EP1961490A1 - Device for spraying a fixing composition - Google Patents

Abstract

The spray device of a cosmetic composition having water, comprises a container equipped with a spray mechanism, a perforated membrane, a piezoelectric actuator for vibrating the membrane in a frequency of 20 KHz to 7 MHz, a unit for contacting the liquid composition contained in the container with internal surface of the membrane, a unit for pressure offset providing reduced pressure to the liquid in contact with the internal surface of the membrane, and additives. The perforations of the membrane allow an interior of the container to communicate with external environment. The spray device of a cosmetic composition having water, comprises a container equipped with a spray mechanism, a perforated membrane, a piezoelectric actuator for vibrating the membrane in a frequency of 20 KHz to 7 MHz, a unit for contacting the liquid composition contained in the container with internal surface of the membrane, a unit for pressure offset providing reduced pressure to the liquid in contact with the internal surface of the membrane, and additives. The perforations of the membrane allow an interior of the container to communicate with external environment, and have an inverse conicity such as transversely crossed surface larger than the external surface of the membrane. The cosmetic composition flows itself in the form of droplets through perforations upto external surface of the membrane, and comprises an anionic, cationic, amphoteric or non-ionic fixing polymer (1-12 wt.%) in a cosmetically acceptable medium. The reduced pressure varies from ambient pressure upto a pressure at which the air is sucked through the perforations in contact with the composition. The contact unit comprises a supply mechanism with bubble generator by capillarity. Perforations with normal conicity are disposed around and to exterior of the perforations with inverse conicity. The additives are alkalizing agent, acidifying agent, silicon, perfumes, conservative agents, UV absorbent agents, colorants and/or anti-corrosion agents.

Description

The present invention relates to a specific spray device, in the form of a spray, comprising a cosmetic composition comprising itself at least one fixing polymer, for styling, shaping and / or maintaining the hairstyle.

The lacquers and hair sprays marketed today are generally composed of a liquid phase containing at least one fixing polymer and propelled by a liquefied gas under reduced pressure, an aerosol generator. Such gases generally include volatile organic compounds (VOCs).

The introduction of new legislation tends to impose a reduction in the amount of volatile organic compounds (VOCs) released into the atmosphere by aerosol-generating gases.

To achieve this reduction, a non-VOC propellant such as HFA 152a can be used to partially or completely substitute the propellants usually used. Nevertheless, the use of this type of gas is not allowed in all countries.

In the case of a conventional aerosol, another solution for limiting the use of VOCs is to introduce a large amount of water into the cosmetic compositions.

The results in terms of quality of use and cosmetic efficacy of cosmetic compositions comprising a large amount of water, are in retreat compared to previous formulations because the presence of water can cause an increased drying time which is not not favorable to obtaining a good level of fixation.

Another way to limit the use of VOCs is not to use propellant gas, using a spraying device equipped with a mechanical pump. Each time the device is actuated, a unit dose of product is delivered to the hair. This discontinuity of the flow can lead to uneven distribution of the product on the hair and a poor maintenance of the hairstyle.

Surprisingly, the Applicant has discovered that the use of a specific spraying device, comprising a container whose nozzle comprises a perforated membrane, actuated by a system producing vibrations and through which the liquid cosmetic composition is transformed into droplets, the system producing vibrations being in particular a piezoelectric system, makes it possible to solve the problems mentioned above when it is used together with a cosmetic composition containing at least one fixing polymer. This joint use leads, without resorting to propellant gases VOC, to an excellent fixation of the hairstyle, compared to the solutions of the prior art described above.

• une membrane perforée, les perforations de la membrane faisant communiquer l'intérieur du récipient avec l'environnement externe,
• un actionneur pour faire vibrer la membrane,
• un moyen pour amener la composition cosmétique liquide contenue dans le récipient au contact d'une surface interne de la membrane,
  la composition cosmétique, sous l'effet des vibrations de la membrane s'écoulant à travers les perforations jusqu'à une surface externe de la membrane d'où elle émerge sous forme de gouttelettes, et
  la composition cosmétique liquide comprenant, dans un milieu cosmétiquement acceptable, au moins un polymère fixant.

The subject of the invention is therefore a device for spraying a cosmetic composition comprising a container equipped with a spraying mechanism comprising:

• a perforated membrane, the perforations of the membrane communicating the interior of the container with the external environment,
• an actuator to vibrate the membrane,
• means for bringing the liquid cosmetic composition contained in the container into contact with an inner surface of the membrane,
  the cosmetic composition, under the effect of vibrations of the membrane flowing through the perforations to an outer surface of the membrane from which it emerges in the form of droplets, and
  the liquid cosmetic composition comprising, in a cosmetically acceptable medium, at least one fixing polymer.

The perforations in the membrane preferably have an inverted conicity, i.e. a larger cross-sectional area on the outer surface of the membrane, facing the external environment, than on the inner surface, making face inside the container.

The spraying device may further comprise a pressure offset means, as described in the application WO95 / 15822 , providing reduced pressure to the liquid in contact with the inner surface of the membrane. The reduced pressure may vary from ambient pressure to the pressure at which air is drawn through the perforations of the membrane in contact with the composition.

Preferably, the perforations on the outer surface of the membrane do not touch each other.

Preferably, the actuator is a piezoelectric actuator, for example designed to vibrate the membrane in a frequency range from 20 KHz to 7 MHz. The energy required for the operation of the piezoelectric actuator can be obtained by means of a generator electrical, for example an electric battery, a battery or a photovoltaic cell that can be optionally coupled to an electronic circuit.

In the spraying mechanism defined above, the means for bringing the liquid cosmetic composition to the surface of the membrane may comprise a capillary feeding mechanism, or alternatively a bubble generating feeding mechanism. Such mechanisms are described for example in the international application WO95 / 15822 .

In particular embodiments of the invention, all the perforations have an inverted conicity, or conversely, the membrane has, in addition, perforations of normal conicity.

By perforation of normal conicity is meant in the sense of the present invention perforations whose cross-sectional area is smaller on the outer surface of the membrane, facing the external environment, than on the inner surface, facing the inside of the container.

When normal conical perforations are present, these are preferably disposed around and outside the inverted conical perforations.

The means for bringing the liquid cosmetic composition to the surface of the membrane may be designed to bring said composition to the inner surface of said membrane, or conversely to be designed to bring said composition to the outer surface of said membrane. Such variants of the spraying device are described, for example, in the international application WO95 / 15822 .

For example, the membrane may be formed of a circular disc with a diameter of 8 mm, electroformed nickel, a thickness of 70 μm having a plurality of perforations. The perforations may have a circular disk-shaped cross-sectional area, the diameter of which varies from 4 to 150 μm on the outer surface of the membrane, facing the external environment, and on the inner surface, facing the inside. of the container, a cross-sectional surface in the form of a circular disc whose diameter varies from 2 to 50 μm, and for example from 10 to 20 μm.

When using the device, the cosmetic composition emerges in the form of droplets whose mean diameter is preferably between 20 and 100 μm, and even more preferably between 30 and 60 μm.

By fixing polymer is meant in the sense of the present invention any polymer capable of providing and / or maintain a shape to a hair.

Any fixing polymer known as such in the field of hair treatments, as well as of course mixtures containing several of these polymers, may be used for the present invention. Cationic, anionic, amphoteric and nonionic fixing polymers are conventionally distinguished.

The cationic fixing polymers which can be used according to the present invention are preferably chosen from polymers containing primary, secondary, tertiary and / or quaternary amine groups which are part of the polymer chain or directly connected thereto, and which have a molecular weight of between 500 and about 5,000,000 and preferably between 1,000 and 3,000,000.

1. (1) les homopolymères ou copolymères dérivés d'esters ou d'amides acryliques ou méthacryliques et comportant au moins un des motifs suivants :
   
   dans lesquels :
   • R_a et R_b représentent chacun un atome d'hydrogène ou un groupe alkyle en C_1-6,
   • R_c désigne un atome d'hydrogène ou un radical CH₃.
   • R_d, R_e et R_f, identiques ou différents, représentent chacun un groupe alkyle en C_1-18 ou un radical benzyle,
   • A est un groupe alkyle linéaire ou ramifié en C_1-6 ou un groupe hydroxyalkyle en C_1-4, et
   • X^- désigne un anion méthosulfate ou halogénure tel qu'un ion chlorure
     ou bromure.
   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, diacétone-acrylamides, acrylamides et méthacrylamides substitués sur l'azote par des groupes alkyle inférieurs, des acides acryliques ou méthacryliques ou leurs esters, des vinyllactames tels que la vinylpyrrolidone ou le vinylcaprolactame, et des esters vinyliques.
   Ainsi, on peut citer parmi les copolymères de la famille (1) :
   • les copolymères d'acrylamide et de méthacrylate de diméthylaminoéthyle quaternisés au sulfate de diméthyle ou avec un halogénure de diméthyle, tels que celui vendu sous la dénomination HERCOFLOC® par la Société HERCULES,
   • les copolymères d'acrylamide et de chlorure de méthacryloyloxyéthyltriméthylammonium décrits 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 méthacryloyloxyéthyltriméthylammonium vendu sous la dénomination RETEN® par la Société HERCULES,
   • les copolymères vinylpyrrolidone/acrylate ou méthacrylate de dialkylaminoalkyle quaternisés 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 demandes de brevets français FR2.077.143 et FR2.393.573 ,
   • les terpolymères méthacrylate de diméthylaminoéthyle/vinylcaprolactame/vinylpyrrolidone tels que le produit commercialisé sous la dénomination GAFFIX VC 713 par la Société ISP, et
   • le copolymère vinylpyrrolidone/méthacrylamide de diméthylaminopropyle quaternisé tel que le produit vendu sous la dénomination GAFQUAT® HS 100 par la Société ISP.
2. (2) les polysaccharides quaternisés décrits plus particulièrement par les brevets américains 3.589.578 et 4.031.307 tels que les gommes de guar contenant des groupements cationiques trialkylammonium.
   De tels produits sont commercialisés notamment sous les dénominations commerciales de JAGUAR® C13 S, JAGUAR® C15 et JAGUAR® C17 par la Société MEYHALL.
3. (3) Les copolymères quaternaires de vinylpyrrolidone et de vinylimidazole tels que les produits commercialisés par BASF sous la dénomination LUVIQUAT® TFC,
4. (4) les chitosanes ou leurs sels, en particulier les acétate, lactate, glutamate, gluconate ou pyrrolidonecarboxylate de chitosane.
   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 pyrrolidonecarboxylate de chitosane vendu sous la dénomination KYTAMER® PC par la Société AMERCHOL.
5. (5) Les dérivés de cellulose cationiques tels que les copolymères de cellulose ou les dérivés de cellulose greffés avec un monomère hydrosoluble comportant un groupe ammonium quaternaire et décrits notamment dans le brevet US 4 131 576 tels que les hydroxyalkylcelluloses, comme les hydroxyméthylhydroxyéthyl- ou hydroxypropylcelluloses greffées notamment avec un sel de méthacryloyloxyéthyltriméthylammonium, de méthacrylamidopropyltriméthylammonium ou de diméthyldiallylammonium.

Among these polymers, mention may be made more particularly of the following cationic polymers:

1. (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the following units:
   
   wherein :
   • R _a and R _b each represent a hydrogen atom or a C _1-6 alkyl group,
   • R _c denotes a hydrogen atom or a CH ₃ radical.
   • R _d , R _e and R _f , which may be identical or different, each represent a C _1-18 alkyl group or a benzyl radical,
   • A is a linear or branched C _1-6 alkyl group or a C _1-4 hydroxyalkyl group, and
   • X ^- denotes a methosulphate or halide anion such as a chloride ion
     or bromide.
   The copolymers of family (1) also contain one or more units derived from comonomers which may be chosen from the family of acrylamides, methacrylamides, diacetone-acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyl groups, acrylic acids or methacrylics or their esters, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.
   Thus, mention may be made, among the copolymers of the family (1):
   • copolymers of dimethylaminoethyl acrylamide and methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as that sold under the name HERCOFLOC® by the company HERCULES,
   • the copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride described for example in the patent application EP-A-080976 and sold under the name BINA QUAT® P 100 by CIBA GEIGY,
   • the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulphate sold under the name Reten® by the company Hercules,
   • quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers, such as the products sold under the name GAFQUAT® by the company ISP, such as, for example, GAFQUAT® 734 or GAFQUAT® 755, or the products called COPOLYMER® 845, 958 and 937. These polymers are described in detail in the French patent applications FR2.077.143 and FR2.393.573 ,
   • dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP, and
   • the quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymer, such as the product sold under the name GAFQUAT® HS 100 by the company ISP.
2. (2) quaternized polysaccharides described more particularly by US Pat. Nos. 3,589,578 and 4,031,307 such as guar gums containing cationic trialkylammonium groups.
   Such products are marketed in particular under the trade names JAGUAR® C13S, JAGUAR® C15 and JAGUAR® C17 by the company MEYHALL.
3. (3) Quaternary copolymers of vinylpyrrolidone and vinylimidazole such as the products marketed by BASF under the name LUVIQUAT® TFC,
4. (4) chitosans or their salts, especially chitosan acetate, lactate, glutamate, gluconate or pyrrolidonecarboxylate.
   Chitosan having a degree of deacetylation of 90.5% by weight sold under the name KYTAN BRUT STANDARD® by ABER TECHNOLOGIES, the chitosan pyrrolidonecarboxylate sold under the name KYTAMER® PC by Amerchol, may be mentioned.
5. (5) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium group and described in particular in the patent US 4,131,576 such as hydroxyalkylcelluloses, such as hydroxymethylhydroxyethyl- or hydroxypropylcelluloses grafted in particular with a salt of methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The marketed products corresponding to this definition are more particularly the products sold under the names CELQUAT® L 200 and CELQUAT® H 100 by the National Starch Company.

The anionic fixing polymers generally used are polymers comprising groups derived from a carboxylic, sulfonic or phosphoric acid and have a weight average molecular weight of between about 500 and 5,000,000.

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 du groupement méthylène voisin, lorsque n est supérieur à 1, par l'intermédiaire d'un hétéroatome tel que oxygène ou soufre, R₃ désigne un atome d'hydrogène, un groupement phényle ou benzyle, R₁ désigne un atome d'hydrogène, un groupement alkyle inférieur ou carboxyle, et R₂ désigne un atome d'hydrogène, un groupement alkyle inférieur, un groupement -CH₂-COOH, phényle ou benzyle.The carboxylic acid groups are provided by unsaturated monomers containing one or two carboxylic acid functions, such as those corresponding to the formula:

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 the neighboring methylene group, when n is greater than 1, via a heteroatom such as oxygen or sulfur, R ₃ denotes a hydrogen atom, a phenyl or benzyl group, R ₁ denotes a hydrogen atom , a lower alkyl or carboxyl group, and R ₂ denotes a hydrogen atom, a lower alkyl group, a group -CH ₂ -COOH, phenyl or benzyl.

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

1. A) les homo- ou copolymères d'acide acrylique ou méthacrylique ou leurs sels et en particulier les produits commercialisés sous les dénominations VERSICOL® E ou K par la Société ALLIED COLLOID, et sous la dénomination ULTRAHOLD® par la Société BASF ; les copolymères d'acide acrylique et d'acrylamide commercialisés sous forme de sel de sodium sous les dénominations RETEN® 421, 423 ou 425 par la Société HERCULES ; les sels de sodium des acides polyhydroxycarboxyliques.
2. B) Les copolymères d'acide acrylique ou d'acide méthacrylique et d'un monomère monoéthylénique tel que l'éthylène, le styrène, les esters vinyliques, les esters d'acide acrylique ou méthacrylique.
   Ces copolymères peuvent être greffés sur un polyalkylène glycol tel que le polyéthylèneglycol et sont éventuellement réticulés.
   De tels polymères sont décrits en particulier dans la demande de brevet français FR 1 222 944 et dans la demande de brevet allemand DE 2 330 956 . On peut notamment citer les copolymères comportant dans leur chaîne un motif acrylamide éventuellement N-alkylé et/ou hydroxyalkylé, tels que ceux décrits dans les demandes de brevet luxembourgeois LU 75370 et LU75371 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 (méth)acrylique et de (méth)acrylate d'alkyle en C₁-C₂₀, par exemple de lauryle (ACRYLDONE® LM de la Société ISP), de tertiobutyle (LUVIFLEX® VBM 70 commercialisé par BASF) ou de méthyle (STEPANHOLD® EXTRA commercialisé par STEPAN), et les terpolymères acide méthacrylique/acrylate d'éthyle/acrylate de tertiobutyle tel que le produit commercialisé sous la dénomination LUVIMER® 100 P par la Société BASF.
3. C) Les copolymères dérivés d'acide crotonique tels que ceux comportant dans leur chaîne des motifs acétate ou propionate de vinyle et éventuellement d'autres monomères tels que les esters allylique, méthallylique ou vinylique d'un acide carboxylique saturé, linéaire ou ramifié, à longue chaîne hydrocarbonée comportant au moins 5 atomes de carbone, ces polymères pouvant éventuellement être greffés et réticulés, ou encore les esters vinylique, allylique ou méthallylique d'un acide carboxylique □- ou □-cyclique.
   De tels polymères sont décrits, entre autres, dans les demandes de brevets français FR 1 222 944 , FR 1 580 545 , FR2 265 782 , FR 2 265 781 , FR 1 564 110 et FR 2 439 798 .
   On peut citer à titre d'exemples de produits commerciaux entrant dans cette classe les résines 28-29-30, 26-13-14 et 28-13-10 commercialisées par la Société NATIONAL STARCH et le MEXOMERE PW proposé par la société CHIMEX.
4. D) Les copolymères dérivés d'acides ou d'anhydrides carboxyliques monoinsaturés en C₄- C₈ choisis parmi :
   • les copolymères comprenant :
     • (ii) un ou plusieurs acides ou anhydrides maléique, fumarique, itaconique et
     • (iii) au moins un monomère choisi parmi les esters vinyliques, les éthers vinyliques, les halogénures vinyliques, les dérivés phénylvinyliques, l'acide acrylique et ses esters, les fonctions anhydride de ces copolymères étant éventuellement monoestérifiées ou monoamidifiées.
       De tels polymères sont décrits en particulier dans les demandes de brevets US 2,047,398 , US 2,723,248 , US 2,102,113 et GB 839,805 et notamment ceux commercialisés sous les dénominations GANTREZ AN ou ES, AVANTAGE® CP par la Société ISP ;
   • les copolymères comprenant (i) un ou plusieurs anhydrides maléique, citraconique ou itaconique et (ii) un ou plusieurs monomères choisis parmi les esters allyliques ou méthallyliques comportant éventuellement un ou plusieurs groupements acrylamide, méthacrylamide, □-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 demandes de brevets français FR 2 350 384 et FR 2 357 241 de la demanderesse.
5. E) Les polyacrylamides comportant des groupements carboxylate.
6. F) Les copolymères acryliques à blocs ramifiés. Dans cette famille on peut en particulier citer les copolymères à blocs ramifiés comprenant comme monomères principaux au moins un acrylate d'alkyle en C1-C20 et/ou au moins un N mono- ou N,N di-(alkyle en C2-C12)(meth)acrylamide et de l'acide acrylique et/ou de l'acide méthacrylique. Ces polymères fixants sont des copolymères à blocs ramifiés ayant une structure constituée de blocs hydrophobes sur lesquels sont fixées, notamment par l'intermédiaire de motifs bifonctionnels, un certain nombre de blocs plus hydrophiles. Ces copolymères présentent au moins deux températures de transition vitreuse.

The preferred carboxylated anionic fixing polymers according to the invention are:

1. 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 under the name ULTRAHOLD® by BASF; copolymers of acrylic acid and acrylamide sold in the form of the sodium salt under the names Reten® 421, 423 or 425 by the company Hercules; sodium salts of polyhydroxycarboxylic acids.
2. B) Copolymers of acrylic acid or methacrylic acid and a monoethylenic monomer such as ethylene, styrene, vinyl esters, esters of acrylic or methacrylic acid.
   These copolymers can be grafted onto a polyalkylene glycol such as polyethylene glycol and are optionally crosslinked.
   Such polymers are described in particular in the French patent application FR 1 222 944 and in the German patent application DE 2,330,956 . Mention may in particular be made of copolymers comprising in their chain an acrylamide unit, optionally N-alkylated and / or hydroxyalkylated, such as those described in the Luxembourg patent applications. LU 75370 and LU75371 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, (meth) acrylic acid and C ₁ -C alkyl (meth) acrylate. ₂₀ , for example lauryl (ACRYLDONE® LM from ISP), tert-butyl (LUVIFLEX® VBM 70 sold by BASF) or methyl (STEPANHOLD® EXTRA marketed by STEPAN), and terpolymers methacrylic acid / ethyl acrylate / tert-butyl acrylate such as the product marketed under the name LUVIMER® 100 P by the company BASF.
3. 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, methallylic or vinyl esters of a saturated carboxylic acid, linear or branched, with long hydrocarbon chain comprising at least 5 carbon atoms, these polymers may optionally be grafted and crosslinked, or the vinyl, allyl or methallyl esters of a □ - or □ -cyclic carboxylic acid.
   Such polymers are described, inter alia, in French patent applications FR 1 222 944 , FR 1 580 545 , FR2 265 782 , FR 2,265,781 , FR 1 564 110 and FR 2,439,798 .
   Examples of commercial products included in this class are resins 28-29-30, 26-13-14 and 28-13-10 marketed by the National Starch Company and the MEXOMERE PW proposed by the company CHIMEX.
4. D) Copolymers derived from C ₄ -C ₈ monounsaturated carboxylic acids or anhydrides chosen from:
   • the copolymers comprising:
     • (ii) one or more maleic, fumaric, itaconic and
     • (iii) 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 patent applications US 2,047,398 , US 2,723,248 , US 2,102,113 and GB 839,805 and in particular those marketed under the names GANTREZ AN or ES, AVANTAGE® CP by the company ISP;
   • copolymers comprising (i) one or more maleic, citraconic or itaconic anhydrides and (ii) one or more monomers chosen from allylic or methallyl esters optionally containing one or more acrylamide, methacrylamide, olefin, 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 the French patent applications FR 2,350,384 and FR 2 357 241 of the plaintiff.
5. E) Polyacrylamides having carboxylate groups.
6. F) branched block acrylic copolymers. In this family, mention may be made in particular of branched block copolymers comprising, as main monomers, at least one C 1 -C 20 alkyl acrylate and / or at least one N mono- or N, N di- (C 2 -C 12) alkyl. (meth) acrylamide and acrylic acid and / or methacrylic acid. These fixing polymers are branched block copolymers having a structure consisting of hydrophobic blocks on which are fixed, especially via bifunctional units, a number of more hydrophilic blocks. These copolymers have at least two glass transition temperatures.

They are described in particular in the patent application WO00 / 40628 .

The branched block copolymers described above are for example proposed under the names EX-SDR-26® and EX-SDR-45® by the company GOODRICH, and EX-SDR-752 (FIXATE G100L from NOVEON).

• Acide acrylique 26 à 36 % en moles
• Acrylate de n-butyle 27,5 à 30,5 % en moles
• Acide méthacrylique 33,3 à 45,3 % en moles
• Méthacrylate d'allyle 0,48 à 0,92 % en moles

Les blocs les plus hydrophobes ont un poids moléculaire de 10 000 à 100 000 et les blocs les plus hydrophobes ont un poids moléculaire de 1000 à 100 000 daltons.These copolymers generally have the following composition:

• Acrylic acid 26 to 36 mol%
• 27.5 to 30.5 mol% n-butyl acrylate
• Methacrylic acid 33.3 to 45.3 mol%
• Allyl methacrylate 0.48 to 0.92 mol%

The most hydrophobic blocks have a molecular weight of 10,000 to 100,000 and the most hydrophobic blocks have a molecular weight of 1000 to 100,000 daltons.

The anionic groups of the anionic fixing polymers of the present invention may also be sulfonic acid groups provided by vinylsulfonic, styrenesulphonic, naphthalenesulphonic or acrylamidoalkylsulphonic units.

• les sels de poly(acide vinylsulfonique) ayant un poids moléculaire moyen en poids compris entre environ 1000 et 100 000 ainsi que les copolymères d'acide vinylsulfonique et d'un comonomère insaturé tel que l'acide acrylique, l'acide méthacrylique, les esters de ces acides, l'acrylamide, les dérivés d'acrylamide, les éthers vinyliques et la vinylpyrrolidone ;
• les sels de poly(acide styrènesulfonique). On peut citer à titre d'exemple deux sels de sodium ayant un poids moléculaire moyen en poids d'environ 500 000 et d'environ 100 000 commercialisés respectivement sous les dénominations FLEXAN® 500 et FLEXAN® 130 par la Société NATIONAL STARCH. Ces composés sont décrits dans le brevet FR 2 198 719 ;
• les sels de poly(acide acrylamidesulfonique), tels que ceux mentionnés dans le brevet US 4,128,631 et plus particulièrement le poly(acide acrylamidoéthyl-propanesulfonique) commercialisé sous la dénomination COSMEDIA POLYMER® HSP 1180 par la Société HENKEL.
• Les polyesters sulfoniques linéaires.

These polymers containing sulphonic acid groups are in particular chosen from:

• poly (vinylsulfonic acid) salts having a weight average molecular weight of between about 1000 and 100,000, and copolymers of vinylsulfonic acid and an unsaturated comonomer such as acrylic acid, methacrylic acid, esters, and the like. of these acids, acrylamide, acrylamide derivatives, vinyl ethers and vinylpyrrolidone;
• poly (styrenesulfonic acid) salts. By way of example, mention may be made of two sodium salts having a weight average molecular weight of about 500 000 and about 100 000 sold respectively under the names FLEXAN® 500 and FLEXAN® 130 by the company National Starch. These compounds are described in the patent FR 2 198 719 ;
• poly (acrylamidesulfonic acid) salts, such as those mentioned in the patent US 4,128,631 and more particularly the poly (acrylamidoethyl-propanesulfonic acid) marketed under the name COSMEDIA POLYMER® HSP 1180 by the company HENKEL.
• Linear sulfonic polyesters.

By polyester sulfonic is meant copoylesters obtained by polycondensation of at least one dicarboxylic acid or one of its esters, at least one diol and at least one difunctional sulfoaryldicarboxylic compound substituted on the aromatic ring by a group - SO3M wherein M represents a hydrogen atom or a metal ion such as Na +, Li + or K +.

The water-dispersible linear sulfonic polyesters generally have a weight average molecular weight of from about 1,000 to 60,000, and preferably from 4,000 to 20,000, as determined by gel permeation chromatography (GPC).

The glass transition temperature (Tg) of these sulfonic polyesters is generally in the range of 10 ° C to 100 ° C. Preferably, the Tg of the polyester or polyesters used is greater than or equal to 50 ° C.

The glass transition temperature (Tg) is measured by differential scanning calorimetry (DSC) according to ASTM D3418-97.

They are described in more detail in the patent applications US 3,734,874 , US 3,779,993 , US 4,119,680 , US 4,300,580 , US 4,973,656 , US 5,660,816 , US 5,662,893 , and US 5,674,479 .

The sulfonic polyesters preferably used in the invention comprise at least units derived from isophthalic acid, sulfoaryl-dicarboxylic acid salt and diethylene glycol, and more particularly the sulphonic polyesters used in the invention are obtained from isophthalic acid, sodium salt of sulphoisophthalic acid, diethylene glycol and 1,4-cyclohexanemethanol.

As examples of sulphonic polyester, there may be mentioned those known under the name INCI Diglycol / CHDM / Isophthalates / SIP, and sold under the trade names "Eastman AQ polymer" (AQ35S, AQ38S, AQ55S, AQ48 Ultra) by the Eastman Chemical Company.
Preferably, the Tg of the polyester or polyesters used is greater than or equal to 50 ° C.

According to the invention, the anionic polymers are preferably chosen from acrylic acid copolymers such as the acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer sold under the name ULTRAHOLD STRONG® by the company BASF, the copolymers derived from crotonic acid such as vinyl acetate terpolymers / p-tert-butylbenzoate / crotonic acid (MEXOMERE PW from CHIMEX) and crotonic acid / vinyl acetate / vinyl neododecanoate terpolymers sold under the name Resin 28-29 By the company National Starch, polymers derived from maleic, fumaric, itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, such as monoesterified methyl vinyl ether / maleic anhydride copolymer sold under the name Gantrez® ES 425 by the company ISP, the copolymer methacrylic acid and ethyl acrylate sold under the name LUVIMER® MAEX by the company BASF, the terpolymer of vinylpyrrolidone / acrylic acid / lauryl alkyl methacrylate sold by the company ISP under the name ACRYLIDONE LM and the vinyl acetate / crotonic acid copolymer sold under the name Luviset® CA 66 by the company BASF and the vinyl acetate / crotonic acid / polyethylene glycol terpolymer under the name ARISTOFLEX® A by the company BASF, linear sulphonic polyesters and in particular the AQ55S from EASTMAN, acrylic copolymers with branched blocks and in particular FIXATE G100L from NOVEON.

The amphoteric fixing polymers that may be used for the present invention are chosen in particular from polymers comprising units B and C statistically distributed in the polymer chain, where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit derived from a monomer having one or more carboxylic acid or sulfonic acid groups. The amphoteric fixing polymers may also comprise zwitterionic units of the carboxybetaine or sulfobetaine type. It may also be cationic main chain polymers containing primary amine groups, secondary, tertiary or quaternary, of which at least one, carries, via a hydrocarbon radical, a carboxylic acid group
or sulfonic acid. The amphoteric fixing polymers may also have an anionic chain derived from α, β-unsaturated dicarboxylic acids, one of whose carbonyl groups has been reacted with a polyamine containing one or more primary or secondary amine groups.

• (1) Les polymères résultant de la copolymérisation d'un monomère vinylique portant un groupement acide carboxylique tel que l'acide acrylique, l'acide méthacrylique, l'acide maléique, l'acide α-chloroacrylique, et d'un monomère vinylique contenant au moins une fonction basique tel que les méthacrylate et acrylate de dialkylaminoalkyle ou les dialkylaminoalkyl(méth)acrylamides. De tels composés sont décrits par exemple dans la demande de brevet américain US 3,836,537 .
• (2) Les polymères comportant des motifs dérivés :
  1. (a) d'au moins un monomère choisi parmi les acrylamides ou méthacrylamides N-alkylés,
  2. (b) d'au moins un comonomère contenant une ou plusieurs fonctions acide carboxylique, et
  3. (c) d'au moins un comonomère basique tel que des esters à substituants amine primaire, secondaire, tertiaire ou quaternaire d'acide acrylique et d'acide méthacrylique, et le produit de quaternisation du méthacrylate de diméthylaminoéthyle avec le sulfate de diméthyle ou diéthyle.
  Les acrylamides ou méthacrymlamides N-alkylés (a) préférés sont ceux portant des radicaux alkyle en C_2-12 , tels que le N-éthylacrylamide, le N-tertiobutylacrylamide, le N-tertio-octylacrylamide, le N-octylacrylamide, le N-décylacrylamide, le N-dodécylacrylamide ainsi que les méthacrylamides correspondants.
  Les comonomères à groupe acide carboxylique (b) sont choisis plus particulièrement parmi les acides acrylique, méthacrylique, crotonique, itaconique, maléique, fumarique ainsi que parmi les monoesters d'alkyle en C₁₄ des acides ou des anhydrides maléique ou fumarique.
  Les comonomères basiques (c) préférés sont le méthacrylate d'aminoéthyle, le méthacrylate de butylaminoéthyle, le méthacrylate de N,N'-diméthylaminoéthyle et le méthacrylate de N-tertiobutylaminoéthyle.
  On utilise en particulier les copolymères dont la dénomination CTFA (4^ième Ed., 1991) est « Octylacrylamide/acrylates/butylaminoéthylméthacrylate copolymer », tels que les produits commercialisés sous la dénomination AMPHOMER® ou LOVOCRYL® 47 par la Société NATIONAL STARCH.
• (3) Les polyaminoamides réticulés et alcoylés, dérivés en partie ou en totalité de polyaminoamides de formule générale :
  
           (II)     -[C(=0)-R₄-C(=0)-Z-]-
  
  dans laquelle R₄ 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'alkyle en C_1-6 de ces acides ou d'un radical dérivant de l'addition de l'un quelconque desdits acides sur une amine bis primaire ou bis secondaire, et Z désigne un radical d'une polyalkylène-polyamine bis-primaire, mono- ou bis-secondaire, et de préférence représente :
  1. a) dans les proportions de 60 à 100 % en moles, le radical :
     
              (III)     -NH-[(CH₂)_x-NH]_p-
     
     où x = 1 et p = 2 ou 3, ou bien x = 3 et p = 2,
     ce radical dérivant de la diéthylènetriamine, de la triéthylènetétraamine ou de la dipropylènetriamine ;
  2. b) dans les proportions de 0 à 40% en moles le radical de formule (III)
     dans lequel x = 2 et p = 1, dérivé de l'éthylènediamine, ou le radical
     
     dérivé de la pipérazine :
  3. c) dans les proportions de 0 à 20 % en moles le radical -NH-(CH₂)₆-NH- dérivé de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition de 0,025 à 0,35 mole par mole de groupement amine, d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les composés di-insaturés, et alcoylés par l'acide acrylique, l'acide chloracétique ou une alcane-sulfone.
  Les acides carboxyliques saturés sont choisis de préférence parmi les acides ayant 6 à 10 atomes de carbone tels que l'acide adipique, l'acide triméthyl-2,2-4-adipique et triméthyl-2,4,4-adipique, l'acide téréphtalique, les acides à double liaison éthylénique comme par exemple les acides acrylique, méthacrylique, itaconique.
  Les alcane-sulfones utilisées dans l'alcoylation sont de préférence la propanesulfone ou la butanesulfone.
  Les sels des agents d'alcoylation sont de préférence les sels de sodium
  ou de potassium.
• (4) Les polymères comportant des motifs zwittérionique de formule :
  
  dans laquelle R₅ désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent chacun un nombre entier de 1 à 3, R₆ et R₇ représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle, éthyle ou propyle, R₈ et R₉ représentent chacun indépendamment un atome d'hydrogène
  ou un radical alkyle, le nombre total d'atomes de carbone dans R₈ et R₉ ne dépassant pas 10.
  Les polymères comprenant de tels motifs de formule (IV) peuvent comporter en outre des motifs dérivés de monomères non zwittérioniques tels que l'acrylate ou le méthacrylate de diméthyle ou de diéthylaminoéthyle, les acrylates ou méthacrylates d'alkyle, les acrylamides ou méthacrylamides ou l'acétate de vinyle.
  A titre d'exemple, on peut citer le copolymère méthacrylate de méthyle/méthacrylate de diméthylcarboxyméthylammonioéthyle tel que le produit commercialisé sous la dénomination DIAFORMER® Z301 par la Société SANDOZ.
• (5) Les polymères dérivés du chitosane comportant des motifs monomères répondant aux formules suivantes :
  
  le motif de formule (V) étant présent dans des proportions comprises entre 0 et 30%, le motif de formule (VI) dans des proportions comprises entre 5 et 50% et le motif de formule (VII) dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (VII), R₁₀ représente un radical de formule :
  
  dans laquelle :
  si q = 0, alors R₁₁, R₁₂ et R₁₃, identiques ou différents, représentent chacun un atome d'hydrogène, un groupe méthyle, hydroxyle, acétoxy ou amino, un groupe monoalcoylamine ou dialcoylamine éventuellement interrompu par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alcoylthio ou sulfo, un groupe alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des radicaux R₁₁, R₁₂ et R₁₃ étant dans ce cas un atome d'hydrogène ; ou si q = 1, alors R₁₁, R₁₂ et R₁₃ représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.
• 6) Les polymères obtenus par N-carboxyalkylation du chitosane, comme le N-carboxyméthylchitosane ou le N-carboxybutylchitosane commercialisé sous la dénomination EVALSAN® par la Société JAN DEKKER.
• (7) Les polymères répondant à la formule générale (IX) :
  
  décrits notamment dans la demande de brevet FR 1 400 366 , dans laquelle R₁₄ représente un atome d'hydrogène ou un radical CH₃O, CH₃CH₂O ou phényle, R₁₅ désigne un atome d'hydrogène ou un radical alkyle inférieur tel que méthyle ou éthyle, R₁₅ désigne un atome d'hydrogène ou un radical alkyle inférieur tel que méthyle ou éthyle, R₁₇ désigne un radical alkyle inférieur tel que méthyle ou éthyle ou un radical répondant à la formule :
  
           -R₁₈-N(R₁₆)₂,
  
  R₁₈ représentant un groupement -CH₂ -CH₂-,-CH₂ -CH₂- CH₂-, -CH2-CH(CH₃)-, et R₁₆ ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux contenant jusqu'à 6 atomes de carbone.
• (8) Les polymères amphotères du type -D-X-D-X-choisis parmi :
  • (a) les polymères obtenus par action d'acide chloroacétique ou de chloroacétate de sodium sur les composés comportant au moins un motif de formule :
    
             (X)     -D-X-D-X-D-
    
    où D désigne un radical :
    
    et X désigne le symbole E ou E', E ou E' identiques ou différents désignant 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 ou de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques, les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sulfoxyde, sulfone, sulfonium, alkylamine, alcénylamine, des groupements hydroxyle, benzylamine, oxyde d'amine, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne.
  • b) Les polymères de formule :
    
             (X')     -D-X'-D-X'-
    
    où D désigne un radical
    
    et X' désigne le symbole E ou E' et au moins une fois E', E ayant la signification indiquée ci-dessus et E' étant 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 bétaïnisée par réaction avec l'acide chloroacétique ou du chloroacétate de soude.
• 9) Les copolymères alkyl(C_1-5)vinyléther/anhydride maléique modifiés partiellement par semi-amidification avec une N,N-dialkylaminoalkylamine telle que la N,N-diméthylaminopropylamine, ou par semi-estérification avec une N,N-dialcanolamine. Ces copolymères peuvent également comporter d'autres comonomères vinyliques tels que le vinylcaprolactame.
  Les polymères fixants amphotères préférés selon l'invention sont ceux de la famille (3) décrite ci-dessus, tels que ceux dont la dénomination CTFA est « Octylacrylamide/acrylates/butylaminoéthyl-méthacrylate copolymer ». On peut citer à titre d'exemple les produits commercialisés sous les dénominations AMPHOMER®, AMPHOMER® LV 71 ou LOVOCRYL® 47 par la Société NATIONAL STARCH.

The amphoteric fixing polymers corresponding to the definition given above are chosen in particular from the following polymers:

• (1) Polymers resulting from the copolymerization of a vinyl monomer bearing a carboxylic acid group such as acrylic acid, methacrylic acid, maleic acid, α-chloroacrylic acid, and a vinyl monomer containing at least one basic function such as dialkylaminoalkyl methacrylate and acrylate or dialkylaminoalkyl (meth) acrylamides. Such compounds are described for example in the US patent application US 3,836,537 .
• (2) polymers having derived units:
  1. (a) at least one monomer chosen from N-alkylated acrylamides or methacrylamides,
  2. (b) at least one comonomer containing one or more carboxylic acid functions, and
  3. (c) at least one basic comonomer such as primary, secondary, tertiary or quaternary amine substituted esters of acrylic acid and methacrylic acid, and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate .
  The preferred N-alkylated acrylamides or methacrylamides (a) are those bearing C _2-12 alkyl radicals, such as N-ethylacrylamide, N-tert-butylacrylamide, N-tert-octylacrylamide, N-octylacrylamide, N-octylacrylamide and N-octylacrylamide. decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.
  The carboxylic acid group comonomers (b) are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic and fumaric acids as well as from the C ₁₄ alkyl monoesters of maleic or fumaric acids or anhydrides.
  Preferred basic comonomers (c) are aminoethyl methacrylate, butylaminoethyl methacrylate, N, N'-dimethylaminoethyl methacrylate and N-tert-butylaminoethyl methacrylate.
  In particular, the copolymers whose CTFA ^(4th Ed. 1991) is "octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer," such as the products sold under the name Amphomer.RTM Lovocryl® or 47 by the company National Starch.
• (3) The crosslinked and alkylated polyaminoamides derived in part or in full from polyaminoamides of general formula:
  
  (II) - [C (= O) -R ₄ -C (= O) -Z -] -
  
  wherein R ₄ represents a divalent radical derived from a saturated dicarboxylic acid, an aliphatic mono- or dicarboxylic acid double bond ethylenic, a C _1-6 alkyl ester of these acids or a radical derived from the addition of any one of said acids to a primary bis or secondary bis amine, and Z denotes a radical of a bis-primary, mono- or bis-secondary polyalkylene polyamine, and preferably represents:
  1. a) in the proportions of 60 to 100 mol%, the radical:
     
     (III) -NH - [(CH ₂ ) _x -NH] _p -
     
     where x = 1 and p = 2 or 3, or x = 3 and p = 2,
     this radical derived from diethylenetriamine, triethylenetetraamine or dipropylenetriamine;
  2. b) in proportions of 0 to 40 mol%, the radical of formula (III)
     in which x = 2 and p = 1, derived from ethylenediamine, or the radical
     
     Piperazine derivative:
  3. c) in the proportions of 0 to 20 mol%, the radical -NH- (CH ₂ ) ₆ -NH- derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of 0.025 to 0.35 mol per mole of amine group, of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, di-unsaturated compounds, and alkylated with acrylic acid, chloroacetic acid or an alkane sulphone.
  The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic acid, trimethyl-2,2-4-adipic acid and trimethyl-2,4,4-adipic acid, terephthalic acid, acids with an ethylenic double bond, for example acrylic, methacrylic or itaconic acids.
  The alkane sulfones used in the alkylation are preferably propanesulfone or butanesulfone.
  The salts of the alkylating agents are preferably the sodium salts
  or potassium.
• (4) Polymers having zwitterionic units of formula:
  
  in which R ₅ denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z each represent an integer from 1 to 3, R ₆ and R ₇ each independently represent a hydrogen atom or a methyl, ethyl or propyl group, R ₈ and R ₉ each independently represent a hydrogen atom
  or an alkyl radical, the total number of carbon atoms in R ₈ and R ₉ not exceeding 10.
  The polymers comprising such units of formula (IV) may further comprise units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate, alkyl acrylates or methacrylates, acrylamides or methacrylamides, or vinyl acetate.
  By way of example, mention may be made of methyl methacrylate / dimethylcarboxymethylammonioethyl methacrylate copolymer such as product marketed under the name DIAFORMER® Z301 by SANDOZ.
• (5) polymers derived from chitosan having monomeric units corresponding to the following formulas:
  
  the unit of formula (V) being present in proportions of between 0 and 30%, the unit of formula (VI) in proportions of between 5 and 50% and the unit of formula (VII) in proportions of between 30 and 90%, it being understood that in this unit (VII), R ₁₀ represents a radical of formula:
  
  in which :
  if q = 0, then R ₁₁ , R ₁₂ and R ₁₃ , which are identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino group, a monoalkylamine or dialkylamine group optionally interrupted by one or more carbon atoms. nitrogen and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio or sulfo groups, an alkylthio group whose alkyl group carries an amino residue, at least one of the radicals R ₁₁ , R ₁₂ and R ₁₃ being in this case a hydrogen atom; or if q = 1, then R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.
• 6) Polymers obtained by N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name EVALSAN® by the company Jan Dekker.
• (7) The polymers having the general formula (IX):
  
  described in particular in the patent application FR 1 400 366 in which R ₁₄ represents a hydrogen atom or a radical CH ₃ O, CH ₃ CH ₂ O or phenyl, R ₁₅ denotes a hydrogen atom or a lower alkyl radical such as methyl or ethyl, R ₁₅ denotes an atom of hydrogen or a lower alkyl radical such as methyl or ethyl, R ₁₇ denotes a lower alkyl radical such as methyl or ethyl or a radical corresponding to the formula:
  
  -R ₁₈ -N (R ₁₆ ) ₂ ,
  
  R ₁₈ representing a -CH ₂ -CH ₂ -, - CH ₂ -CH ₂ - CH ₂ -, -CH 2 -CH (CH ₃₎ -, and R ₁₆ having the meanings mentioned above, as well as the higher homologues of these radicals containing up to 6 carbon atoms.
• (8) Amphoteric polymers of the -DXDX-type chosen from:
  • (a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula:
    
    (X) -DXDXD-
    
    where D denotes a radical:
    
    and X denotes the symbol E or E ', E or E' being identical or different and denoting a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the unsubstituted or group-substituted main chain. hydroxyl and may further comprise oxygen, nitrogen or sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings, the oxygen, nitrogen and sulfur atoms being present in the form of ether groups, thioether sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane.
  • b) polymers of formula:
    
    (X ') -D-X'-D-X'-
    
    where D denotes a radical
    
    and X 'denotes the symbol E or E' and at least once E ', E having the meaning indicated above and E' being a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms. carbon in the main chain, substituted or unsubstituted by one or more hydroxyl radicals and comprising one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and having obligatorily one or several carboxyl functions or one or more functions hydroxyl and betaineized by reaction with chloroacetic acid or chloroacetate of sodium hydroxide.
• 9) The alkyl (C _1-5 ) vinyl ether / maleic anhydride copolymers partially modified by half-amidification with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine, or by semi-esterification with an N, N-dialkanolamine. These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.
  The preferred amphoteric fixing polymers according to the invention are those of the family (3) described above, such as those whose CTFA name is "Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer". By way of example, mention may be made of the products sold under the names AMPHOMER®, AMPHOMER® LV 71 or LOVOCRYL® 47 by the National Starch Company.

Other preferred amphoteric fixing polymers are those of family (4), such as, for example, copolymers of methyl methacrylate and dimethylcarboxymethylammonioethyl methacrylate, sold, for example, under the name DIAFORMER® Z301 by SANDOZ.

The anionic or amphoteric fixing polymers may, if necessary, be partially or completely neutralized. The neutralization agents are, for example, sodium hydroxide, potassium hydroxide, amino-2-methylpropanol, monoethanolamine, triethanolamine or triisopropanolamine, mineral or organic acids such as hydrochloric acid or citric acid.

• les homopolymères de vinylpyrrolidone,
• les copolymères de vinylpyrrolidone et d'acétate de vinyle,
• les polyalkyloxazolines telles que les polyéthyloxazolines proposées par la Société DOW CHEMICAL sous les dénominations PEOX® 50 000 , PEOX® 200 000 et PEOX® 500 000,
• les homopolymères d'acétate de vinyle tels que le produit proposé sous le nom de APPRETAN® EM par la Société HOECHST ou le produit proposé sous le nom de RHODOPAS® A 012 par la Société RHONE POULENC ;
• les copolymères d'acétate de vinyle et d'esters acryliques tels que le produit proposé sous la dénomination RHODOPAS® AD 310 par RHONE POULENC,
• les copolymères d'acétate de vinyle et d'éthylène tels que le produit proposé sous le nom de APPRETAN® TV par la Société HOECHST,
• les copolymères d'acétate de vinyle et d'ester maléique par exemple de maléate de dibutyle tels que le produit proposé sous le nom de APPRETAN® MB EXTRA par la Société HOECHST,
• les copolymères d'éthylène et d'anhydride maléique,
• les homopolymères d'acrylates d'alkyle et les homopolymères de méthacrylates d'alkyle tels que le produit proposé sous la dénomination MICROPEARL® RQ 750 par la Société MATSUMOTO ou le produit proposé sous la dénomination LUHYDRAN® A 848 S par la Société BASF,
• les copolymères d'esters acryliques tels que par exemple les copolymères d'acrylates d'alkyle et de méthacrylates d'alkyle tels que les produits proposés par la Société ROHM & HAAS sous les dénominations PRIMAL AC-261 K et EUDRAGIT NE 30 D, par la Société BASF sous les dénominations ACRONAL® 601, LUHYDRAN® LR 8833 ou 8845, et par la Société HOECHST sous les dénominations APPRETAN® N 9213 ou N 9212,
• les copolymères d'acrylonitrile et d'un monomère non ionique choisi par exemple parmi le butadiène et les (méth) acrylates d'alkyle ; on peut citer les produits proposés sous les dénominations NIPOL® LX 531 B par la Société NIPPON ZEON

ou ceux proposés sous la dénomination CJ 0610 B par la Société ROHM & HAAS,

• les polyuréthannes tels que les produits proposés sous les dénominations ACRYSOL® RM 1020 OU ACRYSOL® RM 2020 par la Société ROHM & HAAS, les produits URAFLEX® XP 401 UZ, URAFLEX® XP et 402 UZ par la Société DSM RESINS,
• les copolymères d'acrylate d'alkyle et d'uréthanne tels que le produit 8538-33 commercialisé par la Société NATIONAL STARCH,
• les polyamides tels que le produit ESTAPOR® LO 11 proposé par la Société RHONE POULENC,
• les gommes de guar non ioniques chimiquement modifiées ou non modifiées.

The nonionic fixing polymers that can be used according to the present invention are chosen for example from:

• homopolymers of vinylpyrrolidone,
• copolymers of vinylpyrrolidone and vinyl acetate,
• polyalkyloxazolines such as the polyethyloxazolines proposed by DOW CHEMICAL under the names PEOX® 50,000, PEOX® 200,000 and PEOX® 500,000,
• vinyl acetate homopolymers such as the product sold under the name APPRETAN® EM by the company HOECHST or the product sold under the name RHODOPAS® A 012 by the company RHONE POULENC;
• copolymers of vinyl acetate and of acrylic esters such as the product sold under the name RHODOPAS® AD 310 by RHONE POULENC,
• copolymers of vinyl acetate and ethylene, such as the product sold under the name APPRETAN® TV by Hoechst,
• copolymers of vinyl acetate and of maleic ester, for example of dibutyl maleate, such as the product sold under the name APPRETAN® MB EXTRA by the company HOECHST,
• copolymers of ethylene and maleic anhydride,
• homopolymers of alkyl acrylates and homopolymers of alkyl methacrylates such as the product sold under the name MICROPEARL® RQ 750 by the company MATSUMOTO or the product sold under the name LUHYDRAN® A 848 S by the company BASF,
• copolymers of acrylic esters such as, for example, copolymers of alkyl acrylates and of alkyl methacrylates such as the products offered by the company ROHM & HAAS under the names PRIMAL AC-261 K and EUDRAGIT NE 30 D, by BASF under the names ACRONAL® 601, LUHYDRAN® LR 8833 or 8845, and by HOECHST under the names APPRETAN® N 9213 or N 9212,
• 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 names Nipol® LX 531 B by the company Nippon Zeon

or those proposed under the name CJ 0610 B by the company ROHM & HAAS,

• polyurethanes such as the products sold under the names Acrysol® RM 1020 or Acrysol® RM 2020 by the company Rohm & Haas, the products Uraflex® XP 401 UZ, Uraflex® XP and 402 UZ by the company DSM Resins,
• copolymers of alkyl acrylate and urethane such as the product 8538-33 sold by National Starch,
• polyamides such as the product ESTAPOR® LO 11 proposed by the company RHONE POULENC,
• chemically modified or unmodified nonionic guar gums.

The unmodified nonionic guar gums are, for example, the products sold under the name VIDOGUM® GH 175 by the company UNIPECTINE and under the name JAGUAR® C by MEYHALL. The modified nonionic guar gums which can be used according to the invention are preferably modified with C _1-8 hydroxyalkyl groups. We can mention by way of example the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups.

These guar gums are well known in the art and may for example be prepared by reaction of the corresponding alkenes oxides, such as, for example, propylene oxides, with guar gum so as to obtain a guar gum modified with hydroxypropyl groups.

Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names Jaguar® HP8, Jaguar® HP60 and Jaguar® HP120, Jaguar® DC 293 and Jaguar® HP 105 by the company Meyhall, or under designation GALACTASOL® 4H4FD2 by AQUALON.

According to the invention, it is also possible to use, as fixing polymers, grafted silicone-type film-forming polymers 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 the 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 patent applications US 4,693,935 , US 4,728,571 and US 4,972,037 .

These polymers are preferably anionic or nonionic.

1. a) de 50 à 90% en poids d'acrylate de tertiobutyle,
2. b) de 0 à 40% en poids d'acide acrylique,
3. c) de 5 à 40% en poids d'un macromère siliconé de formule :
   
   avec v étant un nombre allant de 5 à 700, les pourcentages en poids calculés par rapport au poids total des monomères.

Such polymers are for example the copolymers that can be obtained by radical polymerization from the monomer mixture formed,

1. a) from 50 to 90% by weight of tert-butyl acrylate,
2. b) from 0 to 40% by weight of acrylic acid,
3. c) from 5 to 40% by weight of a silicone macromer of formula:
   
   with v being a number from 5 to 700, the percentages by weight 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 and poly type. alkyl (meth) acrylate and polydimethylsiloxanes (PDMS) on which are grafted, via a thiopropylene type connecting link, polymeric units of the poly (meth) acrylate isobutyl type.

It is also possible to use, as fixing polymers, functionalized polyurethanes, whether silicone or non-silicone.

The polyurethanes particularly targeted by the present invention are those described in the patent applications EP 0 751 162 , EP 0 637 600 , FR 2,743,297 and EP 0 648 485 the plaintiff and the patent application EP 0 656 021 or WO 94/03510 BASF and EP 0 619 111 from the STARCH NATIONAL COMPANY.

As a non-silicone fixing polyurethane, mention may be made of the LUVISET PUR polymer proposed by BASF. As a silicone-fixing polyurethane, mention may be made of the LUVISET Si PUR polymer also proposed by BASF.

The fixing polymer is preferably chosen from silicone or non-silicone polyurethanes, linear sulphonic polyesters, branched block acrylic copolymers, and octylacrylamide / acrylate / butylaminoethyl methacrylate copolymers.

Thus, the particularly preferred fixing polymers may be chosen from AMPHOMER from NATIONAL STARCH, LUVISET Si Pur from BASF, FIXATE G100 from NOVEON, MEXOMERE PW from CHIMEX, AQ 55S from EASTMAN.

Preferably, the fixing polymer or polymers represent from 0.1 to 20% by weight, preferably from 1 to 12% by weight relative to the total weight of the cosmetic composition.

The cosmetic compositions described above may also contain other cosmetically acceptable active agents, such as, for example, surfactants, thickening agents, penetrating agents, perfumes, peptizers, buffers, and various conventional adjuvants such as UV filters, waxes, volatile or nonvolatile silicones, cyclic or linear or branched, organomodified (in particular by amine groups) or not, preservatives, ceramides, pseudoceramides, vegetable, mineral or synthetic oils, vitamins or provitamins such as panthenol, opacifiers, reducing agents, emulsifiers, preservatives, fillers, proteins, moisturizing agents, emollients, softening agents, anti-foam agents, anti-free radical agents, bactericides , sequestering agents, anti-dandruff, antioxidants, basifying agents, polyols, anti-corrosion agents and any other additive conventionally used in cosmetic compositions intended to be applied to the hair.

Silicones are among the preferred additional ingredients.

The silicones that may be used as additives in the cosmetic compositions of the present invention are volatile or cyclic, linear or branched, volatile or non-volatile organic silicones with a viscosity of 5 × 10 ^-6 to 2.5 m. ² / s at 25 ° C and preferably 1.10 ^-5 to 1 m ² / s.

The silicones that can be used in accordance with the invention can be in soluble, dispersed, micro or nano-dispersed form in the composition and in particular be insoluble polyorganosiloxanes in the composition of the invention. They can be in the form of oils, waxes, resins or gums.

Organopolysiloxanes are defined in more detail in Walter NOLL "Chemistry and Technology of Silicones" (1968), Academie Press . They can be volatile or nonvolatile.

• (i) les polydiolkylsiloxanes cycliques comportant de 3 à 7, de préférence de 4 à 5 atomes de silicium. Il s'agit, par exemple, de l'octaméthylcyclotétrasiloxane commercialisé notamment sous le nom de VOLATINE SILICONE® 7207 par UNION CARBIDE ou SILBIONE® 70045 V2 par RHODIA, le décaméthylcyclopentasiloxane commercialisé sous le nom de VOLATILE SILICONE® 7158 par UNION CARBIDE, et SILBIONE® 70045 V5 par RHODIA, ainsi que leurs mélanges.
  On peut également citer les cyclocopolymères du type diméthylsiloxanes/ méthylalkylsiloxane, tel que la "SILICONE VOLATILE FZ 3109" commercialisée par la société UNION CARBIDE, de formule : avec
  
  On peut également citer les mélanges de polydialkyl siloxanes cycliques avec des composés organiques dérivés du silicium, tels que le mélange d'octaméthylcyclotétrasiloxane et de tétratriméthylsilylpentaérythritol (50/50) et le mélange d'octaméthylcyclotétrasiloxane et d'oxy-1,1'(hexa-2,2,2',2',3,3'-triméthylsilyloxy) bis-néopentane ;
• (ii) les polydialkylsiloxanes volatiles linéaires ayant 2 à 9 atomes de silicium et présentant une viscosité inférieure ou égale à 5.10^-6m²/s à 25° C. Il s'agit, par exemple, du décaméthyltétrasiloxane commercialisé notamment sous la dénomination "SH 200" par la société TORAY SILICONE. Des silicones entrant dans cette classe sont également décrites dans l'article publié dans Cosmetics and Toiletries, Vol. 91, Jan. 76, P. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics ".

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and more particularly between:

• (i) cyclic polydiolkylsiloxanes having from 3 to 7, preferably from 4 to 5, silicon atoms. It is, for example, octamethylcyclotetrasiloxane marketed in particular under the name VOLATINE SILICONE® 7207 by UNION CARBIDE or SILBIONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name of VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE® 70045 V5 by RHODIA, as well as their mixtures.
  Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the "VOLATILE SILICONE FZ 3109" marketed by UNION CARBIDE, of formula: with
  
  Cyclic polydialkyl siloxane mixtures with organic compounds derived from silicon may also be mentioned, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '(hexa). -2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane;
• (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 × 10 ^-6 m ² / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name " SH 200 "by the company TORAY SILICONE. Silicones included in this class are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS Volatile Silicone fluids for cosmetics ".

Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups and mixtures thereof are preferably used.

These silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to ASTM 445 Appendix C.

• les huiles SILBIONE® des séries 47 et 70 047 ou les huiles MIRASIL® commercialisées par RHODIA telles que, par exemple l'huile 70 047 V 500 000;
• les huiles de la série MIRASIL® commercialisées par la société RHODIA ;
• les huiles de la série 200 de la société DOW CORNING telles que la DC200 ayant viscosité 60 000 mm²/s ;
• les huiles VISCASIL® de GENERAL ELECTRIC et certaines huiles des séries SF (SF 96, SF 18) de GENERAL ELECTRIC.

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products:

• the SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils marketed by RHODIA, such as, for example, the 70 047 V 500 000 oil;
• the oils of the MIRASIL® series marketed by RHODIA;
• oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm ² / s;
• VISCASIL® oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC.

Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA.

In this class of polydialkylsiloxanes, mention may also be made of the products sold under the names "ABIL WAX® 9800 and 9801" by GOLDSCHMIDT, which are polydialkyl (C ₁ -C ₂₀ ) siloxanes.

The silicone gums that can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high average molecular weights of between 200,000 and 1,000,000 used alone or in a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures.

• les mélanges formés à partir d'un polydiméthylsiloxane hydroxylé en bout de chaîne (ou diméthiconol (CTFA) et d'un poly-diméthylsiloxane cyclique également appelé cyclométhicone (CTFA) tel que le produit Q2 1401 commercialisé par la société DOW CORNING ;
• les mélanges d'une gomme polydiméthyl-siloxane et d'une silicone cyclique tel que le produit SF 1214 Silicone Fluid de la société GENERAL ELECTRIC, ce produit est une gomme SF 30 correspondant à une diméthicone, ayant un poids moléculaire moyen en nombre de 500 000 solubilisée dans l'huile SF 1202 Silicone Fluid correspondant au décaméthylcyclopentasiloxane ;
• les mélanges de deux PDMS de viscosités différentes, et plus particulièrement d'une gomme PDMS et d'une huile PDMS, tels que le produit SF 1236 de la société GENERAL ELECTRIC. Le produit SF 1236 est le mélange d'une gomme SE 30 définie ci-dessus ayant une viscosité de 20 m²/s et d'une huile SF 96 d'une viscosité de 5.10^-6m²/s. Ce produit comporte de préférence 15 % de gomme SE 30 et 85 % d'une huile SF 96.

More particularly useful products according to the invention are mixtures such as:

• mixtures formed from an end-hydroxylated polydimethylsiloxane (or dimethiconol (CTFA) and a cyclic poly-dimethylsiloxane also called cyclomethicone (CTFA) such as the product Q2 1401 sold by the company Dow Corning;
• mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from General Electric, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500 000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;
• mixtures of two PDMS of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m ² / s and an SF 96 oil with a viscosity of 5 × 10 ^-6 m ² / s. This product preferably comprises 15% of SE 30 gum and 85% of an SF 96 oil.

The organopolysiloxane resins used in accordance with the invention are crosslinked siloxane systems containing the units:
R ₂ SiO _2/2 , R ₃ SiO _1/2 , RSiO _3/2 and SiO _4/2
in which R represents an alkyl having 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a C ₁ -C ₄ lower alkyl group, more particularly methyl.

Among these resins may be mentioned the product marketed under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure.

Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu.

The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

In addition to the silicones described above, the organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned above.

The polyalkylarylsiloxanes are particularly chosen from polydimethyl methylphenylsiloxanes and linear and / or branched polydimethyl diphenylsiloxanes with a viscosity ranging from 1 × 10 ^-5 to ⁵ × 10 ^-2 m ² / s at 25 ° C.

• les huiles SILBIONE® de la série 70 641 de RHODIA;
• les huiles des séries RHODORSIL® 70 633 et 763 de RHODIA ;
• l'huile DOW CORNING 556 COSMETIC GRAD FLUID de DOW CORNING ;
• les silicones de la série PK de BAYER comme le produit PK20 ;
• les silicones des séries PN, PH de BAYER comme les produits PN1000 et PH1000 ;
• certaines huiles des séries SF de GENERAL ELECTRIC telles que SF 1023, SF 1154, SF 1250, SF 1265.

Among these polyalkylarylsiloxanes, mention may be made, by way of example, of the products sold under the following names:

• SILBIONE® oils of the 70 641 series from RHODIA;
• RHODORSIL® 70 633 and 763 RHODIA series of oils;
• DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING;
• silicones of the PK series from BAYER, such as the product PK20;
• silicones of the PN and PH series of BAYER, such as the PN1000 and PH1000 products;
• some oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265.

• des groupements polyéthylèneoxy et/ou polypropylèneoxy comportant éventuellement des groupements alkyle en C₆-C₂₄ tels que les produits dénommés diméthicone copolyol commercialisé par la société DOW CORNING sous la dénomination DC 1248 ou les huiles SILWET® L 722, L 7500, L 77, L 711 de la société UNION CARBIDE et l'alkyl (C₁₂)-méthicone copolyol commercialisée par la société DOW CORNING sous la dénomination Q2 5200 ;
• des groupements aminés substitués ou non comme les produits commercialisés sous la dénomination GP 4 Silicone Fluid et GP 7100 par la société GENESEE ou les produits commercialisés sous les dénominations Q2 8220 et DOW CORNING 929 ou 939 par la société DOW CORNING. Les groupements aminés substitués sont en particulier des groupements aminoalkyle en C₁-C₄ ;
• des groupements alcoxylés, comme le produit commercialisé sous la dénomination "SILICONE COPOLYMER F-755" par SWS SILICONES et ABIL WAX® 2428, 2434 et 2440 par la société GOLDSCHMIDT.

Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising:

• polyethyleneoxy and / or polypropyleneoxy groups optionally containing C ₆ -C ₂₄ alkyl groups such as the products known as dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 of UNION CARBIDE and the alkyl (C ₁₂ ) -methicone copolyol marketed by the company Dow Corning under the name Q2 5200;
• substituted or unsubstituted amine groups such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C ₁ -C ₄ aminoalkyl groups;
• alkoxylated groups, such as the product marketed under the name "SILICONE COPOLYMER F-755" by SWS SILICONES and ABIL WAX® 2428, 2434 and 2440 by the company GOLDSCHMIDT.

Preferably, the silicone or silicones are chosen from volatile, linear or cyclic polydimethylsiloxanes and phenyl silicones.

The silicones as described above may be used alone or as a mixture, in an amount of between 0.01 and 20% by weight, preferably between 0.1 and 5% by weight.

Among the preferred additional agents are also the protective agents of the hair fibers.

The protective agents of the hair fibers may be any active agent that is useful for preventing or limiting damage due to physical or chemical attack.

Thus, the protective agent for hair fibers may be chosen from water-soluble, fat-soluble organic UV filters, antiradical agents, antioxidants, vitamins, provitamins, vegetable waxes, ceramides, proteins and mixtures thereof. The organic UV filters (UV radiation filtering systems) are chosen in particular from water-soluble or fat-soluble, silicone or non-silicone filters and nanoparticles of inorganic oxides, the surface of which has optionally been treated to render it hydrophilic or hydrophobic.

The water-soluble organic UV filters may be chosen from, for example, para-aminobenzoic acid and its salts, anthranilic acid and its salts, salicylic acid and its salts, p-hydroxycinnamic acid and its salts, derivatives sulphonic benz-x-azole sulphides (benzothioazoles, benzimidazoles, benzoxazoles) and their salts, sulphonic benzophenone derivatives and their salts, sulphonic benzylidenecamphor derivatives and their salts, quaternary amine substituted benzylidene camphor derivatives and their salts, derivatives of phthalidene-camphorsulphonic acids and their salts, benzotriazole sulphonic derivatives.

It is also possible to use hydrophilic polymers having, in addition and by their chemical nature, photoprotective properties against UV radiation. Mention may be made of polymers containing benzylidene camphor and / or benzotriazole groups, substituted by sulphonic or quaternary ammonium groups.

As liposoluble (or lipophilic) organic UV filters suitable for use in the present invention, mention may be made in particular of: p-aminobenzoic acid derivatives, such as p-aminobenzoic acid esters or amides; salicylic acid derivatives such as esters; benzophenone derivatives; dibenzoylmethane derivatives; diphenylacrylate derivatives; benzofuran derivatives; polymeric UV filters containing one or more silico-organic residues; cinnamic acid esters; camphor derivatives; trianilino-s-triazine derivatives; urocanic acid ethyl ester; benzotriazoles; drifts hydroxyphenyltriazine; bis-resorcinol-dialkylaminotriazine; and their mixtures.

D'autres filtres UV particulièrement préférés selon l'invention sont les dérivés de benzophénones tels que l'UVINUL MS 40 (Acide 2-hydroxy 4-méthoxybenzophénone-5-sulfonique) et l'UVINUL M40 (2-hydroxy-4-méthoxybenzophénone) commercialisés par BASF, les dérivés de benzalmalonates tels que le PARSOL SLX (poly diméthyl/méthyl (3(4-(2,2-bis-éthoxycarbonylvinyl)-phénoxy)-propényl) siloxane) commercialisé par GIVAUDAN-ROURE, les dérivés de benzylidènecamphre tels que le MEXORYL SX (acide b-b'camphosulfonique [1-4 divinylbenzène]) fabriqué par la société CHIMEX, les dérivés de benzimidazole tels que l'EUSOLEX 232 (acide 2-phényl-benzimidazol-5-sulfonique) commercialisé par MERCK.The liposoluble (or lipophilic) UV filter according to the invention is preferably chosen from: octyl salicylate; 4-tert-butyl 4'-methoxydibenzoylmethane (PARSOL 1789 from GIVAUDAN); octocrylene; 2-ethylhexyl 4-methoxy cinnamate (PARSOL MCX) and the following compound of formula (XIII), or 2- (2H-benzotriazol-2-yl) -4-methyl-6- [2-methyl-3- [ 1,3,3,3-tetramethyl-1 - [(trimethylsilyl) oxy] disiloxanyl] propynyl] phenol, described in the patent application EP-A-0 392 883 :

Other particularly preferred UV filters according to the invention are benzophenone derivatives such as UVINUL MS 40 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) and UVINUL M40 (2-hydroxy-4-methoxybenzophenone) marketed by BASF, benzalmalonate derivatives such as PARSOL SLX (poly dimethyl / methyl (3 (4- (2,2-bis-ethoxycarbonylvinyl) phenoxy) propenyl) siloxane) marketed by GIVAUDAN-ROURE, benzylidenecamphor derivatives such as MEXORYL SX (b-b'camphosulfonic acid [1-4 divinylbenzene]) manufactured by the company CHIMEX, benzimidazole derivatives such as EUSOLEX 232 (2-phenyl-benzimidazol-5-sulfonic acid) marketed by MERCK .

The pH can be adjusted to the desired value by means of acidifying or basifying agents well known in the state of the art.

dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en C1-C4 ; R4, R5, R6 et R7, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en C1-C4 ou hydroxyalkyle en C1-C4. De préférence, une triéthanolamine est utilisée comme agent alcalinisant dans les compositions selon l'invention.Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, oxyethylenated and / or oxypropylenated hydroxyalkylamines and ethylene diamines, sodium or potassium hydroxides and compounds of the following formula:

in which R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R4, R5, R6 and R7, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. Preferably, a triethanolamine is used as alkalinizing agent in the compositions according to the invention.

The acidifying agents are conventionally, by way of example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid or sulphonic acids. .

Direct dyes can also be incorporated in the compositions of the invention.

As direct dyes that can be used according to the present invention, mention may be made of neutral, acidic or cationic nitro-benzene direct dyes, acid or cationic neutral azo direct dyes, direct quinone dyes, and in particular neutral, acidic or cationic anthraquinone dyes, and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes.

Among the preservatives, mention may be made of sorbic acid and its salts, parahydroxybenzoic acid esters and phenoxyethanol.

Among the anti-corrosion agents that may be used according to the invention, mention may be made of cyclohexylamine, diammonium phosphate, dilithium oxalate, dimethylamino methylpropanol, dipotassium oxalate and dipotassium phosphate, a disodium phosphate, a disodium pyrophosphate, disodium tetrapropenyl succinate, hexoxyethyl diethylammonium phosphate, nitromethane, potassium silicate, sodium aluminate, sodium hexametaphosphate, sodium metasilicate, sodium molybdate, sodium nitrite, sodium oxalate, silicate sodium, stearamidopropyl dimethicone, tetrapotassium pyrophosphate, and triisopropanolamine.

Thus, preferably, the cosmetic composition described above also comprises a compound chosen from alkalinizing agents, acidifying agents, silicones, organic solvents, perfumes, preserving agents, UV absorbing agents, coloring agents , anti-corrosion agents, and mixtures thereof.

The cosmetic composition according to the invention may comprise water.

The cosmetically acceptable medium of the composition according to the invention may comprise at least one organic solvent.

For the purposes of the present invention, the term "organic solvent" means an organic compound which is liquid at a temperature of 25 ° C. and at atmospheric pressure (760 mmHg).

The organic solvent of the cosmetic composition is generally chosen from C ₁ -C ₆ alcohols, preferably alkanols such as ethanol, propanol and isopropanol, polyols such as glycerol, propylene glycol and pentanediol, benzyl alcohol, and mixtures thereof.

Preferably, the organic solvent is ethanol.

In general, when present, the organic solvent represents from 1 to 98% and preferably from 20 to 95% by weight relative to the total weight of the composition.

The spraying device of a composition according to the invention may in particular be used in non-rinsed application both on dry hair and on damp hair.

The following examples illustrate the present invention.

Examples of formulation Example 1

Composition 1 terpolymer vinyl acetate / p-tert-butyl vinyl benzoate / crotonic acid (65/25/10) Expressed in polymer weight 6.00 g 2-amino-2-methyl-1-propanol 0.60 g Ethylhexyl methoxycinnamate marketed by ROCHE VITAMINS under the name PARSOL MCX 0.05 g Perfume 0.10 g Absolute ethyl alcohol qs 100 g

The composition 1 is packaged in a spraying device as defined above. This device comprises a membrane which itself comprises perforations which have a cross-sectional surface in the form of a circular disc whose diameter varies from 4 to 150 μm on the outer surface of the membrane, facing the external environment, and on the inner surface, facing the interior of the container, a cross-sectional surface in the form of a circular disk whose diameter varies from 2 to 50 .mu.m. This device comprises a piezoelectric actuator capable of vibrating the membrane and an electric battery for supplying the energy required for the piezoelectric actuator. The perforations of the device have an inverted conicity.

When using the device, the cosmetic composition emerges in the form of droplets whose average diameter is between 20 and 100 μm.

Example 2

Composition 2 vinyl acetate terpolymer / p-tert-butyl vinyl benzoate / crotonic acid (65/25/10) Expressed by weight of polymer 6.00 g 2-amino-2-methyl-1-propanol 0.60 g Ethylhexyl methoxycinnamate marketed by ROCHE VITAMINS under the name PARSOL MCX 0.05 g Demineralized Water 14 g Perfume 0.1 g Absolute ethyl alcohol qs 100 g

Composition 2 above is packaged in a spraying device identical to that described in Example 1.

Example 3

Composition 3 LUVISET SI-PUR resin marketed by BASF (polyurethane -6) Expressed in polymer weight 9.00 Ethylhexyl methoxycinnamate marketed by ROCHE VITAMINS under the name PARSOL MCX 0.05 Demineralized water (contained in the polymer in its commercial form) 18 Demineralized water form 18 perfume 0.10 Absolute ethyl alcohol qs 100

Composition 3 above is packaged in a spraying device identical to that described in Example 1.

The spraying device described in Example 1, comprising the composition 1, 2 or 3, as defined above makes it possible to obtain a quality of maintaining the hairstyle and / or an ease of elimination when brushing the hairstyle. which can not be reached usually with known devices without thrusters such as flasks pumps.

The application can be done on both wet and dry hair.

Claims (21)

Apparatus for spraying a cosmetic composition comprising a container equipped with a spraying mechanism comprising: a perforated membrane, the perforations of the membrane communicating the interior of the container with the external environment, an actuator for vibrating the membrane, means for bringing the liquid cosmetic composition contained in the container into contact with an inner surface of the membrane, the cosmetic composition, under the effect of the vibrations of the membrane flowing through the perforations to an external surface of the membrane, from where it emerges in the form of droplets, and the liquid cosmetic composition comprising, in a cosmetically acceptable medium, at least one fixing polymer. Device for spraying a composition according to claim 1, characterized in that the perforations in the membrane have an inverted conicity, that is to say a larger cross-sectional area on the outer surface of the membrane, facing to the external environment, only on the inner surface, facing the inside of the container. A spray device of a composition according to claim 1 or 2, characterized in that it further comprises pressure shifting means providing reduced pressure to the liquid in contact with the inner surface of the membrane. Device for spraying a composition according to claim 3, characterized in that the reduced pressure varies from the ambient pressure to the pressure at which the air is sucked through the perforations of the membrane in contact with the composition. Device for spraying a composition according to claim 1 or 2, characterized in that the perforations on the outer surface of the membrane do not touch each other. Spray device of a composition according to any one of the preceding claims, characterized in that the actuator is a piezoelectric actuator. Device for spraying a composition according to any one of the preceding claims, characterized in that the means for bringing the liquid cosmetic composition to the surface of the membrane comprises a capillary feeding mechanism. Device for spraying a composition according to any one of the preceding claims, characterized in that the means for bringing the liquid cosmetic composition to the surface of the membrane comprises a bubble generator feeding mechanism. Device for spraying a composition according to any one of the preceding claims, characterized in that all the perforations have an inverted conicity. Device for spraying a composition according to any one of claims 1 to 8, characterized in that the membrane further comprises perforations of normal conicity. Spray device of a composition according to claim 10, characterized in that the normal conical perforations are arranged around and outside the inverted conical perforations. Device for spraying a composition according to any one of the preceding claims, characterized in that the actuator is designed to vibrate said membrane in a frequency range from 20 KHz to 7 MHz. Device for spraying a composition according to any one of the preceding claims, characterized in that the fixing polymer is chosen from an anionic, cationic, amphoteric and nonionic fixing polymer. Device for spraying a composition according to any one of the preceding claims, characterized in that the fixing polymer is chosen from copolymers derived from crotonic acid having in their chain acetate or vinyl propionate units and possibly other monomers chosen from allyl, methallyl or vinyl esters of a saturated carboxylic acid, linear or branched, with a long hydrocarbon chain containing at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, and the vinyl, allyl or methallyl esters of an α- or β-cyclic carboxylic acid. Device for spraying a composition according to any one of the preceding claims, characterized in that the fixing polymer is a vinyl acetate terpolymer / p-tert-butyl vinyl benzoate / crotonic acid. Device for spraying a composition according to any one of Claims 1 to 13, characterized in that the fixing polymer is chosen from silicone or non-silicone polyurethanes, linear sulphonic polyesters, branched block acrylic copolymers, and octylacrylamide copolymers. / acrylates / butylaminoéthylméthacrylates. Device for spraying a composition according to any one of the preceding claims, characterized in that the fixing polymer or polymers represent from 0.1 to 20% by weight, preferably from 1 to 12% by weight relative to the total weight of the cosmetic composition. Device for spraying a composition according to any one of the preceding claims, characterized in that the cosmetic composition comprises water. Device for spraying a composition according to any one of the preceding claims, characterized in that it comprises one or more additives chosen from alkalinizing agents, acidifying agents, silicones, perfumes, preserving agents, UV absorbers, coloring agents, anticorrosion agents and mixtures thereof. Device for spraying a composition according to any one of the preceding claims, characterized in that the cosmetically acceptable medium contains at least one organic solvent chosen from C ₁ -C ₆ alcohols, preferably alkanols such as ethanol, propanol and isopropanol, polyols such as glycerol, propylene glycol and pentanediol, benzyl alcohol, and mixtures thereof. Device for spraying a composition according to claim 19, characterized in that the organic solvent is ethanol.