight, even more preferably from 0.1 to 10% by weight. , relative to the total weight of the composition. The compositions according to the invention may also contain at least one thickener other than the homopolymer of acrylic acid, chosen from natural or synthetic, anionic, amphoteric, zwitterionic, nonionic or cationic, associative or non-associative polymeric thickeners and non-polymeric thickeners. such as for example an electrolyte or a sugar.
Les compositions conformes à l'invention peuvent être conditionnées dans un pot, dans un tube, un flacon pompe ou dans un dispositif aérosol usuel en cosmétique. Les compositions selon l'invention peuvent, lorsqu'elles ont destinées à être conditionnées dans un dispositif de type aérosol, contenir au moins un agent propulseur, tel qu'un gaz propulseur.The compositions in accordance with the invention may be packaged in a jar, in a tube, in a pump bottle or in an aerosol device that is usual in cosmetics. The compositions according to the invention may, when they are intended to be packaged in an aerosol-type device, contain at least one propellant, such as a propellant gas.
Le gaz propulseur peut alors être choisi par exemple parmi le diméthyléther, les alcanes en C3 à C5, les hydrocarbures halogènes, et leurs mélanges.The propellant can then be chosen for example from dimethyl ether, C 3 to C 5 alkanes, halogenated hydrocarbons, and mixtures thereof.
Les compositions selon l'invention peuvent en outre contenir au moins un additif choisi parmi les agents nacrants ; les agents opacifiants ; les agents plastifiants ; les filtres solaires ; les parfums ; les colorants ; les conservateurs ; les agents de stabilisation du pH ; les acides ; les bases ; les polyols (par exemple les glycols) ; les charges minérales ; les paillettes, et tout autre additif classiquement utilisé dans le domaine cosmétique.The compositions according to the invention may further contain at least one additive chosen from pearlescent agents; opacifying agents; plasticizers; solar filters; the perfumes ; dyes; conservatives ; pH stabilizers; acids; the basics ; polyols (for example glycols); mineral charges; glitter, and any other additive conventionally used in the cosmetic field.
L'homme de métier veillera à choisir les éventuels additifs et leurs quantités de manière à ce qu'ils ne nuisent pas aux propriétés des compositions de la présente invention.Those skilled in the art will take care to choose the possible additives and their amounts so that they do not adversely affect the properties of the compositions of the present invention.
Ces additifs sont présents dans la composition selon l'invention en une quantité allant de 0 à 50 % en poids par rapport au poids total de la composition.These additives are present in the composition according to the invention in an amount ranging from 0 to 50% by weight relative to the total weight of the composition.
Les compositions selon l'invention peuvent se présenter sous forme de liquides plus ou moins épaissis, de gels, de crèmes, de pâtes ou de moussesThe compositions according to the invention may be in the form of more or less thickened liquids, gels, creams, pastes or foams.
De préférence, elles se présentent sous forme de gels. La composition selon l'invention peut être avantageusement utilisée comme produit capillaire. Elle peut notamment être utilisée comme produit de coiffage, par exemple comme gel de coiffage.Preferably, they are in the form of gels. The composition according to the invention may advantageously be used as a hair product. It may in particular be used as a styling product, for example as a styling gel.
Selon un mode de réalisation préféré, elle est utilisée comme produit de coiffage non rincé, c'est-à-dire pour la mise en forme et/ou le maintien de la coiffure non suivis d'un rinçage.According to a preferred embodiment, it is used as a non-rinsed styling product, that is to say for shaping and / or maintaining the hairstyle not followed by rinsing.
La présente invention concerne également un procédé de traitement cosmétique des cheveux, par exemple un procédé de soin capillaire, ou un procédé de mise en forme et/ou de maintien de la coiffure, qui consiste à appliquer sur les cheveux une quantité efficace d'une composition telle que décrite ci-dessus, puis à effectuer un éventuel rinçage après un éventuel temps de pose.The present invention also relates to a cosmetic hair treatment method, for example a hair care method, or a method of shaping and / or maintaining the hairstyle, which consists in applying to the hair an effective amount of a hair. composition as described above, then to perform a possible rinsing after a possible exposure time.
De préférence, la composition selon l'invention n'est pas rincée.Preferably, the composition according to the invention is not rinsed.
L'exemple suivant est donné à titre illustratif de la présente invention.The following example is given by way of illustration of the present invention.
EXEMPLEEXAMPLE
Dans l'exemple suivant, toutes les quantités sont indiquées en pour cent en poids de matière active (MA) par rapport au poids total de la composition, sauf indication contraire.In the following example, all amounts are given in percent by weight of active ingredient (MA) based on the total weight of the composition, unless otherwise indicated.
Cet exemple illustre la formulation d'un gel coiffant conforme à l'invention. Un tel gel a été préparé à partir des ingrédients indiqués dans le tableau ci-dessous :This example illustrates the formulation of a styling gel according to the invention. Such a gel has been prepared from the ingredients indicated in the table below:
Figure imgf000035_0001
Eau g sp 100%
Figure imgf000035_0001
Water g sp 100%
(1 ) commercialisé sous la dénomination ACUDYNE DHR par la société ROHM & HAAS.(1) marketed under the name ACUDYNE DHR by the company ROHM & HAAS.
(2) commercialisé sous la dénomination CARBOPOL ULTREZ- 10 par la société NOVEON. (2) marketed under the name CARBOPOL ULTREZ-10 by the company NOVEON.
Résultats obtenus :Results obtained:
Les performances de la composition de gel coiffant décrite ci- avant ont été évaluées par des professionnels, sur des panels de modèles.The performance of the styling gel composition described above has been evaluated by professionals on panels of models.
Cette composition permet d'obtenir une très bonne fixation des cheveux, à la fois souple et durable. En particulier, le film de polymère fixant est très peu friable. En outre, cette composition s'est avérée apporter aux cheveux d'excellentes propriétés cosmétiques. En particulier, après démêlage, les cheveux ne sont pas secs, et sont particulièrement doux. This composition provides a very good fixation of the hair, both flexible and durable. In particular, the fixing polymer film is very friable. In addition, this composition has been found to provide the hair with excellent cosmetic properties. In particular, after disentangling, the hair is not dry, and is particularly soft.

Claims

REVENDICATIONS
1. Composition cosmétique comprenant, dans un milieu cosmétiquement acceptable, au moins un homopolymère d'acide acrylique, et au moins un copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), caractérisée en ce que le rapport pondéral entre la quantité de copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) d'une part et la quantité d'homopolymère d'acide acrylique d'autre part est compris entre 0, 1 et 10.Cosmetic composition comprising, in a cosmetically acceptable medium, at least one homopolymer of acrylic acid, and at least one copolymer of acrylate (s) or of methacrylate (s) and of acrylate (s) hydroxyester (s) or of methacrylate (s), characterized in that the weight ratio between the amount of copolymer of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s) on the one hand and the amount of homopolymer of acrylic acid on the other hand is between 0, 1 and 10.
2. Composition selon la revendication 1 , caractérisée en ce que le copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) est obtenu par copolymérisation d'au moins deux monomères :2. Composition according to claim 1, characterized in that the copolymer of acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) or methacrylate (s) is obtained by copolymerization of at least two monomers:
- au moins un premier monomère choisi parmi l'acide acrylique, l'acide méthacrylique, les acrylates et méthacrylates d'alkyle en C l à C4, etat least one first monomer chosen from acrylic acid, methacrylic acid, C 1 to C 4 alkyl acrylates and methacrylates, and
- au moins un second monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en C l à C4.at least one second monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.
3. Composition selon la revendication précédente, caractérisée en ce que ledit copolymère est obtenu par copolymérisation d'au moins trois monomères :3. Composition according to the preceding claim, characterized in that said copolymer is obtained by copolymerization of at least three monomers:
- au moins un premier monomère choisi parmi l'acide acrylique et l'acide méthacrylique,at least one first monomer chosen from acrylic acid and methacrylic acid,
- au moins un deuxième monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, et - au moins un troisième monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en C l à C4. at least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and at least one third monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.
4. Composition selon la revendication précédente, caractérisée en ce que ledit deuxième monomère comprend au moins un acrylate ou méthacrylate d'alkyle en Cl ou C2.4. Composition according to the preceding claim, characterized in that said second monomer comprises at least one C 1 or C 2 alkyl acrylate or methacrylate.
5. Composition selon l'une quelconque des revendications 3 et 4, caractérisée en ce que ledit troisième monomère est choisi parmi l'acrylate d'hydroxyéthyle, le méthacrylate d'hydroxyéthyle, et les mélanges de ces composés.5. Composition according to any one of claims 3 and 4, characterized in that said third monomer is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, and mixtures of these compounds.
6. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend un mélange d'au moins deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s).6. Composition according to any one of the preceding claims, characterized in that it comprises a mixture of at least two copolymers of acrylate (s) or methacrylate (s) and acrylate hydroxyester (s) or of methacrylate (s).
7. Composition selon la revendication précédente, caractérisée en ce qu'elle comprend un mélange de deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), chacun des copolymères étant obtenu par copolymérisation d'au moins trois monomères :7. Composition according to the preceding claim, characterized in that it comprises a mixture of two copolymers of acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) or methacrylate (s), each copolymers being obtained by copolymerization of at least three monomers:
- au moins un premier monomère choisi parmi l'acide acrylique et l'acide méthacrylique,at least one first monomer chosen from acrylic acid and methacrylic acid,
- au moins un deuxième monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, etat least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and
- au moins un troisième monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en C l à C4.at least one third monomer chosen from C 1 to C 4 hydroxyalkyl acrylates and methacrylates.
8. Composition selon la revendication 6, caractérisée en ce qu'elle comprend un mélange de deux copolymères d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), comprenant un premier copolymère obtenu par copolymérisation d'au moins trois monomères: au moins un premier monomère choisi parmi l'acide acrylique et l'acide méthacrylique, - au moins un deuxième monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, et au moins un troisième monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en Cl à C4 ; et un second copolymère obtenu par copolymérisation d'au moins deux monomères : au moins un premier monomère choisi parmi les acrylates et méthacrylates d'alkyle en Cl à C4, et - au moins un second monomère choisi parmi les acrylates et méthacrylates d'hydroxyalkyle en Cl à C4 ; ledit second copolymère ne contenant pas de monomères constitués d'acides carboxyliques insaturés.8. Composition according to claim 6, characterized in that it comprises a mixture of two copolymers of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), comprising a first copolymer obtained by copolymerization of at least three monomers: at least one first monomer chosen from acrylic acid and methacrylic acid; at least one second monomer chosen from C1 to C4 alkyl acrylates and methacrylates, and at least one third monomer selected from C1 to C4 hydroxyalkyl acrylates and methacrylates; and a second copolymer obtained by copolymerization of at least two monomers: at least one first monomer chosen from C1-C4 alkyl acrylates and methacrylates, and at least one second monomer chosen from hydroxyalkyl acrylates and methacrylates. C1 to C4; said second copolymer does not contain monomers consisting of unsaturated carboxylic acids.
9. Composition selon l'une quelconque des revendications 6 à 8, caractérisée en ce que les deux copolymères du mélange possèdent des températures de transition vitreuses différentes.9. Composition according to any one of claims 6 to 8, characterized in that the two copolymers of the mixture have different glass transition temperatures.
10. Composition selon la revendication précédente, caractérisée en ce que l'écart de température de transition vitreuse entre les deux copolymères est supérieur ou égal à 10°C, plus préférentiellement supérieur ou égal à 20°C, et encore plus préférentiellement supérieur ou égal à 30°C.10. Composition according to the preceding claim, characterized in that the difference in glass transition temperature between the two copolymers is greater than or equal to 10 ° C, more preferably greater than or equal to 20 ° C, and even more preferably greater than or equal to at 30 ° C.
1 1. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient au moins 0,01 % en poids de copolymère(s) d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), par rapport au poids total de la composition.1. Composition according to any one of the preceding claims, characterized in that it contains at least 0.01% by weight of copolymer (s) of acrylate (s) or methacrylate (s) and hydroxyester of acrylate (s) or methacrylate (s), relative to the total weight of the composition.
12. Composition selon la revendication précédente, caractérisée en ce qu'elle contient de 0,01 à 20 % en poids de copolymère(s) d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), plus préférentiellement de 0, 1 à 10% en poids, mieux encore de 0,5 à 8 % en poids, par rapport au poids total de la composition.12. Composition according to the preceding claim, characterized in that it contains from 0.01 to 20% by weight of copolymer (s) acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) ) or methacrylate (s), more preferably from 0.1 to 10% by weight, more preferably from 0.5 to 8% by weight, relative to the total weight of the composition.
13. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que Fhomopolymère d'acide acrylique est non réticulé.13. Composition according to any one of the preceding claims, characterized in that the homopolymer of acrylic acid is uncrosslinked.
14. Composition selon l'une quelconque des revendications 1 à 12, caractérisée en ce que Fhomopolymère d'acide acrylique est réticulé en tout ou partie. 14. Composition according to any one of claims 1 to 12, characterized in that the homopolymer of acrylic acid is crosslinked in whole or in part.
15. Composition selon la revendication précédente, caractérisée en ce que Fhomopolymère d'acide acrylique est réticulé avec un éther d'allyle.15. Composition according to the preceding claim, characterized in that the homopolymer of acrylic acid is crosslinked with an allyl ether.
16. Composition selon la revendication précédente, caractérisée en ce que Fhomopolymère d'acide acrylique est réticulé avec un éther d'allyle et de pentaérythritol, avec un éther d'allyle et de sucrose, ou avec un éther d'allyle et de propylène.16. Composition according to the preceding claim, characterized in that the homopolymer of acrylic acid is crosslinked with an allyl ether and pentaerythritol, with an allyl ether and sucrose, or with an allyl ether and propylene.
17. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient au moins 0,01 % en poids d'homopolymère d'acide acrylique, par rapport au poids total de la composition.17. Composition according to any one of the preceding claims, characterized in that it contains at least 0.01% by weight of acrylic acid homopolymer, relative to the total weight of the composition.
18. Composition selon la revendication précédente, caractérisée en ce qu'elle contient de 0,01 à 10 % en poids d'homopolymère d'acide acrylique, de préférence de 0,05 à 5% en poids, mieux encore de 0, 1 à 3 % en poids, par rapport au poids total de la composition.18. Composition according to the preceding claim, characterized in that it contains from 0.01 to 10% by weight of homopolymer of acrylic acid, preferably from 0.05 to 5% by weight, more preferably 0.1% by weight. at 3% by weight, relative to the total weight of the composition.
19. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le rapport pondéral entre la quantité de copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s) d'une part et la quantité d'homopolymère d'acide acrylique d'autre part est compris entre 1 et 8.19. Composition according to any one of the preceding claims, characterized in that the weight ratio between the amount of copolymer of acrylate (s) or methacrylate (s) and hydroxyester acrylate (s) or methacrylate ( s) on the one hand and the amount of acrylic acid homopolymer on the other hand is between 1 and 8.
20. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce que le milieu cosmétiquement acceptable comprend de l'eau et/ou au moins un solvant cosmétiquement acceptable choisi parmi les alcools inférieurs en C1-20. Composition according to any one of the preceding claims, characterized in that the cosmetically acceptable medium comprises water and / or at least one cosmetically acceptable solvent chosen from C 1 - lower alcohols.
C4; les polyols; les éthers de polyols ; les alcanes en C5-C10 ; les cétones en C3 -4; les acétates d'alkyle en C1-C4; le diméthoxyéthane, le diéthoxyéthane ; et leurs mélanges.C 4 ; polyols; polyol ethers; C 5 -C 10 alkanes; C 3 -4 ketones; C 1 -C 4 alkyl acetates; dimethoxyethane, diethoxyethane; and their mixtures.
21. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient également au moins un corps gras, choisi parmi les huiles végétales, les huiles animales, les huiles minérales, les huiles naturelles ou synthétiques, les alcools gras, les cires et leurs mélanges. 21. Composition according to any one of the preceding claims, characterized in that it also contains at least one fatty substance, chosen from vegetable oils, animal oils, mineral oils, natural or synthetic oils, fatty alcohols, waxes and their mixtures.
22. Composition selon la revendication précédente, caractérisée en ce que les corps gras sont présents en une quantité allant de 0, 1 à 30 % en poids, de préférence de 1 à 20 % en poids, par rapport au poids total de la composition. 22. Composition according to the preceding claim, characterized in that the fatty substances are present in an amount ranging from 0.1 to 30% by weight, preferably from 1 to 20% by weight, relative to the total weight of the composition.
23. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient également au moins un tensioactif, choisi parmi les tensioactifs cationiques, les tensioactifs anioniques, les tensioactifs non ioniques, les tensioactifs amphotères ou zwittérioniques. 23. Composition according to any one of the preceding claims, characterized in that it also contains at least one surfactant, selected from cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants.
24. Composition selon la revendication précédente, caractérisée en ce qu'elle contient au moins 0,01 % en poids de tensioactif(s), par rapport au poids total de la composition.24. Composition according to the preceding claim, characterized in that it contains at least 0.01% by weight of surfactant (s), relative to the total weight of the composition.
25. Composition selon la revendication précédente, caractérisée en ce qu'elle contient de 0,01 à 20 % en poids de tensioactif(s), de préférence de 0,05 à 4 % en poids, par rapport au poids total de la composition.25. Composition according to the preceding claim, characterized in that it contains from 0.01 to 20% by weight of surfactant (s), preferably from 0.05 to 4% by weight, relative to the total weight of the composition. .
26. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend en outre au moins une silicone ou un dérivé de silicone, sous forme soluble, dispersée ou micro-dispersée.26. Composition according to any one of the preceding claims, characterized in that it further comprises at least one silicone or a silicone derivative, in soluble, dispersed or micro-dispersed form.
27. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle comprend au moins un polymère fixant additionnel différent du copolymère d'acrylate(s) ou de méthacrylate(s) et d'hydroxyester d'acrylate(s) ou de méthacrylate(s), de nature anionique, cationique, non ionique ou amphotère.27. Composition according to any one of the preceding claims, characterized in that it comprises at least one additional fixing polymer other than acrylate (s) copolymer or methacrylate (s) and acrylate hydroxyester (s). or of methacrylate (s), of anionic, cationic, nonionic or amphoteric nature.
28. Composition selon la revendication précédente, caractérisée en ce qu'elle contient au moins 0,01 % en poids de polymère fixant additionnel, par rapport au poids total de la composition. 28. Composition according to the preceding claim, characterized in that it contains at least 0.01% by weight of additional fixing polymer, relative to the total weight of the composition.
29. Composition selon la revendication précédente, caractérisée en ce qu'elle contient de 0,01 à 20% en poids de polymère fixant additionnel, de préférence de 0,05 à 15% en poids, mieux encore de 0, 1 à 10 % en poids par rapport au poids total de la composition. 29. Composition according to the preceding claim, characterized in that it contains from 0.01 to 20% by weight of additional fixing polymer, preferably from 0.05 to 15% by weight, more preferably from 0.1 to 10% by weight. by weight relative to the total weight of the composition.
30. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle contient en outre au moins un additif choisi parmi les agents nacrants ; les agents opacifiants ; les agents plastifiants ; les filtres solaires ; les parfums ; les colorants ; les conservateurs ; les agents de stabilisation du pH ; les acides ; les bases ; les polyols; les charges minérales ; les paillettes, et tout autre additif classiquement utilisé dans le domaine cosmétique.30. Composition according to any one of the preceding claims, characterized in that it further contains at least one additive chosen from pearlescent agents; opacifying agents; plasticizers; solar filters; the perfumes ; dyes; conservatives ; pH stabilizers; acids; the basics ; polyols; mineral charges; glitter, and any other additive conventionally used in the cosmetic field.
31. Composition selon l'une quelconque des revendications précédentes, caractérisée en ce qu'elle se présente sous forme de liquide plus ou moins épaissi, de gel, de crème, de pâte ou de mousse.31. Composition according to any one of the preceding claims, characterized in that it is in the form of a more or less thickened liquid, gel, cream, paste or foam.
32. Composition selon la revendication précédente, caractérisée en ce qu'elle se présente sous forme de gel.32. Composition according to the preceding claim, characterized in that it is in gel form.
33. Procédé de traitement cosmétique des cheveux, caractérisé en ce qu'il consiste à appliquer sur les cheveux une quantité efficace d'une composition selon l'une quelconque des revendications précédentes, puis à effectuer un éventuel rinçage après un éventuel temps de pose.33. A cosmetic hair treatment method, characterized in that it consists in applying to the hair an effective amount of a composition according to any one of the preceding claims, then to perform a possible rinsing after a possible exposure time.
34. Procédé selon la revendication précédente, caractérisé en ce que la composition n'est pas rincée. 34. Process according to the preceding claim, characterized in that the composition is not rinsed.
35. Utilisation d'une composition selon l'une quelconque des revendications 1 à 32, comme produit capillaire.35. Use of a composition according to any one of claims 1 to 32, as a hair product.
36. Utilisation d'une composition selon l'une quelconque des revendications 1 à 32, pour la mise en forme et/ou le maintien de la coiffure. 36. Use of a composition according to any one of claims 1 to 32, for shaping and / or maintaining the hairstyle.
PCT/FR2007/050873 2006-03-03 2007-03-02 Cosmetic composition comprising an acrylic acid homopolymer and an acrylate or methacrylate and acrylate or methacrylate hydroxyester copolymer, and the use thereof as a hair care product WO2007099269A2 (en)

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