EP1051146A1 - Hairstyling composition comprising a polymer with particular characteristics and an ionic film forming polymer - Google Patents

Hairstyling composition comprising a polymer with particular characteristics and an ionic film forming polymer

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Publication number
EP1051146A1
EP1051146A1 EP99956077A EP99956077A EP1051146A1 EP 1051146 A1 EP1051146 A1 EP 1051146A1 EP 99956077 A EP99956077 A EP 99956077A EP 99956077 A EP99956077 A EP 99956077A EP 1051146 A1 EP1051146 A1 EP 1051146A1
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EP
European Patent Office
Prior art keywords
polymer
polymers
chosen
vinyl
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99956077A
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German (de)
French (fr)
Inventor
Henri Samain
Christine Dupuis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LOreal SA
Original Assignee
LOreal SA
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Publication date
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Publication of EP1051146A1 publication Critical patent/EP1051146A1/en
Ceased legal-status Critical Current

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Classifications

    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/368—Carboxylic acids; Salts or anhydrides thereof with carboxyl groups directly bound to carbon atoms of aromatic rings
    • 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
    • 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
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; 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
    • A61K8/817—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87—Polyurethanes
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/899—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing sulfur, e.g. sodium PG-propyldimethicone thiosulfate copolyol
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures
    • A61K2800/594—Mixtures of polymers

Definitions

  • the subject of the invention is a styling composition
  • a styling composition comprising, in a cosmetically acceptable medium, at least one polymer (A) with particular characteristics and at least " one polymer (B) chosen from anionic, cationic or amphoteric film-forming polymers.
  • A polymer
  • B polymer chosen from anionic, cationic or amphoteric film-forming polymers.
  • a method of shaping or maintaining hair using this composition as well as its use for the formulation of styling products such as hairsprays, sprays or mousses, with a view to obtaining the maintenance or the hairstyle shaping.
  • the most common hair products for fixing the hair on the cosmetics market are aerosol or pump spray compositions such as hairsprays, sprays or mousses, essentially consisting of a solution, most often alcoholic or hydroalcoholic and a film-forming polymer soluble in water or in alcohol, mixed with various cosmetic adjuvants.
  • these hair formulations such as mousses, gels and especially sprays and aerosol lacquers intended to maintain the shape of the hairstyle do not yet allow the hairstyle to resist satisfactorily the various natural movements of life such as walking, head movements or gusts of wind.
  • the polymers used for the formulation of these hair products are anionic, amphoteric or nonionic film-forming polymers, which lead to the formation of films having a more or less hard and brittle nature.
  • the polymer is too brittle, the percentage of elongation at break measured on the film is low, that is to say generally less than 2% and the holding of the hairstyle is not ensured over time.
  • these polymers have already been mixed with plasticizers and obtained more flexible and non-friable coatings.
  • these films are deformable and plastic, that is to say that after deformation, they recover very little of their initial shape. If the holding of the hairstyle is improved, it is not yet satisfactory since the shape of the hairstyle changes over time.
  • compositions comprising a combination of film-forming polymers, such as, for example, a cellulose polymer and an acrylic polymer.
  • film-forming polymers such as, for example, a cellulose polymer and an acrylic polymer.
  • the subject of the invention is a styling composition
  • a cosmetically acceptable medium comprising, in a cosmetically acceptable medium:
  • a rate of elongation at break ( ⁇ r ) greater than or equal to 300%; (ii) a recovery at 300 seconds (R 30 o) greater than or equal to 45%; and (iii) when the recovery at 300 seconds is between 45 and 60%, then the elongation is less than 1300%;
  • Another object of the present invention relates to a method of shaping or maintaining the hairstyle comprising the use of this composition.
  • Yet another object of the present invention relates to the use of this composition for the manufacture of hair cosmetic compositions, with a view to obtaining maintenance or shaping of the hairstyle.
  • the polymers (A) particularly targeted by the present invention are those distributed by Goodrich under the names Avalure AC 315® and V29®.
  • the term film obtained by drying at room temperature (22 ⁇ 2 ° C) and at a relative humidity level of 50% ⁇ 5% means the film obtained under these conditions from a mixture with 6% of active material (ai) of polymer A with ethanol or water, the quantity of mixture being adapted to obtain, in a teflon matrix, a film with a thickness of 500 ⁇ 50 ⁇ m. Drying is continued until the weight of the film no longer changes, which represents approximately 12 days.
  • Polymers A soluble or partially soluble in ethanol are tested in ethanol.
  • the other polymers are tested in water in soluble or dispersed form.
  • the rate of elongation at break and the recovery rate are evaluated by means of the tests described below.
  • the film is cut into test pieces of rectangular shape, length 80 mm and width 15 mm.
  • the tests are carried out on a device marketed under the name Lloyd or marketed under the name Zwic under the same conditions of temperature and humidity as for drying, that is to say a temperature of 22 ⁇ 2 ° C. and a relative humidity level of 50 ⁇ 5%.
  • test pieces are drawn at a speed of 20mm / min and the distance between the jaws is 50 ⁇ 1 mm.
  • the stress is relaxed by imposing a return speed equal to the traction speed, ie 20mm / min and the elongation of the test piece is measured in percentage, after return to zero load ( ⁇ j).
  • R300 (( ⁇ max- ⁇ oo) / ⁇ max ) x 100
  • cationic, anionic or amphoteric film-forming polymers (B) which can be used in accordance with the invention are described below.
  • the cationic film-forming polymers which can be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked to it, and having a molecular weight of between 500 and around 5,000,000 and preferably between 1,000 and 3,000,000.
  • R3 denotes a hydrogen atom or a CH3 radical
  • A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms
  • R4, R5, R ⁇ . identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical;
  • R-] and R2 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms;
  • X denotes a methosulfate anion or a halide such as chloride or bromide.
  • the copolymers of family (1) also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls, acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
  • Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by the company MEYHALL.
  • chitosans or their salts are in particular the acetate, lactate, glutamate, gluconate or the pyrrolidone carboxylate of chitosan.
  • chitosan having a deacetylation rate of 90.5% by weight sold under the name KYTAN BRUT STANDARD by the company ABER TECHNOLOGIES
  • chitosan pyrrolidone carboxylate sold under the name KYTAMER PC by the company AMERCHOL.
  • the anionic film-forming polymers generally used are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acid and have a molecular weight of between approximately 500 and 5,000,000. 1) The carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula
  • n is an integer from 0 to 10
  • A denotes a methylene group, optionally linked 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
  • R7 denotes a hydrogen atom, a phenyl or benzyl group
  • R ⁇ denotes a hydrogen atom, a lower alkyl or carboxyl group
  • Rg denotes a hydrogen atom, a lower alkyl group; a group -CH2-COOH, phenyl or benzyl;
  • a lower alkyl radical preferably denotes a group having 1 to 4 carbon atoms and in particular, methyl and ethyl.
  • anionic film-forming polymers with carboxylic groups preferred according to the invention are:
  • 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 ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain such as those containing at least 5 carbon atoms, these polymers possibly being able to be grafted and crosslinked or else a vinyl, allylic or methallylic ester of an ⁇ - or ⁇ -cyclic carboxylic acid.
  • Such polymers are described inter alia in French patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH.
  • copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified;
  • monomers chosen from vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified;
  • copolymers comprising (i) one or more maleic, citraconic, itaconic anhydrides and (ii) one or more monomers chosen from allylic or methaliylic esters optionally comprising one or more acrylamide, methacrylamide, ⁇ -olefin groups, acrylic or methacrylic esters, acrylic or methacrylic or vinylpyrrolidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.
  • monomers chosen from allylic or methaliylic esters optionally comprising one or more acrylamide, methacrylamide, ⁇ -olefin groups, acrylic or methacrylic esters, acrylic or methacrylic or vinylpyrrolidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.
  • the polymers comprising the sulfonic groups are polymers comprising vinyisulfonic, styrene sulfonic, naphthalene sulfonic or acrylamido alkylsulfonic units.
  • polymers can in particular be chosen from - the salts of polyvinylsulfonic acid having a molecular weight of between approximately 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 the vinylpyrrolidone.
  • an unsaturated comonomer such as acrylic or methacrylic acids and their esters as well as acrylamide or its derivatives, vinyl ethers and the vinylpyrrolidone.
  • the anionic film-forming polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate / tert-butyl vinyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold 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 / mono ester maleic anhydride copolymer sold under the name GANTREZ ES
  • the most particularly preferred anionic film-forming polymers are chosen from the methyl ester / maleic mono esterified anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tertiobutylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the vinyl acetate / tert-butyl vinyl benzoate / crotonic acid terpolymers and the crotonic acid / acetate terpolymers of vinyl / vinyl neododecanoate sold under the name Resin 28-29-30 by the company NATIONAL STARCH, the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX OR MAE by
  • amphoteric film-forming polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed statistically in the polymer chain where B denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or else B and C can denote groups deriving from zwitterionic monomers of carboxybetaines or of sulphobetaines; B and C can also denote 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 sulphonic group linked via a hydrocarbon radical or else B and C are part of a chain of a polymer with an ethylene ⁇ , ⁇ -dicarboxylic unit, one of the " carboxylic groups of which has been caused to react with a polyamine comprising one or more
  • amphoteric film-forming 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-chloroacrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic atom
  • dialkylaminoalkylmethacrylate and acrylate the dialkylaminoalkylmethacrylamide and acrylamide.
  • polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
  • the N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups of which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl acrylamide, N-tertiooctyl acrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides.
  • the acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.
  • the preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.
  • Copolymers are particularly used, the name CTFA (4th Ed., 1991) being Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
  • RJ Q represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or from d 'a radical derived from the addition of any one of said acids with a primary bis or secondary bis amino
  • Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100 mol%, the radical
  • the saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic, trimethyl-2,2,4-adipic acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
  • the alca ⁇ es sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
  • R-] -] denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group
  • y and z represents an integer from 1 to 3
  • 2 and R-13 represent a hydrogen, methyl, ethyl or propyl atom
  • R14 and R-15 represent an atom of hydrogen or an alkyl radical such that the sum of the carbon atoms in R1 and R15 does not exceed 10.
  • the polymers comprising such units may also contain 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.
  • non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.
  • the copolymer of methyl methacrylate / dimethyl carboxymethylammonio ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
  • R 16 represents a radical of formula:
  • R17, R ⁇ ] 8 and R19 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 several nitrogen atoms and / or optionally substituted by one or more amino, hydroxyl, carboxyl, alcolylthio groups, sulfonic, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R-17, R ⁇
  • 8 and Rig being in this case a hydrogen atom; or if q 1, R-17, RJ S and R19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
  • R20 represents a hydrogen atom, a CH3O, CH3CH2O, phenyl radical
  • R21 denotes hydrogen or a lower alkyl radical such as methyl, ethyl
  • R22 denotes hydrogen or a lower alkyl radical such as methyl, ethyl
  • R23 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R24- ⁇ (R22) 2.
  • R 24 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH 3 ) -, R 2 2 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms.
  • Amphoteric polymers of the -DXDX- type chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:
  • E or E ' denote a bivalent radical which is a straight or branched chain alkylene radical containing up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 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 groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, 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 bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloroacetate.
  • (9) (C 1 -C 5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine.
  • These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
  • amphoteric film-forming polymers which are particularly preferred according to the invention are those of the family (3) such as the copolymers whose name CTFA is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the names AMPHOMER, AMHOMER LV 71 or LOVOCRYL 47 by the company NATIONAL STARCH and those of the family (4) such as the copolymers of methyl methacrylate / dimethyl carboxymethylammonio ethyl methylmethacrylate, for example sold under the name DIAFORMER Z301 by the company SANDOZ.
  • family (3) such as the copolymers whose name CTFA is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the names AMPHOMER, AMHOMER LV 71 or LOVOCRYL 47 by the company NATIONAL STARCH
  • those of the family (4)
  • film-forming anionic polymers of grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted on said main chain.
  • These polymers are for example described in patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0582 152 and WO 93 / 23009 and US patents 4,693,935, US 4,728,571 and US 4,972,037.
  • Such polymers are, for example, the copolymers capable of being obtained by radical polymerization from the mixture of monomers consisting of: a) 50 to 90% by weight of tert-butyl acrylate; b) 0 to 40% by weight of acrylic acid; c) 5 to 40% by weight of silicone macromer of formula:
  • v being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.
  • grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, mixed polymer units of the poly (meth) acrylic acid type and of the poly type. alkyl (meth) acrylate and polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, polymeric units of the isobutyl poly (meth) acrylate type.
  • PDMS polydimethylsiloxanes
  • polyurethanes particularly targeted by the present invention are those described in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0 648 485 of which the Applicant is the Holder, as well as patent EP 0 656 021 or WO 94 / 03510 from the company BASF and EP 0 619 111 from the company National Starch.
  • the film-forming polymer (s) (A) are preferably present at concentrations of between 0.05 and 20% by weight, more preferably between 0.1 and 15% by weight, and more preferably between 0.25 and 10% by weight relative to the total weight of the composition.
  • the film-forming polymer (s) (B) are preferably present at concentrations of between 0.05 and 20% by weight, more preferably between 0.1 and 15% by weight, and more preferably between 0.25 and 10% by weight relative to the total weight of the composition.
  • the polymer concentrations (A) and (B) are advantageously chosen, so that the ratio of the polymer concentration (A) to the polymer concentration (B) is between 4000 and 0.002.
  • the cosmetically acceptable medium is preferably constituted by water or one or more cosmetically acceptable solvents such as alcohols or water-solvent mixtures (s), these solvents preferably being C ⁇ -C 4 alcohols.
  • composition of the invention may also contain at least one additive chosen from thickeners, surfactants, perfumes, preservatives, sun filters, proteins, vitamins, non-fixing polymers, and any other additive conventionally used in cosmetic compositions intended to be applied to the hair.
  • compositions can be packaged in various forms, in particular in pump dispensers or in aerosol containers, in order to ensure application of the composition in vaporized form or in the form of foam.
  • forms of packaging are indicated, for example, when it is desired to obtain a spray, a lacquer or a foam for fixing or treating the hair.
  • the compositions according to the invention can also be in the form of creams, gels, emulsions, lotions or waxes.
  • composition according to the invention when packaged in the form of an aerosol in order to obtain a lacquer or a foam, it comprises at least one propellant which can be chosen from volatile hydrocarbons such as n-butane, propane, isobutane, pentane, a chlorinated and / or fluorinated hydrocarbon and their mixtures.
  • propellants such as n-butane, propane, isobutane, pentane, a chlorinated and / or fluorinated hydrocarbon and their mixtures.
  • Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen, compressed air can also be used as a propellant.
  • Mixtures of propellants can also be used.
  • dimethyl ether is used.
  • the propellant is present at a concentration between 5 and 90% by weight relative to the total weight of the composition in the aerosol device and, more particularly, at a concentration between 10 and 60%.
  • compositions according to the invention can be applied to dry or damp hair.
  • styling compositions are produced, all comprising Avalure AC315 as polymer (A).
  • One of the styling compositions is in accordance with the prior art and comprises ethyl cellulose as a film-forming polymer (B).
  • the other 4 styling compositions are in accordance with the present invention and comprise an amphoteric, anionic or cationic film-forming polymer.
  • compositions 1 to 5 packaged in aerosol are applied to locks of Eurochestian hair of length 18 cm and 20 grams.
  • compositions according to the present invention provide significantly better performance in terms of softness and disentangling than the compositions comprising a combination of polymers according to the prior art.

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Abstract

The invention concerns a hairstyling composition comprising, in a cosmetically acceptable medium: (1) at least a polymer (A) selected such that the film obtained by drying of a mixture of said polymer (A) with ethanol or water, at room temperature and at a relative moisture content of 50 % has a mechanical profile defined by at least: (i) an ultimate elongation rate (εr) not less than 300 % ; (ii) a creep at 300 seconds (R300) not less than 45 % ; and (iii) when the creep at 300 seconds ranges between 45 and 60 %, the elongation is less than 1300 % ; (2) at least a film forming polymer (B) different from polymer (A) and selected among anionic, cationic or amphoteric film forming polymers. The invention also concerns a hairstyling or hair-fixing method using said composition and its use for formulating hairstyling products such as lacquers, sprays and foams for hairstyling and hair fixing.

Description

COMPOSITION DE COIFFAGE COMPRENANT UN POLYMERE AUX CARACTERISTIQUES PARTICULIERES ET UN POLYMERE FILMOGENE HAIRDRESSING COMPOSITION COMPRISING A POLYMER WITH SPECIAL CHARACTERISTICS AND A FILM-FORMING POLYMER
IONIQUEIONIC
L'invention a pour objet une composition de coiffage comprenant, dans un milieu cosmétiquement acceptable, au moins un polymère (A) aux caractéristiques particulières et au moins" un polymère (B) choisi parmi les polymères filmogènes anioniques, cationiques ou amphotères. Elle vise également un procédé de mise en forme ou de maintien des cheveux à l'aide de cette composition ainsi que son utilisation pour la formulation de produits de coiffage tels que les laques, les sprays ou les mousses, en vue d'obtenir le maintien ou la mise en forme de la coiffure.The subject of the invention is a styling composition comprising, in a cosmetically acceptable medium, at least one polymer (A) with particular characteristics and at least " one polymer (B) chosen from anionic, cationic or amphoteric film-forming polymers. also a method of shaping or maintaining hair using this composition as well as its use for the formulation of styling products such as hairsprays, sprays or mousses, with a view to obtaining the maintenance or the hairstyle shaping.
Les produits capillaires pour la fixation des cheveux les plus répandus sur le marché de la cosmétique sont des compositions à pulvériser en aérosol ou en flacon pompe tels que les laques, les sprays ou les mousses, essentiellement constituées d'une solution le plus souvent alcoolique ou hydroalcoolique et d'un polymère filmogène soluble dans l'eau ou dans l'alcool, en mélange avec divers adjuvants cosmétiques.The most common hair products for fixing the hair on the cosmetics market are aerosol or pump spray compositions such as hairsprays, sprays or mousses, essentially consisting of a solution, most often alcoholic or hydroalcoholic and a film-forming polymer soluble in water or in alcohol, mixed with various cosmetic adjuvants.
Toutefois, ces formulations capillaires telles que les mousses, gels et surtout les sprays et les laques aérosols destinées à maintenir la forme de la coiffure ne permettent encore pas à la coiffure de résister de manière satisfaisante aux différents mouvements naturels de la vie comme la marche, les mouvements de tête ou les coups de vent.However, these hair formulations such as mousses, gels and especially sprays and aerosol lacquers intended to maintain the shape of the hairstyle do not yet allow the hairstyle to resist satisfactorily the various natural movements of life such as walking, head movements or gusts of wind.
Les polymères utilisés pour la formulation de ces produits capillaires sont des polymères filmogènes anioniques, amphotères ou non ioniques, qui conduisent à la formation de films possédant un caractère plus ou moins dur et cassant. Lorsque le polymère est trop cassant, le pourcentage d'allongement à la rupture mesuré sur le film est faible, c'est-à-dire en général inférieur à 2 % et la tenue de la coiffure n'est pas assurée dans le temps.The polymers used for the formulation of these hair products are anionic, amphoteric or nonionic film-forming polymers, which lead to the formation of films having a more or less hard and brittle nature. When the polymer is too brittle, the percentage of elongation at break measured on the film is low, that is to say generally less than 2% and the holding of the hairstyle is not ensured over time.
Pour remédier à ce problème, on a déjà mélangé ces polymères avec des plastifiants et obtenu des revêtements plus souples et non friables. Toutefois, ces films sont déformables et plastiques, c'est-à-dire qu'après déformation, ils ne récupèrent que très peu de leur forme initiale. Si la tenue de la coiffure est améliorée, elle n'est pas encore satisfaisante puisque la forme de la coiffure évolue dans le temps.To remedy this problem, these polymers have already been mixed with plasticizers and obtained more flexible and non-friable coatings. However, these films are deformable and plastic, that is to say that after deformation, they recover very little of their initial shape. If the holding of the hairstyle is improved, it is not yet satisfactory since the shape of the hairstyle changes over time.
Des résultats plus satisfaisants en terme de tenue ont été obtenus avec des compositions comprenant une association de polymères filmogènes, tels que par exemple un polymère cellulosique et un polymère acrylique. Toutefois, ces compositions ne donnent encore pas entièrement satisfaction, dans la mesure où les cheveux perdent certaines de leurs propriétés cosmétiques naturelles.More satisfactory results in terms of resistance have been obtained with compositions comprising a combination of film-forming polymers, such as, for example, a cellulose polymer and an acrylic polymer. However, these compositions are not yet entirely satisfactory, insofar as the hair loses some of its natural cosmetic properties.
On recherche donc des compositions cosmétiques pour le maintien et/ou la fixation de la coiffure qui procurent à la chevelure, outre une fixation durable, de bonnes propriétés cosmétiques, notamment un bon démêlage, de la douceur et un aspect agréable.We are therefore looking for cosmetic compositions for maintaining and / or fixing the hairstyle which provide the hair, in addition to lasting fixation, with good cosmetic properties, in particular good disentangling, softness and a pleasant appearance.
De manière surprenante et inattendue, la Demanderesse a découvert qu'il était possible de remédier aux problèmes techniques évoqués ci-dessus, en utilisant certaines associations spécifiques de polymères.Surprisingly and unexpectedly, the Applicant has discovered that it is possible to remedy the technical problems mentioned above, by using certain specific combinations of polymers.
L'invention a pour objet composition de coiffage comprenant, dans un milieu cosmétiquement acceptable:The subject of the invention is a styling composition comprising, in a cosmetically acceptable medium:
(1 ) au moins un polymère (A) choisi de telle sorte qu'un film obtenu par séchage d'un mélange de ce polymère (A) avec de l'éthanol ou de l'eau, à température ambiante et à un taux d'humidité relative de 50 %, présente un profil mécanique défini par au moins:(1) at least one polymer (A) chosen such that a film obtained by drying a mixture of this polymer (A) with ethanol or water, with ambient temperature and at a relative humidity level of 50%, has a mechanical profile defined by at least:
(i) un taux d'allongement à la rupture (εr) supérieur ou égal à 300 %; (ii) une recouvrance à 300 secondes (R30o) supérieure ou égale à 45 %; et (iii) lorsque la recouvrance à 300 secondes est comprise entre 45 et 60 %, alors l'allongement est inférieur à 1300 %;(i) a rate of elongation at break (ε r ) greater than or equal to 300%; (ii) a recovery at 300 seconds (R 30 o) greater than or equal to 45%; and (iii) when the recovery at 300 seconds is between 45 and 60%, then the elongation is less than 1300%;
(2) au moins un polymère (B) filmogène et différent du polymère (A) et choisi parmi les polymères filmogènes anioniques, cationiques ou amphotères.(2) at least one film-forming polymer (B) different from the polymer (A) and chosen from anionic, cationic or amphoteric film-forming polymers.
Un autre objet de la présente invention concerne un procédé de mise en forme ou de maintien de la coiffure comprenant la mise en œuvre de cette composition.Another object of the present invention relates to a method of shaping or maintaining the hairstyle comprising the use of this composition.
Encore un autre objet de la présente invention concerne l'utilisation de cette composition pour la fabrication de compositions cosmétiques capillaires, en vue d'obtenir un maintien ou une mise en forme de la coiffure.Yet another object of the present invention relates to the use of this composition for the manufacture of hair cosmetic compositions, with a view to obtaining maintenance or shaping of the hairstyle.
Les polymères (A) particulièrement visés par la présente invention sont ceux distribués par Goodrich sous l'appellation Avalure AC 315® et V29®.The polymers (A) particularly targeted by the present invention are those distributed by Goodrich under the names Avalure AC 315® and V29®.
Au sens de la présente invention, on entend par film obtenu par séchage à température ambiante (22 ± 2°C) et à un taux d'humidité relative de 50 % ± 5%, le film obtenu dans ces conditions à partir d'un mélange à 6 % de matière active (m. a.) de polymère A avec de l'éthanol ou de l'eau, la quantité de mélange étant adaptée pour obtenir dans une matrice en téflon, un film d'épaisseur de 500 ± 50 μm. Le séchage est poursuivi jusqu'à ce que le poids du film n'évolue plus, ce qui représente environ 12 jours. Les polymères A solubles ou partiellement solubles dans l'éthanol sont testés dans l'éthanol. Les autre polymères sont testés dans l'eau sous forme soluble ou dispersée. Au sens de la présente invention, le taux d'élongation à la rupture et le taux de recouvrance sont évalués aux moyens des essais décrits ci-après.For the purposes of the present invention, the term film obtained by drying at room temperature (22 ± 2 ° C) and at a relative humidity level of 50% ± 5% means the film obtained under these conditions from a mixture with 6% of active material (ai) of polymer A with ethanol or water, the quantity of mixture being adapted to obtain, in a teflon matrix, a film with a thickness of 500 ± 50 μm. Drying is continued until the weight of the film no longer changes, which represents approximately 12 days. Polymers A soluble or partially soluble in ethanol are tested in ethanol. The other polymers are tested in water in soluble or dispersed form. Within the meaning of the present invention, the rate of elongation at break and the recovery rate are evaluated by means of the tests described below.
Pour effectuer les essais de traction, le film est découpé en éprouvettes de forme rectangulaire, de longueur 80 mm et de largeur 15 mm.To carry out the tensile tests, the film is cut into test pieces of rectangular shape, length 80 mm and width 15 mm.
Les essais sont réalisés sur un appareil commercialisé sous l'appellation Lloyd ou commercialisé sous l'appellation Zwic dans les mêmes conditions de températures et d'humidité que pour le séchage, c'est-à-dire une température de 22 ± 2 °C et un taux d'humidité relative de 50 ± 5 %.The tests are carried out on a device marketed under the name Lloyd or marketed under the name Zwic under the same conditions of temperature and humidity as for drying, that is to say a temperature of 22 ± 2 ° C. and a relative humidity level of 50 ± 5%.
Les éprouvettes sont étirées à la vitesse de 20mm/mn et la distance entre les mors est de 50 ± 1 mm.The test pieces are drawn at a speed of 20mm / min and the distance between the jaws is 50 ± 1 mm.
Pour déterminer la recouvrance instantanée (Ri), on procède comme suit:To determine the instantaneous recovery (Ri), we proceed as follows:
- on étire l'éprouvette de 150 % (εmax) c'est-à-dire 1 ,5 fois sa longueur initiale do)- the specimen is stretched by 150% (ε max ), that is to say 1.5 times its initial length do)
- on relâche la contrainte en imposant une vitesse de retour égale à la vitesse de traction, soit 20mm/mn et on mesure l'allongement de l'éprouvette en pourcentage , après retour à charge nulle (εj).- the stress is relaxed by imposing a return speed equal to the traction speed, ie 20mm / min and the elongation of the test piece is measured in percentage, after return to zero load (εj).
La recouvrance instantanée en % (Ri) est donnée par la formule ci-après:The instant recovery in% (Ri) is given by the following formula:
Ri = ((εmaχ - εi)/ εmaχ) x 100Ri = ((ε ma χ - εi) / ε ma χ) x 100
Pour déterminer la recouvrance à 300 secondes, on maintient à contrainte nulle pendant 300 secondes supplémentaires, l'éprouvette ayant subi les opérations précédentes, et on mesure son taux d'allongement en pourcentage (ε30o). La recouvrance à 300 secondes en % (R300) est donnée par la formule ci-après:To determine the recovery at 300 seconds, the specimen having undergone the preceding operations is maintained at zero stress for an additional 300 seconds, and its percentage elongation rate is measured (ε 30 o). The recovery at 300 seconds in% (R300) is given by the following formula:
R300 = ((εmax- ε oo)/ εmax) x 100R300 = ((εmax- ε oo) / ε max ) x 100
Les polymères filmogènes (B) cationiques, anioniques ou amphotères utilisables conformément à l'invention sont décrits ci-après.The cationic, anionic or amphoteric film-forming polymers (B) which can be used in accordance with the invention are described below.
Les polymères filmogènes cationiques utilisables selon la présente invention sont de préférence choisis parmi les polymères comportant des groupements aminé primaire, secondaire, tertiaire et/ou quaternaire faisant partie de la chaîne polymère ou directement reliés à celle-ci, et ayant un poids moléculaire compris entre 500 et environ 5.000.000 et de préférence entre 1000 et 3.000.000.The cationic film-forming polymers which can be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and / or quaternary amine groups forming part of the polymer chain or directly linked to it, and having a molecular weight of between 500 and around 5,000,000 and preferably between 1,000 and 3,000,000.
Parmi ces polymères, on peut citer plus particulièrement les polymères cationiques suivants:Among these polymers, there may be mentioned more particularly the following cationic polymers:
(1 ) les homopolymères ou copolymères dérivés d'esters ou d'amides acryliques ou méthacryliques et comportant au moins un des motifs de formules suivantes:(1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulas:
--
dans lesquelles:in which:
R3 désigne un atome d'hydrogène ou un radical CH3; A est un groupe alkyle linéaire ou ramifié de 1 à 6 atomes de carbone ou un groupe hydroxyalkyle de 1 à 4 atomes de carbone ;R3 denotes a hydrogen atom or a CH3 radical; A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms;
R4, R5, Rβ. identiques ou différents, représentent un groupe alkyle ayant de 1 à 18 atomes de carbone ou un radical benzyle; R-] et R2 représentent hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone;R4, R5, Rβ. identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical; R-] and R2 represent hydrogen or an alkyl group having from 1 to 6 carbon atoms;
X désigne un anion méthosulfate ou un halogénure tel que chlorure ou bromure.X denotes a methosulfate anion or a halide such as chloride or bromide.
Les copolymères de la famille (1 ) contiennent en outre un ou plusieurs motifs dérivant de comonomères pouvant être choisis dans la famille des acrylamides, méthacrylamides, diacétones acrylamides, acrylamides et méthacrylamides substitués sur l'azote par des alkyles inférieurs, des acides acryliques ou méthacryliques ou leurs esters, des vinyllactames tels que la vinylpyrrolidone ou le vinylcaprolactame, des esters vinyliques.The copolymers of family (1) also contain one or more units deriving from comonomers which can be chosen from the family of acrylamides, methacrylamides, diacetones, acrylamides, acrylamides and methacrylamides substituted on nitrogen by lower alkyls, acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters.
Ainsi, parmi ces copolymères de la famille (1 ), on peut citer :Thus, among these copolymers of family (1), there may be mentioned:
- les copolymères d'acrylamide et de diméthylaminoéthyl méthacrylate quaternisé au sulfate de diméthyle ou avec un halogénure de diméthyle tels que celui vendu sous la dénomination HERCOFLOC par la société HERCULES,- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide such as that sold under the name HERCOFLOC by the company HERCULES,
- les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyltriméthyl- ammonium décrit par exemple dans la demande de brevet EP-A-080976 et vendus sous la dénomination BINA QUAT P 100 par la société CIBA GEIGY, - le copolymère d'acrylamide et de méthosulfate de méthacryloyloxyéthyl- triméthylammonium vendu sous la dénomination RETEN par la société HERCULES,- the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described for example in patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY, - the copolymer of acrylamide and methosulfate methacryloyloxyethyltrimethylammonium sold under the name RETEN by the company HERCULES,
- les copolymères vinylpyrrolidone / acrylate ou méthacrylate de dialkylaminoalkyle quatemisés ou non, tels que les produits vendus sous la dénomination "GAFQUAT" par la société ISP comme par exemple "GAFQUAT 734" ou "GAFQUAT 755" ou bien les produits dénommés "COPOLYMER 845, 958 et 937". Ces polymères sont décrits en détail dans les brevets français 2.077.143 et 2.393.573,- vinylpyrrolidone / acrylate or methacrylate of dialkylaminoalkyl copolymers, whether or not quaternized, such as the products sold under the name "GAFQUAT" by the company ISP, for example "GAFQUAT 734 "or" GAFQUAT 755 "or the products called" COPOLYMER 845, 958 and 937 ". These polymers are described in detail in French patents 2,077,143 and 2,393,573,
- les terpolymères méthacrylate de diméthyl amino éthyle/ vinylcaprolactame/ vinylpyrrolidone tel que le produit vendu sous la dénomination GAFFIX VC 713 par la société ISP,- dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers such as the product sold under the name GAFFIX VC 713 by the company ISP,
- et le copolymère vinylpyrrolidone / méthacrylamidë de diméthylaminopropyle quaternisé tel que le produit vendu sous la dénomination "GAFQUAT HS 100" par la société ISP.- And the vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymer such as the product sold under the name "GAFQUAT HS 100" by the company ISP.
(2) les polysaccharides quatemisés décrits plus particulièrement dans les brevets américains 3.589.578 et 4.031.307 tel que les gommes de guar contenant des groupements cationiques trialkylammonium.(2) the quaternized polysaccharides described more particularly in US patents 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups.
De tels produits sont commercialisés notamment sous les dénominations commerciales de JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 par la société MEYHALL.Such products are marketed in particular under the trade names of JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 by the company MEYHALL.
(3) les copolymères quaternaires de vinylpyrrolidone et de vinylimidazole tels que les produits commercialisés par BASF sous l'appellation Luviquat FC;(3) quaternary copolymers of vinylpyrrolidone and of vinylimidazole such as the products sold by BASF under the name Luviquat FC;
(4) les chitosanes ou leurs sels; les sels utilisables sont en particulier les acétate, lactate, glutamate, gluconate ou le pyrrolidone carboxylate de chitosane .(4) chitosans or their salts; the salts which can be used are in particular the acetate, lactate, glutamate, gluconate or the pyrrolidone carboxylate of chitosan.
Parmi ces composés, on peut citer le chitosane ayant un taux de désacétylation de 90,5% en poids vendu sous la dénomination KYTAN BRUT STANDARD par la société ABER TECHNOLOGIES, le pyrrolidone carboxylate de chitosane vendu sous la dénomination KYTAMER PC par la société AMERCHOL . Les polymères filmogènes anioniques généralement utilisés sont des polymères comportant des groupements dérivés d'acide carboxylique, sulfonique ou phosphorique et ont un poids moléculaire compris entre environ 500 et 5.000.000. 1 ) Les groupements carboxyliques sont apportés par des monomères mono ou diacides carboxyliques insaturés tels que ceux répondant à la formuleAmong these compounds, there may be mentioned chitosan having a deacetylation rate of 90.5% by weight sold under the name KYTAN BRUT STANDARD by the company ABER TECHNOLOGIES, chitosan pyrrolidone carboxylate sold under the name KYTAMER PC by the company AMERCHOL. The anionic film-forming polymers generally used are polymers comprising groups derived from carboxylic, sulfonic or phosphoric acid and have a molecular weight of between approximately 500 and 5,000,000. 1) The carboxylic groups are provided by mono or unsaturated dicarboxylic acid monomers such as those corresponding to the formula
dans laquelle n est un nombre entier de 0 à 10, A 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 que oxygène ou soufre, R7 désigne un atome d'hydrogène, un groupement phényle ou benzyle, Rβ désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, Rg désigne un atome d'hydrogène, un groupement alkyle inférieur; un groupement -CH2-COOH, phényle ou benzyle ;in which n is an integer from 0 to 10, A denotes a methylene group, optionally linked 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, R7 denotes a hydrogen atom, a phenyl or benzyl group, Rβ denotes a hydrogen atom, a lower alkyl or carboxyl group, Rg denotes a hydrogen atom, a lower alkyl group; a group -CH2-COOH, phenyl or benzyl;
Dans la formule précitée un radical alkyle inférieur désigne de préférence un groupement ayant 1 à 4 atomes de carbone et en particulier, méthyle et éthyle.In the above formula a lower alkyl radical preferably denotes a group having 1 to 4 carbon atoms and in particular, methyl and ethyl.
Les polymères filmogènes anioniques à groupements carboxyliques préférés selon l'invention sont :The anionic film-forming polymers with carboxylic groups preferred according to the invention are:
A) Les homo- ou copolymères d'acide acrylique ou méthacrylique ou leurs sels et en particulier les produits vendus sous les dénominations VERSICOL E ou K par la société ALLIED COLLOID et ULTRAHOLD par la société BASF. Les copolymères d'acide acrylique et d'acrylamide vendus sous la forme de leur sel de sodium sous les dénominations RETEN 421 , 423 ou 425 par la Société HERCULES, les sels de sodium des acides polyhydroxycarboxyliques.A) Homo- or copolymers of acrylic or methacrylic acid or their salts and in particular the products sold under the names VERSICOL E or K by the company ALLIED COLLOID and ULTRAHOLD by the company BASF. Copolymers of acrylic acid and acrylamide sold in the form of their salt sodium under the names RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids.
B) Les copolymères des acides acrylique ou méthacrylique avec un monomère monoéthylénique tel que 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 1.222.944 et la demande allemande 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 75370 et 75371 ou proposés sous la dénomination QUADRAMER par la Société AMERICAN CYANAMID. 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 tel que celui vendu par la société ISP sous la dénomination ACRYLIDONE LM et les terpolymères acide méthacrylique/ acrylate d'éthyle/ acrylate de tertiobutyle tel que le produit vendu sous la dénomination LUVIMER 100 P par la société BASF.B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1,222,944 and German application 2,330,956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and / or hydroxyalkylated as described in particular in the applications for Luxembourg patents 75370 and 75371 or offered under the name QUADRAMER by the company AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C1 -C4 alkyl methacrylate and of terpolymers of vinylpyrrolidone, of acrylic acid and of C1-C20 alkyl methacrylate, for example of lauryl, such as that sold by the ISP under the name ACRYLIDONE LM and the methacrylic acid / ethyl acrylate / tert-butyl acrylate terpolymers such as the product sold under the name LUVIMER 100 P by the company 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 esters allylique ou méthallylique, éther vinylique ou ester vinylique d'un acide carboxylique saturé linéaire ou ramifié à longue chaîne hydrocarbonée tels que ceux comportant au moins 5 atomes de carbone, ces polymères pouvant éventuellement être greffés et réticulés ou encore un ester vinylique, allylique ou méthallylique d'un acide carboxylique α- ou β-cyclique. De tels polymères sont décrits entre autres dans les brevets français 1.222.944, 1.580.545, 2.265.782, 2.265.781 , 1.564.110 et 2.439.798. Des produits commerciaux entrant dans cette classe sont les résines 28-29-30, 26-13-14 et 28-13-10 vendues par la société NATIONAL STARCH. D) les copolymères dérivés d'acides ou d'anhydrides carboxyliques monoinsaturés en C4-C8 choisis parmi :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 ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain such as those containing at least 5 carbon atoms, these polymers possibly being able to be grafted and crosslinked or else a vinyl, allylic or methallylic ester of an α- or β-cyclic carboxylic acid. Such polymers are described inter alia in French patents 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products falling into this class are resins 28-29-30, 26-13-14 and 28-13-10 sold by the company NATIONAL STARCH. D) copolymers derived from C 4 -C 8 monounsaturated carboxylic acids or anhydrides chosen from:
- les copolymères comprenant (i) un ou plusieurs acides ou anhydrides maléique, fumarique, itaconique et (ii) au moins un monomère choisis 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 2.047.398, 2.723.248, 2.102.113, le brevet GB 839.805 et notamment ceux vendus sous les dénominations GANTREZ AN ou ES par la société ISP.- the copolymers comprising (i) one or more maleic, fumaric, itaconic acids or anhydrides and (ii) at least one monomer chosen from vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl 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 2,047,398, 2,723,248, 2,102,113, GB patent 839,805 and in particular those sold under the names GANTREZ AN or ES by the company ISP.
- les copolymères comprenant (i) un ou plusieurs anhydrides maléique, citraconique, itaconique et (ii) un ou plusieurs monomères choisis parmi les esters allyliques ou méthaliyliques 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. Ces polymères sont par exemple décrits dans les brevets français 2.350.384 et- the copolymers comprising (i) one or more maleic, citraconic, itaconic anhydrides and (ii) one or more monomers chosen from allylic or methaliylic esters optionally comprising one or more acrylamide, methacrylamide, α-olefin groups, acrylic or methacrylic esters, acrylic or methacrylic or vinylpyrrolidone acids in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. These polymers are for example described in French patents 2,350,384 and
2.357.241 de la demanderesse.2,357,241 by the plaintiff.
E) les polyacrylamides comportant des groupements carboxylates.E) polyacrylamides containing carboxylate groups.
Les polymères comprenant les groupements sulfoniques sont des polymères comportant des motifs vinyisulfonique, styrène sulfonique, naphtalène sulfonique ou acrylamido alkylsulfonique.The polymers comprising the sulfonic groups are polymers comprising vinyisulfonic, styrene sulfonic, naphthalene sulfonic or acrylamido alkylsulfonic units.
Ces polymères peuvent être notamment choisis parmi - les sels de l'acide polyvinylsulfonique ayant un poids moléculaire compris 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 l'acrylamide ou ses dérivés, les éthers vinyliques et la vinylpyrrolidone.These polymers can in particular be chosen from - the salts of polyvinylsulfonic acid having a molecular weight of between approximately 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 the vinylpyrrolidone.
- les sels de l'acide polystyrène sulfonique les sels de sodium ayant un poids moléculaire d'environ 500.000 et d'environ 100.000 vendus respectivement sous les dénominations Flexan 500 et Flexan 130 par National Starch. Ces composés sont décrits dans le brevet FR 2.198.719.the salts of polystyrene sulfonic acid the sodium salts having a molecular weight of approximately 500,000 and approximately 100,000 sold respectively under the names Flexan 500 and Flexan 130 by National Starch. These compounds are described in patent FR 2,198,719.
- les sels d'acides polyacrylamide sulfoniques ceux mentionnés dans le brevet US 4.128.631 et plus particulièrement l'acide polyacrylamidoéthylpropane sulfonique vendu sous la dénomination COSMEDIA POLYMER HSP 1180 par Henkel.- The salts of polyacrylamide sulfonic acids those mentioned in US Pat. No. 4,128,631 and more particularly polyacrylamidoethylpropane sulfonic acid sold under the name COSMEDIA POLYMER HSP 1180 by Henkel.
Selon l'invention, les polymères filmogènes anioniques sont de préférence choisis parmi les copolymères d'acide acrylique tels que le terpolymère acide acrylique / acrylate d'éthyle / N-tertiobutylacrylamide vendu sous la dénomination ULTRAHOLD STRONG par la société BASF, les copolymères dérivés d'acide crotonique tels que les terpolymères acétate de vinyle / tertio- butyl benzoate 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 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 le copolymère méthylvinyléther/anhydride maléique mono estérifié vendu sous la dénomination GANTREZ ES 425 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, le copolymère d'acide méthacrylique et d'acrylate d'éthyle vendu sous la dénomination LUVIMER MAEX ou MAE par la société BASF, le copolymère acétate de vinyle/acide crotonique vendu sous la dénomination LUVISET CA 66 par la société BASF et le copolymère acétate de vinyle/acide crotonique greffé par du polyéthylèneglycol sous la dénomination ARISTOFLEX A par la société BASF.According to the invention, the anionic film-forming polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers derived from crotonic acid such as the vinyl acetate / tert-butyl vinyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold 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 / mono ester maleic anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, metha acid copolymers and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the acid copolymer methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX or MAE by the company BASF, the vinyl acetate / crotonic acid copolymer sold under the name LUVISET CA 66 by the company BASF and the grafted vinyl acetate / crotonic acid copolymer with polyethylene glycol under the name ARISTOFLEX A by the company BASF.
Les polymères filmogènes anioniques les plus particulièrement préférés sont choisis parmi le copolymère méthylvinyléther / anhydride maléique mono estérifié vendu sous la dénomination GANTREZ ES 425 par la société ISP, le terpolymère acide acrylique / acrylate d'éthyle / N-tertiobutylacrylamide vendu 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-butyl benzoate 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, le copolymère d'acide méthacrylique et d'acrylate d'éthyle vendu sous la dénomination LUVIMER MAEX OU MAE par la société BASF, le terpolymère de vinylpyrrolidone / acide acrylique/méthacrylate de lauryle vendu sous la dénomination ACRYLIDONE LM par la société ISP.The most particularly preferred anionic film-forming polymers are chosen from the methyl ester / maleic mono esterified anhydride copolymer sold under the name GANTREZ ES 425 by the company ISP, the acrylic acid / ethyl acrylate / N-tertiobutylacrylamide terpolymer sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the vinyl acetate / tert-butyl vinyl benzoate / crotonic acid terpolymers and the crotonic acid / acetate terpolymers of vinyl / vinyl neododecanoate sold under the name Resin 28-29-30 by the company NATIONAL STARCH, the copolymer of methacrylic acid and ethyl acrylate sold under the name LUVIMER MAEX OR MAE by the company BASF, the terpolymer vinylpyrrolidone / acrylic acid / lauryl methacrylate sold s or the name ACRYLIDONE LM by the company ISP.
Les polymères filmogènes 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; 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 radical 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.The amphoteric film-forming polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed statistically in the polymer chain where B denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and C denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulphonic groups or else B and C can denote groups deriving from zwitterionic monomers of carboxybetaines or of sulphobetaines; B and C can also denote 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 sulphonic group linked via a hydrocarbon radical or else B and C are part of a chain of a polymer with an ethylene α, β-dicarboxylic unit, one of the " carboxylic groups of which has been caused to react with a polyamine comprising one or more primary or secondary amine groups.
Les polymères filmogènes amphotères répondant à la définition donnée ci- dessus plus particulièrement préférés sont choisis parmi les polymères suivants :The amphoteric film-forming 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 maléique, 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 dialkylaminoalkylméthacrylate et acrylate, les dialkylamino- alkylméthacrylamide 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-chloroacrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as more particularly the dialkylaminoalkylmethacrylate and acrylate, the dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in US Patent 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'azote par un radical 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. Les acrylamides ou méthacrylamides N-substitués plus particulièrement préférés selon l'invention sont les groupements dont les radicaux alkyle contiennent de 2 à 12 atomes de carbone et plus particulièrement le N- éthylacrylamide, le N-tertiobutyl acrylamide, le N-tertiooctyl acrylamide, le N- octylacrylamide, le N-décylacrylamide, le N-dodécylacrylamide ainsi que les méthacrylamides correspondants. 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.(2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on nitrogen by an alkyl radical, b) from at least one acidic comonomer containing one or more carboxylic groups reactants, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. The N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups of which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutyl acrylamide, N-tertiooctyl acrylamide, N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide as well as the corresponding methacrylamides. The acid comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, 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 butyl aminoéthyle, de N,N'-diméthylaminoéthyle, de N-tertio-butylaminoéthyle. On utilise particulièrement les copolymères dont la dénomination CTFA (4ème Ed., 1991 ) est Octylacrylamide / acrylates / butylaminoethyl méthacrylate copolymer tels que les produits vendus sous la dénomination AMPHOMER ou LOVOCRYL 47 par la société NATIONAL STARCH.The preferred basic comonomers are aminoethyl, butyl aminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates. Copolymers are particularly used, the name CTFA (4th Ed., 1991) being Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company NATIONAL STARCH.
(3) les polyamino amides réticulés et alcoylés partiellement ou totalement dérivant de polyaminoamides de formule générale :(3) crosslinked and alkylated polyamino amides partially or totally derived from polyaminoamides of general formula:
— EΞC0 — RÎÔ — co — z-^— C")- EΞ C0 - R ÎÔ - co - z - ^ - C ")
dans laquelle R-J Q représente un radical 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 radical dérivant de l'addition de l'un quelconque desdits acides avec une aminé bis primaire ou bis secondaire, et Z désigne un radical d'une polyalkylène-polyamine bis-primaire, mono ou bis-secondaire et de préférence représente : a) dans les proportions de 60 à 100 moles %, le radicalin which RJ Q represents a divalent radical derived from a saturated dicarboxylic acid, from a mono or dicarboxylic acid with ethylene double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or from d 'a radical derived from the addition of any one of said acids with a primary bis or secondary bis amino, and Z denotes a radical of a bis-primary, mono or bis-secondary polyalkylene polyamine and preferably represents: a ) in the proportions of 60 to 100 mol%, the radical
où x=2 et p=2 ou 3, ou bien x=3 et p=2 ce radical dérivant de la diéthylène triamine, de la triéthylène tétraamine ou de la dipropylène triamine; b) dans les proportions de 0 à 40 moles % le radical (IV) ci-dessus, dans lequel x=2 et p=1 et qui dérive de l'éthylèπediamine, ou le radical dérivant de la pipérazine : where x = 2 and p = 2 or 3, or else x = 3 and p = 2 this radical deriving from diethylene triamine, triethylene tetraamine or dipropylene triamine; b) in the proportions of 0 to 40 mol% the radical (IV) above, in which x = 2 and p = 1 and which is derived from ethylèπediamine, or the radical deriving from piperazine:
/ \ N N/ \ N N
\ / c) dans les proportions de 0 à 20 moles % le radical -NH-(CH2)β-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par 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 alcoylés par action d'acide acrylique, d'acide chloracétique ou d'une alcane sultone ou de leurs sels.\ / c) in the proportions of 0 to 20 mol% the radical -NH- (CH2) β -NH- derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides , dianhydrides, bis unsaturated derivatives, using 0.025 to 0.35 mole of crosslinking agent by amino group of polyaminoamide and alkylated by the action of acrylic acid, chloracetic 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 l'acide 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 acid and trimethyl-2,4,4-adipic, terephthalic acid, ethylenic double bond such as for example acrylic, methacrylic, itaconic acids.
Les alcaπes sultones utilisées dans l'alcoylation sont de préférence la propane ou la butane sultone, les sels des agents d'alcoylation sont de préférence les sels de sodium ou de potassium.The alcaπes sultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.
(4) les polymères comportant des motifs zwittérioniques de formule :(4) polymers comprising zwitterionic units of formula:
dans laquelle R-] -] désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représente un nombre entier de 1 à 3, R-| 2 et R-13 représentent un atome d'hydrogène, méthyle, éthyle ou propyle, R14 et R-15 représentent un atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R1 et R15 ne dépasse pas 10. in which R-] -] denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represents an integer from 1 to 3, R- | 2 and R-13 represent a hydrogen, methyl, ethyl or propyl atom, R14 and R-15 represent an atom of hydrogen or an alkyl radical such that the sum of the carbon atoms in R1 and R15 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 diethylaminoethyle ou des alkyle acrylates ou méthacrylates, des acrylamides ou méthacrylamides ou l'acétate de vinyle. A titre d'exemple, on peut citer le copolymère de méthacrylate de méthyle / diméthyl carboxyméthylammonio éthylméthacrylate de méthyle tel que le produit vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ.The polymers comprising such units may also contain 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. By way of example, there may be mentioned the copolymer of methyl methacrylate / dimethyl carboxymethylammonio ethyl methacrylate such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.
(5) les polymères dérivés du chitosane comportant des motifs monomères répondant aux formules suivantes :(5) polymers derived from chitosan containing monomer units corresponding to the following formulas:
le motif D étant présent dans des proportions comprises entre 0 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 radical de formule : the motif D being present in proportions of between 0 and 30%, the motif E in proportions of between 5 and 50% and the motif F in proportions of between 30 and 90%, it being understood that in this motif F, R 16 represents a radical of formula:
^18 R 19 17^ 18 R 19 17
dans laquelle si q=0, R17, R<] 8 et R19, 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, alcolylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des radicaux R-17, R<| 8 et Rig étant dans ce cas un atome d'hydrogène ; ou si q=1 , R-17, R-J S et R19 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, R17, R < ] 8 and R19, 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 several nitrogen atoms and / or optionally substituted by one or more amino, hydroxyl, carboxyl, alcolylthio groups, sulfonic, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals R-17, R <| 8 and Rig being in this case a hydrogen atom; or if q = 1, R-17, RJ S and R19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
(6) Les polymères dérivés de la N-carboxyalkylation du chitosane comme le N-carboxyméthyl chitosane ou le N-carboxybutyl chitosane vendu sous la dénomination "EVALSAN" par la société JAN DEKKER.(6) Polymers derived from the N-carboxyalkylation of chitosan such as N-carboxymethyl chitosan or N-carboxybutyl chitosan sold under the name "EVALSAN" by the company JAN DEKKER.
(7) Les polymères répondant à la formule générale (VI) par exemple décrits dans le brevet français 1 400 366 :(7) The polymers corresponding to the general formula (VI), for example described in French patent 1,400,366:
dans laquelle R20 représente un atome d'hydrogène, un radical CH3O, CH3CH2O, phényle, R21 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R22 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R23 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule : -R24-Ν(R22)2. R24 représentant un groupement -CH2-CH2- , -CH2-CH2-CH2- , -CH2-CH(CH3)- , R22 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone. (8) Des 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 : in which R20 represents a hydrogen atom, a CH3O, CH3CH2O, phenyl radical, R21 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R22 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R23 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R24-Ν (R22) 2. R 24 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH 3 ) -, R 2 2 having the meanings mentioned above, as well as the higher homologs of these radicals and containing up to 6 carbon atoms. (8) Amphoteric polymers of the -DXDX- type chosen from: a) the polymers obtained by the action of chloracetic acid or sodium chloroacetate on the compounds comprising at least one unit of formula:
-D-X-D-X-D- (VII) où D désigne un radical-D-X-D-X-D- (VII) where D denotes a radical
/ \ N N/ \ N N
\ / et X désigne le symbole E ou E', E ou E' identiques ou différents désignent un radical bivalent qui est un radical 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, alkénylamine, des groupements hydroxyle, benzylamine, oxyde d'aminé, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne. b) Les polymères de formule :\ / and X denote the same or different symbol E or E ', E or E' denote a bivalent radical which is a straight or branched chain alkylene radical containing up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 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 groups, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane. b) The polymers of formula:
-D-X-D-X- (VI I') où D désigne un radical-D-X-D-X- (VI I ') where D denotes a radical
/ \ N N/ \ N N
\ / 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 radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs radicaux 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.\ / and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloracetic acid or sodium chloroacetate.
(9) les copolymères alkyl(C1 -C5)vinyléther / anhydride maléique modifié partiellement par semiamidification avec une N,N-dialkylaminoalkylamine telle que la N,N-diméthylaminopropylamine ou par semiestérification avec une N,N- dialcanolamine. Ces copolymères peuvent également comporter d'autres comonomères vinyliques tels que le vinylcaprolactame.(9) (C 1 -C 5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semiesterification with an N, N-dialcanolamine. These copolymers can also contain other vinyl comonomers such as vinylcaprolactam.
Les polymères filmogènes amphotères particulièrement préférés selon l'invention sont ceux de la famille (3) tels que les copolymères dont la dénomination CTFA est Octylacrylamide/acrylates/butylaminoethylmethacrylate copolymer tels que les produits vendus sous les dénominations AMPHOMER, AMHOMER LV 71 ou LOVOCRYL 47 par la société NATIONAL STARCH et ceux de la famille (4) tels que les copolymère de méthacrylate de méthyle / diméthyl carboxyméthylammonio éthylméthacrylate de méthyle par exemple vendu sous la dénomination DIAFORMER Z301 par la société SANDOZ.The amphoteric film-forming polymers which are particularly preferred according to the invention are those of the family (3) such as the copolymers whose name CTFA is Octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer such as the products sold under the names AMPHOMER, AMHOMER LV 71 or LOVOCRYL 47 by the company NATIONAL STARCH and those of the family (4) such as the copolymers of methyl methacrylate / dimethyl carboxymethylammonio ethyl methylmethacrylate, for example sold under the name DIAFORMER Z301 by the company SANDOZ.
Selon l'invention, on peut également utiliser les polymères anioniques filmogènes de type siiiconés greffés comprenant une portion polysiloxane et une portion constituée d'une chaîne organique non-siliconée, l'une des deux portions constituant la chaîne principale du polymère l'autre étant greffée sur la dite chaîne principale. Ces polymères sont par exemple décrits dans les demandes de brevet EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 et WO 95/00578, EP-A-0582 152 et WO 93/23009 et les brevets US 4,693,935, US 4,728,571 et US 4,972,037.According to the invention, it is also possible to use film-forming anionic polymers of grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer the other being grafted on said main chain. These polymers are for example described in patent applications EP-A-0 412 704, EP-A-0 412 707, EP-A-0 640 105 and WO 95/00578, EP-A-0582 152 and WO 93 / 23009 and US patents 4,693,935, US 4,728,571 and US 4,972,037.
De tels polymères sont par exemple les copolymères susceptibles d'être obtenus par polymérisation radicalaire à partir du mélange de monomères constitué par : a) 50 à 90% en poids d'acrylate de tertiobutyle ; b) 0 à 40% en poids d'acide acrylique ; c) 5 à 40% en poids de macromère siliconé de formule :Such polymers are, for example, the copolymers capable of being obtained by radical polymerization from the mixture of monomers consisting of: a) 50 to 90% by weight of tert-butyl acrylate; b) 0 to 40% by weight of acrylic acid; c) 5 to 40% by weight of silicone macromer of formula:
CH, ( CH2 ) 3 CH3 CH, (CH 2 ) 3 CH 3
avec v étant un nombre allant de 5 à 700 ; les pourcentages en poids étant calculés par rapport au poids total des monomères. with v being a number ranging from 5 to 700; the weight percentages being calculated relative to the total weight of the monomers.
D'autres exemples de polymères siliconés greffés sont notamment des polydiméthylsiloxanes (PDMS) sur lesquels sont greffés, par l'intermédiaire d'un chaînon de raccordement de type thiopropylène, des motifs polymères mixtes du type acide poly(méth)acrylique et du type poly(méth)acrylate d'alkyle et des polydiméthylsiloxanes (PDMS) sur lesquels sont greffés, par l'intermédiaire d'un chaînon de raccordement de type thiopropylène, des motifs polymères du type poly(méth)acrylate d'isobutyle.Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, mixed polymer units of the poly (meth) acrylic acid type and of the poly type. alkyl (meth) acrylate and polydimethylsiloxanes (PDMS) onto which are grafted, via a thiopropylene-type connecting link, polymeric units of the isobutyl poly (meth) acrylate type.
On peut aussi utiliser, comme polymères filmogènes, des polyuréthannes fonctionnalisés, siliconés ou non.It is also possible to use, as film-forming polymers, functionalized polyurethanes, silicone or not.
Les polyuréthannes particulièrement visés par la présente invention sont ceux décrits dans les brevets EP 0 751 162, EP 0 637 600, FR 2 743 297 et EP 0 648 485 dont la Demanderesse est Titulaire, ainsi que le brevets EP 0 656 021 ou WO 94/03510 de la Société BASF et EP 0 619 111 de la Société National Starch.The polyurethanes particularly targeted by the present invention are those described in patents EP 0 751 162, EP 0 637 600, FR 2 743 297 and EP 0 648 485 of which the Applicant is the Holder, as well as patent EP 0 656 021 or WO 94 / 03510 from the company BASF and EP 0 619 111 from the company National Starch.
Dans les compositions conformes à l'invention, le ou les polymères filmogènes (A) sont, de préférence, présents à des concentrations comprises entre 0,05 et 20 % en poids, plus préférentiellement comprises entre 0,1 et 15 % en poids, et plus préférentiellement entre 0,25 et 10 % en poids par rapport au poids total de la composition.In the compositions in accordance with the invention, the film-forming polymer (s) (A) are preferably present at concentrations of between 0.05 and 20% by weight, more preferably between 0.1 and 15% by weight, and more preferably between 0.25 and 10% by weight relative to the total weight of the composition.
Dans les compositions conformes à l'invention, le ou les polymères filmogènes (B) sont de préférence présents à des concentrations comprises entre 0,05 et 20 % en poids, plus préférentiellement comprises entre 0,1 et 15 % en poids, et plus préférentiellement entre 0,25 et 10 % en poids par rapport au poids total de la composition.In the compositions in accordance with the invention, the film-forming polymer (s) (B) are preferably present at concentrations of between 0.05 and 20% by weight, more preferably between 0.1 and 15% by weight, and more preferably between 0.25 and 10% by weight relative to the total weight of the composition.
On choisit avantageusement les concentrations en polymères (A) et (B), de sorte que le rapport de la concentration en polymère (A) à la concentration en polymère (B) soit compris entre 4000 et 0,002.The polymer concentrations (A) and (B) are advantageously chosen, so that the ratio of the polymer concentration (A) to the polymer concentration (B) is between 4000 and 0.002.
Le milieu cosmétiquement acceptable est, de préférence, constitué par de l'eau ou un ou plusieurs solvants cosmétiquement acceptables tels que des alcools ou des mélanges eau-solvant(s), ces solvants étant de préférence des alcools en Cι-C4.The cosmetically acceptable medium is preferably constituted by water or one or more cosmetically acceptable solvents such as alcohols or water-solvent mixtures (s), these solvents preferably being Cι-C 4 alcohols.
Parmi ces alcools, on peut citer l'éthanol, l'isopropanol. L'éthanol est particulièrement préféré.Among these alcohols, mention may be made of ethanol and isopropanol. Ethanol is particularly preferred.
La composition de l'invention peut également contenir au moins un additif choisi parmi les épaississants, les tensioactifs, les parfums, les conservateurs, les filtres solaires, les protéines, les vitamines, les polymères non fixants, et tout autre additif classiquement utilisé dans les compositions cosmétiques destinées à être appliquées sur les cheveux.The composition of the invention may also contain at least one additive chosen from thickeners, surfactants, perfumes, preservatives, sun filters, proteins, vitamins, non-fixing polymers, and any other additive conventionally used in cosmetic compositions intended to be applied to the hair.
Bien entendu, l'homme de l'art veillera à choisir le ou les éventuels composés à ajouter à la composition selon l'invention de manière telle que les propriétés avantageuses attachées intrinsèquement à la composition conforme à l'invention ne soient pas, ou substantiellement pas, altérées par l'addition envisagée.Of course, those skilled in the art will take care to choose the possible compound or compounds to be added to the composition according to the invention in such a way that the advantageous properties intrinsically attached to the composition in accordance the invention is not, or is not substantially, altered by the proposed addition.
Ces compositions peuvent être conditionnées sous diverses formes, notamment dans des flacons pompes ou dans des récipients aérosols, afin d'assurer une application de la composition sous forme vaporisée ou sous forme de mousse. De telles formes de conditionnement sont indiquées, par exemple, lorsqu'on souhaite obtenir un spray, une laque ou une mousse pour la fixation ou le traitement des cheveux. Les compositions conformes à l'invention peuvent aussi se présenter sous la forme de crèmes, de gels, d'émulsions, de lotions ou de cires.These compositions can be packaged in various forms, in particular in pump dispensers or in aerosol containers, in order to ensure application of the composition in vaporized form or in the form of foam. Such forms of packaging are indicated, for example, when it is desired to obtain a spray, a lacquer or a foam for fixing or treating the hair. The compositions according to the invention can also be in the form of creams, gels, emulsions, lotions or waxes.
Lorsque la composition selon l'invention est conditionnée sous forme d'aérosol en vue d'obtenir une laque ou une mousse, elle comprend au moins un agent propulseur qui peut être choisi parmi les hydrocarbures volatils tels que le n- butane, le propane, l'isobutane, le pentane, un hydrocarbure chloré et/ou fluoré et leurs mélanges. On peut également utiliser en tant qu'agent propulseur le gaz carbonique, le protoxyde d'azote, le diméthyléther (DME), l'azote, l'air comprimé. On peut aussi utiliser des mélanges de propulseurs. De préférence, on utilise le diméthyl éther.When the composition according to the invention is packaged in the form of an aerosol in order to obtain a lacquer or a foam, it comprises at least one propellant which can be chosen from volatile hydrocarbons such as n-butane, propane, isobutane, pentane, a chlorinated and / or fluorinated hydrocarbon and their mixtures. Carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen, compressed air can also be used as a propellant. Mixtures of propellants can also be used. Preferably, dimethyl ether is used.
Avantageusement, l'agent propulseur est présent à une concentration comprise entre 5 et 90 % en poids par rapport au poids total de la composition dans le dispositif aérosol et, plus particulièrement, à une concentration comprise entre 10 et 60 %.Advantageously, the propellant is present at a concentration between 5 and 90% by weight relative to the total weight of the composition in the aerosol device and, more particularly, at a concentration between 10 and 60%.
Les compositions conformes à l'invention peuvent être appliquées sur des cheveux secs ou humides.The compositions according to the invention can be applied to dry or damp hair.
L'invention va être plus complètement illustrée à l'aide de l'exemple non limitatif suivant. Tous les pourcentages sont des pourcentages relatifs en poids par rapport au poids total de la composition et m. a. signifie matière active. On utilise les polymères indiqués ci-après:The invention will be more fully illustrated with the aid of the following nonlimiting example. All the percentages are relative percentages by weight relative to the total weight of the composition and ma means active material. The polymers indicated below are used:
Avalure AC 315 polymère acrylique commercialisé parAvalure AC 315 acrylic polymer marketed by
GoodrichGoodrich
Amphomer polymère amphotère octylacrylamide / acrylates / butylaminoéthyl méthacrylate commercialisé par la société NATIONAL STARCHAmphomeric amphoteric octylacrylamide / acrylates / butylaminoethyl methacrylate marketed by the company NATIONAL STARCH
LuvitecVPI 55K72 polymère cationique vinyl pyrrolidone /vinylimidazole commercialisé par BASFLuvitecVPI 55K72 cationic polymer vinyl pyrrolidone / vinylimidazole marketed by BASF
Polymère X polymère anionique acide crotonique/acétate de vinyle / tertiobutylate de vinylePolymer X anionic polymer crotonic acid / vinyl acetate / vinyl tert-butylate
VS80 polymère anionique à squelette polysiloxanique greffé par des monomères non siliconésVS80 anionic polymer with polysiloxane backbone grafted with non-silicone monomers
EXEMPLEEXAMPLE
On réalise 5 compositions de coiffage comprenant toutes de l'Avalure AC315 en tant que polymère (A). L'une des compositions de coiffage est conforme à l'art antérieur et comprend de l'éthyl cellulose en tant que polymère filmogène (B). Les 4 autres compositions de coiffage sont conformes à la présente invention et comprennent un polymère filmogène amphotère, anionique ou cationique.5 styling compositions are produced, all comprising Avalure AC315 as polymer (A). One of the styling compositions is in accordance with the prior art and comprises ethyl cellulose as a film-forming polymer (B). The other 4 styling compositions are in accordance with the present invention and comprise an amphoteric, anionic or cationic film-forming polymer.
Le tableau 1 ci-après résume les formulations réalisées.Table 1 below summarizes the formulations produced.
Tableau 1Table 1
On applique les compositions 1 à 5 conditionnées en aérosol (composition, DME 35 %) sur des mèches de cheveux eurochâtains de longueur 18 cm et de 20 grammes.The compositions 1 to 5 packaged in aerosol (composition, DME 35%) are applied to locks of Eurochestian hair of length 18 cm and 20 grams.
On évalue la douceur et la facilité de démêlage des cheveux après application de ces compositions sur les cheveux au moyen d'un test sensoriel avec un panel de 5 personnes. Les notes attribuées vont de 0 (mauvaise performance) à 50 (excellente performance). Le démêlage évalué est la facilité du repassage du peigne après un premier démêlage pour rompre les soudures polymère- cheveu. Les résultats obtenus sont résumés dans le tableau 2 ci-après. Tableau 2The softness and ease of disentangling of the hair is evaluated after application of these compositions to the hair by means of a sensory test with a panel of 5 people. The marks awarded range from 0 (poor performance) to 50 (excellent performance). The disentangling evaluated is the ease of ironing the comb after a first disentangling to break the polymer-hair welds. The results obtained are summarized in Table 2 below. Table 2
Il en résulte que les compositions conformes à la présente invention procurent des performances nettement meilleures en terme de douceur et de démêlage que les compositions comprenant une association de polymères conforme à l'art antérieur. It follows that the compositions according to the present invention provide significantly better performance in terms of softness and disentangling than the compositions comprising a combination of polymers according to the prior art.

Claims

REVENDICATIONS
1. Composition de coiffage comprenant, dans un milieu cosmétiquement acceptable:1. Styling composition comprising, in a cosmetically acceptable medium:
(1 ) au moins un polymère (A) choisi de telle sorte qu'un film obtenu par séchage d'un mélange de ce polymère (A) avec de l'éthanol ou de l'eau, à température ambiante et à un taux d'humidité relative de 50 %, présente un profil mécanique défini par au moins:(1) at least one polymer (A) chosen such that a film obtained by drying a mixture of this polymer (A) with ethanol or water, at room temperature and at a rate d relative humidity of 50%, has a mechanical profile defined by at least:
(i) un taux d'allongement à la rupture (εr) supérieur ou égal à 300 %; (ii) une recouvrance à 300 secondes (R300) supérieure ou égale à 45 %; et (iii) lorsque la recouvrance à 300 secondes est comprise entre 45 et 60 %, alors l'allongement est inférieur à 1300 %; (2) au moins un polymère (B) filmogène et différent du polymère (A) et choisi parmi les polymères filmogènes anioniques, cationiques ou amphotères.(i) a rate of elongation at break (ε r ) greater than or equal to 300%; (ii) a recovery at 300 seconds (R 300 ) greater than or equal to 45%; and (iii) when the recovery at 300 seconds is between 45 and 60%, then the elongation is less than 1300%; (2) at least one film-forming polymer (B) different from the polymer (A) and chosen from anionic, cationic or amphoteric film-forming polymers.
2. Composition selon la revendication précédente, caractérisée par le fait que le polymère (B) est un polymère anionique choisi parmi : - les polymères comportant des motifs carboxyliques dérivant de monomères mono ou diacides carboxyliques insaturés de formule:2. Composition according to the preceding claim, characterized in that the polymer (B) is an anionic polymer chosen from: - polymers comprising carboxylic units derived from mono or unsaturated dicarboxylic acid monomers of formula:
dans laquelle n est un nombre entier de 0 à 10, A désigne un groupement méthylène, éventuellement relié à l'atome de carbone du groupement iπsaturé ou au groupement méthylène voisin lorsque n est supérieur à 1 par l'intermédiaire d'un hétéroatome tel que oxygène ou soufre, R7 désigne un atome d'hydrogène, un groupement phényle ou benzyle, Rβ désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, Rg désigne un atome d'hydrogène, un groupement alkyle inférieur, un groupement -CH2-COOH, phényle ou benzyle ;in which n is an integer from 0 to 10, A denotes a methylene group, optionally linked to the carbon atom of the iπsaturated group or to the neighboring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur, R7 denotes a hydrogen atom, a phenyl or benzyl group, Rβ denotes an atom hydrogen, a lower alkyl or carboxyl group, Rg denotes a hydrogen atom, a lower alkyl group, a -CH2-COOH, phenyl or benzyl group;
- les polymères comprenant des motifs dérivant d'acide sulfonique tels que des motifs vinylsulfonique, styrènesulfonique, acrylamido alkylsulfonique.- polymers comprising units derived from sulfonic acid such as vinylsulfonic, styrenesulfonic, acrylamido alkylsulfonic units.
3. Composition selon la revendication précédente, caractérisée en ce que le polymère filmogène anionique est choisi parmi :3. Composition according to the preceding claim, characterized in that the anionic film-forming polymer is chosen from:
- les copolymères d'acide acrylique tels que le terpolymère acide acrylique/acrylate d'éthyle/N-tertiobutylacrylamide ;- acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer;
- les copolymères dérivés d'acide crotonique tels que les terpolymères acétate de vinyle / tertio-butyl benzoate de vinyle / acide crotonique et les terpolymères acide crotonique/acétate de vinyle/néododécanoate de vinyle;- copolymers derived from crotonic acid such as the vinyl acetate / vinyl tert-butyl benzoate / crotonic acid terpolymers and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers;
- 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 méthyivinyléther/anhydride maléique mono estérifié ;- polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenyl vinyl derivatives, acrylic acid and its esters such as methyivinyl ether / maleic anhydride mono ester copolymers ;
- les copolymères d'acide méthacrylique et de méthacrylate de méthyle ;- copolymers of methacrylic acid and methyl methacrylate;
- le copolymère d'acide méthacrylique et d'acrylate d'éthyle; - le copolymère acétate de vinyle/acide crotonique ;- the copolymer of methacrylic acid and ethyl acrylate; - the vinyl acetate / crotonic acid copolymer;
- le terpolymère acétate de vinyle/acide crotonique/polyéthylèneglycol.- the vinyl acetate / crotonic acid / polyethylene glycol terpolymer.
4. Composition selon la revendication 1 , caractérisée en ce que le polymère filmogène (B) est un polymère amphotère choisi parmi les polymères comportant des motifs dérivant: a) d'au moins un monomère choisi parmi les acrylamides ou les méthacrylamides substitués sur l'azote par un radical alkyle, b) d'au moins un comonomère acide contenant un ou plusieurs groupements carboxyliques réactifs, et c) 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 quatemisation du méthacrylate de diméthylaminoéthyle avec le sulfate de diméthyle ou diéthyle.4. Composition according to claim 1, characterized in that the film-forming polymer (B) is an amphoteric polymer chosen from polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen by an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amino substituent acids acrylic and methacrylic and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.
5. Composition selon la revendication 1 , caractérisée par le fait que le polymère filmogène (B) est un polymère cationique choisi parmi :5. Composition according to claim 1, characterized in that the film-forming polymer (B) is a cationic polymer chosen from:
- le copolymère d'acrylamide et de diméthylaminoéthyl méthacrylate quatemisé au sulfate de diméthyle, les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyltriméthylammonium, - le copolymère d'acrylamide et de méthosulfate de méthacryloyloxyéthyltriméthylammonium,- the copolymer of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate, the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, - the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate,
- les copolymères vinylpyrrolidone / acrylate ou méthacrylate de dialkylaminoalkyle quaternisés ou non,- vinylpyrrolidone / acrylate or methacrylate of dialkylaminoalkyl quaternized or not,
- les terpolymère méthacrylate de diméthyl amino éthyle/ vinylcaprolactame/ vinylpyrrolidone,- dimethyl amino ethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymer,
- et le copolymère vinylpyrrolidone / méthacrylamide de diméthylaminopropyle quaternisé.- and the vinylpyrrolidone / methacrylamide dimethylaminopropyl quaternized copolymer.
6. Composition selon la revendication 1 , caractérisée par le fait que le polymère (B) est un polymère anionique de type silicone greffé comportant une portion polysiloxane et une portion constituée d'une chaîne organique non siliconée, l'une des deux portions constituant la chaîne principale du polymère , l'autre étant greffée sur ladite chaîne principale.6. Composition according to claim 1, characterized in that the polymer (B) is an anionic polymer of the grafted silicone type comprising a polysiloxane portion and a portion consisting of a non-silicone organic chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said main chain.
7. Composition selon la revendication 1 , caractérisée par le fait que le polymère filmogène (B) est un polyuréthanne fonctionnalisé, silicone ou non.7. Composition according to claim 1, characterized in that the film-forming polymer (B) is a functionalized polyurethane, silicone or not.
8. Composition selon l'une quelconque des revendications précédentes, caractérisée par le fait qu'elle contient en outre des additifs cosmétiques conventionnels choisis dans le groupe comprenant les corps gras, les agents épaississants, les adoucissants, les agents anti-mousse, les agents hydratants, les agents antiperspirants, les agents alcalinisants, les colorants, les pigments, les parfums, les conservateurs, les tensioactifs, les protéines et les vitamines.8. Composition according to any one of the preceding claims, characterized in that it also contains conventional cosmetic additives chosen from the group comprising fatty substances, thickening agents, softeners, anti-foaming agents, agents moisturizers, antiperspirants, basifying agents, dyes, pigments, perfumes, preservatives, surfactants, proteins and vitamins.
9. Dispositif aérosol formé par un récipient contenant une composition selon l'une quelconque des revendications précédentes et un gaz propulseur, ainsi qu'un moyen de distribution de la composition.9. An aerosol device formed by a container containing a composition according to any one of the preceding claims and a propellant gas, as well as a means of dispensing the composition.
10. Procédé de maintien ou de mise en forme de la coiffure, caractérisé par le fait qu'il comprend la mise en œuvre d'une composition conforme à l'une quelconque des revendications 1 à 8.10. A method of maintaining or shaping the hairstyle, characterized in that it comprises the use of a composition according to any one of claims 1 to 8.
11. Utilisation d'une composition selon l'une quelconque des revendications 1 à 8, pour la fabrication d'un produit cosmétique capillaire, en vue de maintenir et/ou de fixer la coiffure. 11. Use of a composition according to any one of claims 1 to 8, for the manufacture of a hair cosmetic product, with a view to maintaining and / or fixing the hairstyle.
EP99956077A 1998-11-26 1999-11-18 Hairstyling composition comprising a polymer with particular characteristics and an ionic film forming polymer Ceased EP1051146A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9814906 1998-11-26
FR9814906A FR2786391B1 (en) 1998-11-26 1998-11-26 HAIRDRESSING COMPOSITION COMPRISING A POLYMER WITH SPECIAL CHARACTERISTICS AND AN IONIC FILM-FORMING POLYMER
PCT/FR1999/002831 WO2000030594A1 (en) 1998-11-26 1999-11-18 Hairstyling composition comprising a polymer with particular characteristics and an ionic film forming polymer

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EP1051146A1 true EP1051146A1 (en) 2000-11-15

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EP (1) EP1051146A1 (en)
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KR (1) KR100391699B1 (en)
CN (1) CN1205908C (en)
AU (1) AU745846B2 (en)
BR (1) BR9907723A (en)
FR (1) FR2786391B1 (en)
PL (1) PL341980A1 (en)
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WO (1) WO2000030594A1 (en)

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RU2183449C2 (en) 2002-06-20
AU745846B2 (en) 2002-04-11
JP2004307516A (en) 2004-11-04
JP2002530310A (en) 2002-09-17
CN1205908C (en) 2005-06-15
BR9907723A (en) 2000-10-17
RU2000122453A (en) 2004-03-20
US6391292B1 (en) 2002-05-21
KR100391699B1 (en) 2003-07-12
KR20010034408A (en) 2001-04-25
CN1295459A (en) 2001-05-16
FR2786391A1 (en) 2000-06-02
FR2786391B1 (en) 2002-08-02
PL341980A1 (en) 2001-05-07
AU1276700A (en) 2000-06-13
WO2000030594A1 (en) 2000-06-02

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