FR2880536A1 - Cosmetic capillary treatment composition, useful as enamel for hair, comprises a non-ionic or anionic fixing polymer different from polyurethanes, a sulfonated polymer, a polyol and a propellant agent - Google Patents

Abstract

Cosmetic capillary treatment composition (A) (aerosol form), comprises, a non ionic or anionic fixing polymer (I) different from polyurethanes, optionally a sulfonated polymer (II) (partially or completely neutralized), comprising a unit derived from a monomer with ethylenic non-saturation containing sulfonic group, a polyol and a propellant agent in a medium. Independent claims are included for: (1) an aerosol device; and (2) the process of applying (A) comprises spraying (A) directly on the hair or applying with fingers.

Description

Cosmetic aerosol composition comprising at least one fixing polymer

  anionic or nonionic, at least one sulfonated polymer, at least one polyol and a propellant

  The present invention relates to a hair cosmetic treatment composition and a hair styling method.

  Styling products, such as lacquers, packaged in the form of an aerosol spray, generally contain fixing polymers in a cosmetically acceptable alcoholic or aqueous-alcoholic medium.

  The conditioning in aerosol form allows a regular distribution on the whole of the hair.

  However, fixing the hairstyle is almost immediate, it is not easy, if not impossible to structure the hairstyle with the hands.

  The Applicant has surprisingly found that by using an aerosol capillary cosmetic treatment composition combining an anionic or nonionic fixing polymer, a polyol, an associative or non-associative polymer comprising a unit derived from an unsaturated monomer. Ethylene sulfonic group and a propellant, we obtained a shaping of the hairstyle by simple finger work without obtaining instant hardening and freezing conventionally encountered with the usual products of fixation.

  This composition also has the advantage of obtaining on the fingers or on the hands a lasting crackling effect conferring on the composition an original rheological character, thus bringing a feeling of freshness to the application.

  This composition also has the advantage of spreading well on the hair and the application can be done on both dry hair and wet hair.

  In the case of an application on wet hair, drying in the open air or hair dryer can be achieved. The result is a soft and natural hairstyle.

  The invention therefore relates to a cosmetic hair treatment composition as described below.

  Another object of the present invention is a styling process using the composition according to the invention.

  Other objects, features and aspects of the invention will emerge even more clearly on reading the description.

  The cosmetic hair treatment composition in the form of an aerosol according to the invention comprises, in a cosmetically acceptable medium, at least one anionic or nonionic fixing polymer other than polyurethanes, at least one partially or totally neutralized sulphonated polymer or not, comprising at least one unit derived from an ethylenically unsaturated monomer containing a sulfonic group, at least one polyol, and a propellant.

  By cosmetically acceptable medium is meant a medium compatible with the hair.

  The sulfonated polymers according to the invention are associative or non-associative polymers which are sulfonated, partially or totally neutralized or not, comprising at least one unit derived from an ethylenically unsaturated monomer containing a sulfonic group, and optionally comprising at least one hydrophobic part.

  For the purposes of the present invention, the term "associative polymer" means any polymer having at least one hydrophilic part and at least one terminal or pendant fatty chain containing at least 10 carbon atoms. This type of polymer is likely to interact with itself or with particular compounds such as surfactants to lead to a thickening of the medium.

  For the purposes of the present invention, the term "partially neutralized" means sulphonic groups in salified form present in the polymer in a proportion of 1% to 99%.

  The hydrophobic part optionally present in the polymers of the invention preferably comprises from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms, more preferably still from 6 to 18 carbon atoms, more particularly from 10 to 18 carbon atoms. carbon atoms and more particularly from 12 to 18 carbon atoms.

  Preferably, the sulphonated polymers in accordance with the invention are partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, aqueous ammonia) or an organic base such as mono-, di- or tri-ethanolamine, an aminomethylpropanediol, N methylglucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds.

  The sulphonated polymers in accordance with the invention generally have a number-average molecular weight ranging from 1000 to 20,000,000 g / mol, preferably ranging from 20,000 to 5,000,000 g / mol and more preferably still from 100,000 to 1,500 g / mol. 000 g / mole.

  The sulfonated polymers according to the invention may be crosslinked or non-crosslinked.

  Preferably, crosslinked sulfonated polymers are chosen.

  When they are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for crosslinking the polymers obtained by radical polymerization.

  Examples that may be mentioned include divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol or tetraethylene glycol di (meth) acrylate. trimethylolpropane triacrylate, methylenebisacrylamide, methylene-bismethacrylamide, triallylamine, triallylcyanurate, diallyl maleate, tetraallylethylenediamine, tetra-allyloxyethane, trimethylolpropane diallyl ether, allyl (meth) acrylate, allyl ethers of alcohols of the series of sugars, or other allyl- or vinylethers of polyfunctional alcohols, as well as the allylic esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures of these compounds.

  Methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA) will be used more particularly. The degree of crosslinking generally varies from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.

  The ethylenically unsaturated monomers containing a sulfonic group are chosen in particular from vinylsulfonic acid, styrenesulphonic acid, (meth) acrylamido (C 1 -C 22) alkylsulphonic acids and N- (C 1 -C 22) alkyl (meth) acids. acrylamido (C 1 -C 22) alkylsulfonic acids such as undecyl-acrylamido-methanesulfonic acid and their partially or totally neutralized forms.

  Preferably, the ethylenically unsaturated monomer containing a sulfonic group is such that the sulphonic group or groups are not attached to an aromatic ring.

  More preferably, the (meth) acrylamido (C 1 -C 22) alkylsulphonic acids, such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulphonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, acid 2- methacrylamidododecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or completely neutralized forms.

  More particularly, use will be made of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms.

  The sulphonated polymers in accordance with the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or a C6-C22 din-alkylamine, and such as those described in the patent application WO00 / 31154 (forming part of the content of the description). These polymers may also contain, in addition, other units derived from hydrophilic monomers containing ethylenic unsaturation and not containing a fatty chain.

  These ethylenically unsaturated monomers having no fatty chain may be chosen for example from (meth) acrylic acids, their 13-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, the (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof.

  The sulfonated polymers may be chosen from amphiphilic copolymers of AMPS and at least one hydrophobic ethylenically unsaturated monomer comprising at least one more particularly from 12 to 18 carbon atoms.

  These same copolymers may also contain one or more units derived from ethylenically unsaturated monomers having no fatty chain, such as (meth) acrylic acids, their (3) alkyl substituted derivatives or their esters obtained with monohydric alcohols or mono or polyamines. alkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof.

  These copolymers are described in particular in patent application EP-A-750899, patent US 5089578 and in the following Yotaro Morishima publications: hydrophobic part having from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms, more preferably still 6 to 18 carbon atoms, more preferably 10 to 18 carbon atoms and more Self-assembling amphiphilic polyelectrolytes and their nanostructures - Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. Miscellanous formation of random copolymers of 2- (acrylamido) -2-methylpropanesulfonate and a non-ionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering (Macromolecules 2000, Vol. 33, No. 10-3694-3704; Solution properties of non-ionic moieties covalently bound to a polyelectrolyte: known effects on rheological behavior - Langmuir, 2000, Vol.16, N 12, 5324-5332; Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) 2-methylpropanesulfonate and associative macromonomers - Polym. Preprint, Div. Polym. Chem. 1999, 40 (2), 220-221.

  The hydrophobic monomers with ethylenic unsaturation of these particular copolymers are preferably chosen from the acrylates or acrylamides of formula (I) below: CH 2 (I) O = C CH 2 -CH (R 5) 1 -O x R 2 in which R 2, and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is O or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms, more preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more particularly 10 to 18 carbon atoms, and more particularly still 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

  The radical R2 is preferably chosen from linear C6-C18 alkyl (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C12) radicals). or adamantane (C10)); perfluorinated C 6 -C 18 alkyl radicals (for example the group of formula (CH 2) 2 (CF 2) 9-CF 3); the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, the linear alkyl radicals and more particularly the nodecyl radical are more particularly preferred.

  According to a particularly preferred form of the invention, the monomer of formula (I) comprises at least one alkylene oxide unit (x a1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly ethylene oxide units. The number of oxyalkylenated units generally varies from 3 to 100 and more preferably from 3 to 50 and even more preferably from 7 to 25.

  Among these polymers, mention may be made of: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 16) alkyl (meth) units acrylamide or (C 8 -C 16) alkyl (meth) acrylate units with respect to the polymer, such as those described in EP-A-750,899; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-C18) alkylacrylamide units, such as those described in US Patent 5089578.

  Mention may also be made of the uncrosslinked copolymers of partially or completely neutralized AMPS and of dodecyl methacrylate as well as the uncrosslinked or crosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide, such as those described in US Pat. Morishima articles quoted above.

  Copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of the following formula (II) are more particularly mentioned: ## STR2 ## in which X + is a proton, an alkali metal cation , an alkaline-earth metal cation or the ammonium ion, and units of the following formula (III): wherein X denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R, has the same meaning as that indicated above in formula (I) and R4 denotes a linear or branched C6-C22 and more preferably C10-C22 alkyl.

  Particularly preferred polymers are those where x = 25, R denotes methyl and R4 represents n-dodecyl; they are described in the articles of Morishima mentioned above.

  The polymers for which X + denotes sodium or ammonium are more particularly preferred.

  The sulphonated polymers in accordance with the invention can be obtained by conventional methods of radical polymerization in the presence of one or more initiators, such as, for example, azobisisobutyronitrile (AIBN), azobisdimethylvaleronitrile or ABAH (2,2-azobis). [2-amidinopropane] hydrochloride), organic peroxides such as dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, etc., inorganic peroxidized compounds such as potassium persulfate or ammonium, or H2O2 optionally in the presence of reducing agents.

  They are especially obtained by radical polymerization in tert-butanol medium in which they precipitate.

  By using precipitation polymerization in tert-butanol, it is possible to obtain a particularly favorable particle size distribution of the polymer for its uses.

  The particle size distribution of the polymer can be determined, for example, by laser diffraction or image analysis.

  An interesting distribution for polymer type and determined by image analysis is as follows: 60.2% less than 423 microns, 52.0% less than 212 microns, 26.6% less than 106 microns, 2.6% less than 45 microns and 26.6% greater than 850 microns.

  The reaction may be conducted at a temperature between 0 and 150 C, preferably between 10 and 100 C, either at atmospheric pressure or under reduced pressure. It can also be carried out under an inert atmosphere, and preferably under nitrogen.

  According to this process, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or one of its sodium or ammonium salts, with a (meth) acrylic acid ester, has been polymerized and, -d a C10-C18 alcohol oxyethylenated with 8 moles of ethylene oxide (GENAPOL C-080 from the company HOECHST / CLARIANT), -an oxo C11 oxyethylenated by 8 moles of ethylene oxide (GENAPOL UD-080 from the company HOECHST / CLARIANT), -an oxo alcohol C11 oxyethylenated with 7 moles of ethylene oxide (GENAPOL UD-070 from Hoechst / Clariant), -a C12 alcohol C14 oxyethylenated with 7 moles of ethylene oxide (GENAPOL LA-070 from the company HOECHST / CLARIANT), - a C12-C14 alcohol oxyethylenated with 9 moles of ethylene oxide (GENAPOL LA-090 from HOECHST / CLARIANT), a C12-C14 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL LA-110 from the company HOECHST / CLARIANT), -an alcohol C16-C18 oxyethylenated by 8 moles of oxide ethylene (GENAPOL T-080 from the company HOECHST / CLARIANT), a C16-C18 alcohol oxyethylenated with 15 moles of ethylene oxide (GENAPOL T-150 from the company HOECHST / CLARIANT), -d a C16-C18 alcohol oxyethylenated with 11 moles of ethylene oxide (GENAPOL T110 from the company HOECHST / CLARIANT), -a C16-C18 alcohol oxyethylenated with 20 moles of ethylene oxide (GENAPOL T -200 from the company HOECHST / CLARIANT), - a C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide (GENAPOL T-250 from the company HOECHST / CLARIANT), -an alcohol C18- C22 oxyethylenated with 25 moles of ethylene oxide and / or an iso C16-C18 alcohol oxyethylenated with 25 moles of ethylene oxide.

  The molar concentration in% of the units of formula (II) and units of formula (III) in the polymers according to the invention will vary according to the desired cosmetic application and the rheological properties of the desired formulation. It can vary between 0.1 and 99.9 mol%.

  Preferably for the most hydrophobic polymers, the molar proportion in units of formula (I) or (III) varies from 50.1 to 99.9%, more particularly from 70 to 95% and even more particularly from 80 to 90%. .

  Preferably for the low hydrophobic polymers, the molar proportion of units of formula (I) or (III) ranges from 0.1 to 50%, more particularly from 5 to 25% and even more particularly from 10 to 20%.

  The distribution of the monomers in the polymers of the invention may be, for example, alternating, block (including multiblock) or any.

  According to the invention, it is preferred that the polymers have pendant heat-sensitive chains whose aqueous solution has a viscosity which, above a certain threshold temperature, increases, or remains substantially constant, as the temperature increases.

  Even more particularly, polymers whose aqueous solution has a viscosity which is low below a first threshold temperature and which, above this first threshold temperature, increases towards a maximum when the temperature increases, and which, at above a second threshold temperature decreases again as the temperature increases. In this context, it is preferred that the viscosity of the polymer solutions below the first threshold temperature is from 5 to 50%, in particular from 10 to 30% of the maximum viscosity at the second threshold temperature.

  These polymers, preferably, lead in the water to a demixing phenomenon by heating resulting in curves having, as a function of temperature and concentration, a minimum called LCST (Lower Critical Solution Temperature).

  The viscosities (measured at 25 ° C. on the Brookfield needle 7 viscometer) of the 1% aqueous solutions are preferably 20,000 mPa. s to 100,000 mPa.s and more particularly from 60,000 mPa.s to 70,000 mPa.s.

  The sulphonated polymers in accordance with the invention are preferably present in an amount ranging from 0.01% to 30% by weight, more preferably between 0.1% and 20% by weight and even more preferably from 0.5% to 15% by weight. % by weight relative to the total weight of the hair treatment composition.

  The anionic fixing polymers according to the invention are polymers containing groups derived from carboxylic or phosphoric acid and have a number-average molecular mass of between about 500 and 5,000,000.

  For the purposes of the present invention, the term "fixing polymer" means any polymer that makes it possible to impart a shape or maintain a shape to a given hair.

  The carboxylic groups are provided by unsaturated mono- or di-carboxylic acid monomers such as those having the formula: wherein n is an integer from 0 to 10, A, denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the neighboring methylene group when n is greater than 1, by means of a heteroatom such as oxygen or sulfur, R denotes a hydrogen atom, a phenyl or benzyl group, R8 denotes a hydrogen atom, a lower alkyl or carboxyl group, R9 denotes a hydrogen atom, a lower alkyl group, a -CH2-COOH group, phenyl or benzyl group.

  In the abovementioned formula, a lower alkyl group preferably denotes a group having 1 to 4 carbon atoms and in particular the methyl and ethyl groups.

  The anionic fixing polymers containing carboxylic groups which are preferred according to the invention are: 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 ALLIED COLLOID, and ULTRAHOLD by BASF, copolymers of acrylic acid and acrylamide sold in the form of their sodium salts under the names RETEN 421, 423 or 425 by the company HERCULES, the sodium salts of polyhydroxycarboxylic acids.

  B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid, optionally grafted onto a polyalkylene glycol such as polyethylene glycol, and optionally crosslinked. Such polymers are described in particular in French Patent No. 1,222,944 and German Application No. 2,330,956, copolymers of this type comprising in their chain an acrylamide unit optionally N-alkylated and / or hydroxyalkylated as described in particular in the US Pat. Luxembourg patent applications Nos. 75370 and 75371 or proposed under the name QUADRAMER by AMERICAN CYANAMID. Mention may also be made of copolymers of acrylic acid and of C 1 -C 4 alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of C 1 -C 20 alkyl methacrylate, for example lauryl, such as sold by ISP under the name ACRYLIDONE LM and methacrylic acid / ethyl acrylate / tert-butyl acrylate terpolymers such as the product marketed under the name LUVIMER 100 P by the company BASF.

  Mention may also be made of methacrylic acid / acrylic acid / ethyl acrylate / methyl methacrylate copolymers in aqueous dispersion, sold under the name AMERHOLD DR 25 by the company AMERCHOL.

  C) Crotonic acid copolymers, such as those comprising in their chain vinyl acetate or propionate units, and optionally other monomers such as allyl or methallyl esters, vinyl ethers or vinyl esters of a saturated carboxylic acid, linear or branched, long hydrocarbon chain, such as those comprising at least 5 carbon atoms, these polymers may optionally be grafted or crosslinked, or another monomer vinyl ester, allyl or methallylique a carboxylic acid a- or p-cyclic . Such polymers are described, inter alia, in French patents No. 1,222,944, 1,580,545, 2,265,782, 2,265,781, 1,564,110 and 2,439,798. Commercial products in this class are resins 28-29. 30, 26-13-14 and 28-13-10 marketed by the company National Starch.

  D) copolymers of C 4 -C 8 monounsaturated carboxylic acids or anhydrides chosen from 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, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers being optionally monoesterified or monoamidified. Such polymers are described in particular in US Pat. Nos. 2,047,398, 2,723,248, 2,102,113 and GB No. 839,805. Commercial products are especially those sold under the names Gantrez AN or ES by the company ISP.

  copolymers comprising (i) one or more maleic, citraconic, itaconic anhydride units and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, aolefin, acrylic or methacrylic acid, acidic groups acrylic or methacrylic or vinylpyrrolidone in their chain, the anhydride functions of these copolymers being optionally monoesterified or monoamidified.

  These polymers are for example described in French patents Nos. 2,350,384 and 2,357,241 of the applicant.

  E) Polyacrylamides having carboxylate groups.

  According to the invention, the anionic fixing polymers are preferably chosen from acrylic acid copolymers such as acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers sold in particular under the name ULTRAHOLD STRONG by the company BASF, the copolymers derived therefrom. crotonic acid such as vinyl acetate terpolymers / vinyl tert-butylbenzoate / crotonic acid and the crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold in particular under the name Resin 28- 29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, such as the monoesterified methyl vinyl ether / maleic anhydride copolymers sold, for example, under the name GANTREZ by ISP, copolymers methacrylic acid and methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the copolymers of methacrylic acid and ethyl acrylate sold under the name Luvimer MAEX or MAE by the company BASF and the copolymers vinyl acetate / crotonic acid sold in particular under the name Luviset CA 66 by the company BASF and polyvinyl glycol-grafted vinyl acetate / crotonic acid copolymers sold under the name ARISTOFLEX A by the company BASF.

  Among the above-mentioned anionic fixing polymers, it is more particularly preferred to use in the context of the present invention the monoesterified methyl vinyl ether / maleic anhydride copolymers sold under the name Gantrez ES 425 by the company ISP, the acrylic acid / ethyl acrylate terpolymers. N-tert-butylacrylamide sold under the name ULTRAHOLD STRONG by the company BASF, the copolymers of methacrylic acid and of methyl methacrylate sold under the name EUDRAGIT L by the company ROHM PHARMA, the terpolymers vinyl acetate / tert-butylbenzoate / crotonic acid and the crotonic acid / vinyl acetate / neododecanoate vinyl terpolymers sold under the name Resin 28-29-30 by the company National Starch, the copolymers of methacrylic acid and ethyl acrylate sold under the name Luvimer MAEX OR MAE by BASF, vinylpyrrolidone / acid terpolymers acrylic / lauryl methacrylate sold under the name ACRYLIDONE LM by the company ISP.

  The nonionic fixing polymers that can be used according to the present invention are chosen, for example, from: polyalkyloxazolines; homopolymers of vinyl acetate; vinyl acetate copolymers such as, for example, copolymers of vinyl acetate and acrylic ester, copolymers of vinyl acetate and ethylene, or copolymers of vinyl acetate and of maleic ester, for example, dibutyl maleate; homopolymers and copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates such as the products offered by the company Rohm & Haas under the names PRIMAL AC-261 K and EUDRAGIT NE 30 D, by the company BASF under the name 8845, by the company HOECHST under the name APPRETAN N9212; copolymers of acrylonitrile and of a nonionic monomer chosen, for example, from butadiene and alkyl (meth) acrylates; mention may be made of the products sold under the name CJ 0601 B by the company Rohm &Haas; homopolymers of styrene; styrene copolymers such as, for example, styrene and alkyl (meth) acrylate copolymers such as Mowilith LDM 6911, Mowilith DM 611 and Mowilith LDM 6070 products supplied by Hoechst, RHODOPAS SD 215 and RHODOPAS DS 910 offered by RHONE POULENC; copolymers of styrene, alkyl methacrylate and alkyl acrylate; copolymers of styrene and butadiene; or copolymers of styrene, butadiene and vinylpyridine; polyamides; homopolymers of vinyllactam different from homopolymers of vinylpyrrolidone, such as polyvinylcaprolactam sold under the name Luviskol PLUS by the company BASF; and copolymers of vinyllactam such as a poly (vinylpyrrolidone / vinyllactam) copolymer sold under the trade name Luvitec VPC 55K65W by the company BASF, polyvinylpyrrolidone / vinyl acetate copolymers, such as those sold under the name PVPVA S630L by the ISP company, Luviskol VA 73, VA 64, VA 55, VA 37 and VA 28 by BASF; and poly (vinylpyrrolidone / vinyl acetate / vinyl propionate) terpolymers, for example, the one marketed under the name Luviskol VAP 343 by the company BASF. The alkyl groups of the nonionic polymers mentioned above preferably have 1 at 6 carbon atoms.

  According to the invention, it is also possible to use fixing polymers of the ionic grafted or nonionic silicone type, comprising a polysiloxane part and a part consisting of a non-silicone organic chain, one of the two parts constituting the main chain of the polymer and the other being grafted onto said main chain.

  These polymers are for example described in patent applications EP-AO 412 704, EP-AO 412 707, EP-AO 640 105 and WO 95/00578, EP-A-0 582 152 and WO 93/23009 and US Patents 4,693,935, US 4,728,571 and US 4,972,037.

  These polymers may be amphoteric, anionic or nonionic, and they are preferably anionic or nonionic.

  Such polymers are, for example, the copolymers that can be obtained by radical polymerization from the monomer mixture formed: a) from 50 to 90% by weight of t-butyl acrylate, b) from 0 to 40% by weight acrylic acid, c) from 5 to 40% by weight of a silicone macromer of the formula ## STR3 ## wherein CH 2 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 where v is a number from 5 to 700, the percentages by weight being calculated with respect to the total weight of the monomers.

  Other examples of grafted silicone polymers are, in particular, polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connection link, mixed polymeric units of the poly (meth) acrylic acid type and poly (alkyl) (meth) acrylate), and polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connecting member, polymeric units of the polyisobutyl (meth) acrylate type. .

  Another type of silicone fixing polymers that may be mentioned is the Luviflex Silk product marketed by BASF.

  The anionic or nonionic fixing polymers are preferably present in an amount of between 0.1% and 30% by weight, more preferably between 0.2% and 15% by weight and even more preferably between 0.5% and 10% by weight. weight relative to the total weight of the cosmetic hair treatment composition.

  The polyols of the invention are preferably compounds comprising from 3 to 100 carbon atoms and from 2 to 20 hydroxyl groups. They may furthermore in their structure have other functional groups and in particular carbonyl or carboxyl groups.

  They can be linear or branched and their carbon chain can be interrupted by oxygen atoms.

  These polyols will preferably be chosen from propylene glycol, glycerol, diols and triols containing 5 to 10 carbon atoms, polyethylene glycols, mono or polysaccharides and their reduction products (glucitols) or oxidation products (gluconic acids).

  Even more preferentially, the polyols will be chosen from glycerol, polyethylene glycols and sorbitol. Sorbitol is especially preferred.

  The polyols are preferably present in an amount of between 0.01% and 20% by weight, preferably between 0.1% and 10% and even more preferentially between 0.2 and 15% by weight relative to the total weight of the cosmetic composition of hair treatment.

  All propellants well known in the art can be used in the present invention, such as hydrocarbon gases, such as C3-5 alkanes, for example, propane, n-butane, isobutane; fluorinated gases such as, for example, chlorodifluoromethane, dichlorodifluoromethane, 1,1-difluoroethane, chlorodifluoroethane, dichlorotetrafluoroethane; nitrogen, air and carbon dioxide; dimethyl ether; and their mixtures.

  Preferably, dimethyl ether, hydrocarbon gases, or mixtures thereof are used, such as, for example, mixtures of dimethyl ether and C3-5 alkanes. Even more preferentially, dimethyl ether is used.

  The propellants are preferably used in an amount greater than 20% by weight, preferably between 20% and 70% by weight and even more preferably between 20% and 50% by weight relative to the total weight of the cosmetic composition of the present invention. hair treatment.

  The cosmetically acceptable medium comprises water and / or a cosmetically acceptable solvent such as a lower alcohol C1-C4, such as ethanol, isopropanol, tert-butanol, n-butanol, ethers of polyols; and their mixtures.

  The water content is preferably between 20% and 80% by weight relative to the total weight of the composition.

  The composition according to the invention may furthermore comprise conventional cosmetic additives chosen from reducing agents such as thiols, fatty substances, thickening agents, mineral or organic agents other than the sulphonated polymers of the invention, softeners and pearlescent agents. antifoam agents, sunscreens, antiperspirants, acidifying agents, alkalizing agents, dyes, pigments, perfumes, preservatives, nonionic, anionic, cationic and amphoteric surfactants, sequestering agents, polymers, volatile or nonvolatile silicones, vegetable, animal, mineral or synthetic oils, proteins, ceramides and pseudoceramides, vitamins, plasticizing agents and mixtures thereof.

  Those skilled in the art will take care to choose any additives and their amount so that they do not affect the properties of the compositions of the invention.

  These additives are preferably present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.

  The hair treatment compositions in accordance with the invention are packaged in an aerosol device that is usual in cosmetics.

  The present invention also relates to an aerosol device containing the cosmetic composition as described above.

  The present invention also relates to a cosmetic hair treatment process which consists in vaporizing an effective amount of a composition as described above, directly on the hair or via the fingers, to rinse or not after a possible exposure time .

  Preferably, the composition is not rinsed.

  According to a preferred embodiment of the invention, the composition can be used as hair lacquer.

  The following example illustrates the present invention and should not be considered in any way as limiting the invention.

EXAMPLE

  A styling product is prepared in the form of an aerosol spray. The amounts are indicated in% by weight relative to the total weight of the composition: the name Aristoflex HMS by the company CLARIANT 0.9% Ethanol 19% - Sorbitol 0.45% - Dimethyl ether 35% - Water qs 100% This is sprayed styling product on the hair and shaping the hairstyle. This gives a good hold of the hairstyle. In addition, this composition crackles in the hand and induces a lasting effect of freshness.

  PVP (60) / VA (40) sold by BASF 5.0% - Polyacrylamidomethylpropanesulfonic acid partly neutralized with ammonia and highly crosslinked, available under US Pat.

Claims (61)

  1. Cosmetic hair treatment composition, in the form of an aerosol, characterized in that it comprises, in a cosmetically acceptable medium, at least one anionic or nonionic fixing polymer other than polyurethanes, at least one partially or partially sulfonated polymer. completely neutralized or not, comprising at least one unit derived from an ethylenically unsaturated monomer containing sulfonic group, - at least one polyol, and - a propellant.   2. Treatment composition according to claim 1, characterized in that the fixing polymer is anionic and selected from homopolymers or copolymers of acrylic and methacrylic acid, crotonic acid copolymers, copolymers of carboxylic acids or anhydrides. mono unsaturated C4-C8, polyacrylamides with carboxylate group, anionic grafted silicone polymers.   3. Treatment composition according to claim 1, characterized in that the fixing polymer is nonionic and selected from polyalkyloxazolines, homopolymers and copolymers of vinyl acetate, homopolymers and copolymers of acrylic esters, copolymers of acrylonitrile styrene homopolymers and copolymers, polyamides, vinyllactam homopolymers other than vinylpyrrolidone homopolymers, vinylactam copolymers and nonionic grafted silicone polymers.   4. Treatment composition according to any one of claims 1 to 3, characterized in that the sulfonated polymer has a hydrophobic portion having from 6 to 50 carbon atoms.   5. Treatment composition according to characterized in that the hydrophobic portion of the comprises from 6 to 22 carbon atoms.   6. Treatment composition according to characterized in that the hydrophobic portion of the comprises from 6 to 18 carbon atoms.   7. Treatment composition according to characterized in that the hydrophobic portion of the comprises from 10 to 18 carbon atoms.   8. Treatment composition according to characterized in that the hydrophobic portion of the comprises from 12 to 18 carbon atoms.   9. Treatment composition according to one of the preceding claims, characterized in that said sulfonated polymers are neutralized partially or totally by a mineral or organic base.   10. Treatment composition according to any one of the preceding claims, characterized in that the sulfonated polymers have a number average molecular weight ranging from 1000 to 20 000 000 g / mol.   11. Treatment composition according to claim 10, characterized in that the sulfonated polymers have a number average molecular weight ranging from 20,000 to 5,000,000 g / mol.   12. The treatment composition as claimed in claim 11, characterized in that the number-average molecular weight of the sulphonated polymer or polymers varies from 100,000 to 1,500,000 g / mol.   13. Treatment composition according to any one of the preceding claims, characterized in that the sulphonated polymer or polymers are prepared by radical polymerization by precipitation in tert-butanol.   14. Treatment composition according to any one of the preceding claims, characterized in that the sulphonated polymer or polymers are crosslinked or non-crosslinked.   claim 4, sulfonated polymer claim 5, sulfonated polymer claim 6, sulfonated polymer claim 7, any sulfonated polymer such as 15. Treatment composition according to claim 14, characterized in that the sulphonated polymer or polymers are crosslinked.   16. Treatment composition according to claim 15, characterized in that the one or more crosslinking agents are chosen from olefinically polyunsaturated compounds.   17. Treatment composition according to claim 16, characterized in that the crosslinking agent or agents are selected from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA).   18. Treatment composition according to claim 14 to 17, characterized in that the degree of crosslinking preferably ranges from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.   19. Treatment composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer containing sulfonic group is chosen from vinylsulfonic acid, styrene sulfonic acid, (meth) acrylamido acids (C, - C22) alkylsulphonic acids, N- (C 1 -C 22) alkyl (meth) acrylamido (C 1 -C 22) alkylsulphonic acids and their partially or totally neutralized forms.   20. Treatment composition according to claim 19, characterized in that the ethylenically unsaturated monomer containing sulfonic group is chosen from acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2acryamido-n-butanesulfonic acid, 2-acrylamido-2,4,4trimethylpentanesulphonic acid, 2-methacrylamido-dodecylsulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and their partially or completely neutralized forms.   21. Treatment composition according to any one of claims 19 or 20, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its forms partially or totally neutralized.   22. Treatment composition according to claim 21, characterized in that the sulfonated polymer (s) is (are) chosen from the random polymers of AMPS modified by reaction with a nmono (C6C22) alkylamine or a di-n- (C6-C22) alkylamine .   23. Treatment composition according to any one of claims 21 or 22, characterized in that the sulfonated polymer or polymers further contain at least one unit derived from an ethylenically unsaturated monomer having no fatty chain.   24. Treatment composition according to claim 23, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their alkyl derivatives substituted at 13, and their esters obtained with mono alcohols or mono- or polyalkylene glycols, or from (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures thereof.   25. Treatment composition according to any one of claims 1 to 21, characterized in that the sulfonated polymer or polymers are chosen from amphiphilic copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation comprising at least a part hydrophobic having from 6 to 50 carbon atoms.   26. Treatment composition according to claim 25, characterized in that the hydrophobic part comprises from 6 to 22 carbon atoms.   27. Treatment composition according to claim 26, characterized in that the hydrophobic part comprises from 6 to 18 carbon atoms.   28. Treatment composition according to claim 27, characterized in that the hydrophobic part comprises from 10 to 18 carbon atoms.   29. Treatment composition according to claim 28 characterized in that the hydrophobic portion comprises from 12 to 18 carbon atoms.   30. Treatment composition according to any one of claims 25 to 29, characterized in that the hydrophobic monomer ethylenically unsaturated is selected from acrylates or acrylamides of formula (I) following (I) Y [CH2-CH (R3 R 1 and R 3, which may be identical or different, denote a hydrogen atom or a linear or branched C 1 -C 6 alkyl radical, preferably methyl; Y is O or NH; R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms, more preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more particularly 10 to 18 carbon atoms, and more particularly still 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.   31. Treatment composition according to claim 30, characterized in that the hydrophobic radical R2 is chosen from linear, branched or cyclic C6-C18 alkyl radicals; C 6 -C 18 perfluorinated alkyl radicals; the cholesteryl radical or a cholesterol ester; polycyclic aromatic groups.   32. Treatment composition according to any one of claims 30 or 31, characterized in that the monomer of formula (I) additionally comprises at least one alkylene oxide unit (x> 1).   33. Treatment composition according to any one of claims 30 to 32, characterized in that the monomer of formula (I) further comprises at least one polyoxyalkylene chain.   34. Treatment composition according to claim 33, characterized in that the polyoxyalkylene chain consists of ethylene oxide units and / or propylene oxide units.   35. Treatment composition according to claim 34, characterized in that the polyoxyalkylene chain consists solely of ethylene oxide units.   36. Treatment composition according to any one of claims 30 to 35, characterized in that the number of oxyalkylenated units ranges from 3 to 100.   37. Treatment composition according to claim 36, characterized in that the number of oxyalkylenated units ranges from 3 to 50.   38. Treatment composition according to claim 37, characterized in that the number of oxyalkylenated units varies from 7 to 25.   39. Treatment composition according to any one of claims 25 to 31, characterized in that the sulfonated polymer is chosen from: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 16) alkyl (meth) acrylamide units or (C 8 -C 16) alkyl (meth) acrylate units, based on the polymer; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-C18) alkylacrylamide units, relative to the polymer .   40. Treatment composition according to any one of claims 25 to 31, characterized in that the sulfonated polymer is chosen from: - uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecyl methacrylate, - copolymers crosslinked or uncrosslinked partially or completely neutralized AMPS and ndodecylmethacrylamide.   41. Treatment composition according to any one of claims 25 to 38, characterized in that the sulfonated polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below: CH3 Wherein X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, and units of the following formula (III): ## STR2 ## wherein x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R, has the same meaning as that indicated above in formula (I) and R4 denotes a linear or branched C6-C22 and more preferably C10-C22 alkyl.   42. A treatment composition according to claim 41, wherein x = 25, R1 is methyl and R4 is ndodecyl.   43. Treatment composition according to claim 30 or 41, characterized in that the molar proportion in% of the units of formula (I) or of formula (III) in the polymers ranges from 50.1 to 99.9%.   44. Treatment composition according to claim 30 or 41, characterized in that the molar proportion in% of units of formula (I) or units of formula (III) in the polymers ranges from 0.1 to 50%.   45. A treatment composition according to any one of the preceding claims, characterized in that the anionic or nonionic fixing polymer is present in an amount of 0.1% to 30% by weight, preferably 0.2% to 15% by weight. % by weight and even more preferably from 0.5% to 10% by weight relative to the total weight of the composition.   46. Treatment composition according to any one of the preceding claims, characterized in that the sulfonated polymer is present in an amount of from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight and more preferably from 0.5% to 15% by weight relative to the total weight of the composition.   47. Treatment composition according to any one of the preceding claims, characterized in that the polyol has from 3 to 100 carbon atoms and from 2 to 20 hydroxyl groups.   48. Treatment composition according to any one of the preceding claims, characterized in that the polyol is a diol or a triol having 5 to 10 carbon atoms, a polyethylene glycol, mono- or polysaccharides or their reduced or oxidized forms, propylene glycol. or glycerol.   49. Treatment composition according to any one of the preceding claims, characterized in that the polyol is sorbitol.   50. Treatment composition according to any one of the preceding claims, characterized in that the polyol is present in an amount of from 0.01% to 20% by weight, preferably from 0.1% to 10% and even more preferably from 0.2 to 15% by weight relative to the total weight of the composition 51. Treatment composition according to any one of the preceding claims, characterized in that the propellant is selected from dimethyl ether, hydrocarbon gases, fluorinated gases and mixtures thereof.   52. Treatment composition according to any one of the preceding claims, characterized in that the propellant is dimethyl ether.   53. Treatment composition according to any one of the preceding claims, characterized in that the amount of propellant is greater than 20% by weight relative to the total weight of the composition.   54. Treatment composition according to any one of the preceding claims, characterized in that the amount of propellant is between 20% and 70% by weight and even more preferably between 20% and 50% by weight relative to the weight. total of the composition.   55. Treatment composition according to any one of the preceding claims, characterized in that the cosmetically acceptable medium comprises water and / or a cosmetically acceptable solvent.   56. Treatment composition according to claim 55, characterized in that the cosmetically acceptable solvent is chosen from C1-C4 lower alcohols, polyol ethers and mixtures thereof.   57. Treatment composition according to claim 55 or 56, characterized in that the cosmetically acceptable solvent is chosen from ethanol, isopropanol and tert-butanol.   58. Treatment composition according to any one of the preceding claims, characterized in that the aqueous composition further comprises one or more usual cosmetic additives chosen from reducing agents such as thiols, fatty substances, thickeners, minerals or organic agents. , softeners, pearlescent agents, defoamers, sunscreens, antiperspirants, acidifying agents, alkalizing agents, dyes, pigments, perfumes, preservatives, nonionic, anionic, cationic surfactants and amphoteric, sequestering agents, polymers, volatile or nonvolatile silicones, vegetable, animal, mineral or synthetic oils, proteins, ceramides and pseudoceramides, vitamins, plasticizers and mixtures thereof.   59. An aerosol device characterized in that it contains the cosmetic treatment composition according to any one of the preceding claims.   60. A styling process, characterized in that the cosmetic treatment composition according to any one of claims 1 to 58 is sprayed directly onto the hair to be shaped or via the fingers.   61. Use of the cosmetic treatment composition according to any one of claims 1 to 58 as hairspray.