WO2011157796A1 - Cosmetic composition comprising a branched sulphonic polyester and a particular thickener and uses in hair styling - Google Patents

Abstract

The present application relates to a cosmetic composition comprising, in a cosmetically acceptable medium: (i)one or more branched sulphonic polyesters, and (ii) one or more polyvinyl alcohols. The present application also relates to the uses of this composition especially for the styling and the shaping of the hair.

Description

COSMETIC COMPOSITION COMPRISING A BRANCHED

SULPHONIC POLYE STER AND A PARTICULAR THICKENER AND

USES IN HAIR STYLING

The present invention relates to novel cosmetic compositions comprising one or more branched sulphonic po lyesters and one or more polyvinyl alcoho ls as thickening polymers, and also to the uses of these compositions, especially in styling.

The present invention also relates to a method of styling keratin materials using these compositions .

The use o f branched sulphonic po lyesters in hair styling and fixing compositions is known and described, for example, in patent applications EP 0 966 946, WO 98/38969 and WO 99/63955.

Nevertheless, the use of branched sulphonic polyesters is not without drawbacks :

^■ the use of these polyesters in hair lacquers containing large quantities o f alcoho l generally gives good styling properties but does not make it possible to obtain sufficient lacquering power;

■ the application o f these polyesters in the form o f lacquers with a high alcoho l content gives the hair, after brushing, a dry feel; this undesirable phenomenon is particularly noticeable for dyed hair; and

^■ these polyesters are generally in semi-so lid form, this property often makes their use difficult, in particular it is often difficult to ensure a homogeneous distribution o f these po lyesters over all the hair to be treated.

Unexpectedly and advantageously, the Applicant has demonstrated that the use of one or more branched sulphonic polyesters with one or more thickening polymers of polyvinyl alcohol type makes it possible to overcome the aforementioned drawbacks.

One subj ect of the present invention is thus a cosmetic composition comprising one or more branched sulphonic polyesters and one or more polyvinyl alcohols .

The compositions obtained are in the form o f gels, mousses, sprays, creams or pastes .

The compositions according to the present invention are easy to prepare and to apply. They remain satisfactorily localized, without runs, at the point of application. The compositions according to the present invention may be applied without a reduction in viscosity over time.

Moreover, the compositions according to the present invention make it possible to give the hairstyle a natural and long-lasting form retention.

Another subj ect of the present invention is a method for styling keratin materials, preferably human keratin materials and in particular the hair, which uses the compositions according to the invention.

Another subj ect of the present invention is the uses of the compositions according to the invention, especially for styling and shaping of keratin materials, preferably human keratin materials and in particular the hair.

Other features, aspects, subj ects and advantages of the invention will appear even more clearly on reading the description and examples that fo llow.

The expression "po lyvinyl alcoho l" is understood within the present application to mean a po lymer comprising -CH₂CH(OH)- groups .

The branched sulphonic po lyesters used in the compositions o f the present invention are known in the prior art. Their structure and synthesis are described in documents WO 95/ 1 8 19 1 , WO 97/08261 and WO 97/20899.

Preferred, in particular, are branched sulphonic polyesters obtained by po lycondensation o f:

(a) at least one dicarboxylic acid that does not bear a sulphonic functional group, (b) at least one dio l or a mixture o f a dio l and of a diamine,

(c) at least one monomer comprising two identical or different reactive functional groups chosen from hydroxyl, amino and carboxyl groups, and that bears, in addition, at least one sulphonic functional group , and

(d) at least one monomer comprising at least three identical or different reactive functional groups chosen from hydroxyl, amino and carboxyl groups.

The dicarboxylic acids that form the units (a) may be aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids and mixtures of such acids.

Mention may be made, by way o f examp le, of 1 ,4- cyclohexanedioic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, 1 ,3 -cyclohexanedioic acid, phthalic acid, terephthalic acid and isophthalic acid and mixtures of such acids.

The dio ls that form the units (b) are chosen, for example, from alkanedio ls and polyalkylenedio ls, and mention may be made, by way of example, of ethylene glyco l, propylene glycol, diethylene glycol, triethylene glycol and polypropylene glycol.

The diamines capable of forming one part of the units (b) are preferably chosen from alkanediamines and polyoxyalkylene diamines.

The expression "sulphonic functional group" of the units (c) encompasses both the sulphonic acid functional group (-SO3H) and the corresponding salified functional groups obtained by neutralization o f the sulphonic acid functional group with a base, for example an alkali metal hydroxide.

The sulphonic functional groups are preferably in the form which is neutralized by an organic or inorganic base.

The units (c) are derived, for example, from dicarboxylic acids, dicarboxylic acid esters, glycols and hydroxy acids, all bearing at least one sulphonic group , in acid and/or neutralized form, preferably in neutralized form.

The units (c) bearing at least one sulphonic functional group preferably represent from 2 to 15 mol% of the total amount of monomers .

The units (d) derived from multifunctional monomers are preferably present in an amount between 0. 1 and 40 mol% relative to the total amount of monomers .

The multifunctional monomers forming the units (d) are chosen, for examp le, from trimethylo lethane, trimethylo lpropane, glycerol, pentaerythrito l, sorbito l, trimellitic anhydride, erythrito l, threito l, dipentaerythrito l, pyromellitic dianhydride and dimethylpropionic acid.

The branched sulphonic po lyesters may comprise, in addition to the four types o f units (a) to (d) described above, units (e) derived from monomers comprising two different reactive functional groups, chosen for example from hydroxy carboxylic acids and amino carboxylic acids or mixtures thereof.

These units (e) may represent up to 40 mo l% o f the total amount of monomers (a), (b), (c), (d) and (e).

Of course, the branched sulphonic polymers used in the present invention are preferably obtained from a mixture of monomers in which the number o f equivalents of carboxylic acid functional groups is substantially equal to the number of equivalents of hydroxyl functional groups and o f amino functional groups which may be present.

The branched sulphonic polymers used in the styling compositions of the present invention are known and so ld, for example, by Eastman. Mention may be made, as a preferred commercial product, of the product sold under the name AQ 1350^® by Eastman.

The composition according to the present invention advantageously comprises from 0.2 to 1 5 %, preferably from 0.5 to 10%> by weight of one or more branched sulphonic polyesters relative to the total weight of the composition.

The composition according to the present invention also contains one or more polyvinyl alcohols. The latter are present as thickening polymers.

For the purposes of the present invention, the expression "thickening polymer" means a polymer capable, by its presence, of increasing the viscosity of the medium by at least 50 centipoise at 25°C and at a shear rate of 1 s^"1. Preferably, the thickening polymer has, at 1% in water or a 50/50 water/alcohol mixture by weight at 25°C, a viscosity of greater than 100 centipoise at a shear rate of 1 s^"1. These viscosities may be measured in particular with viscometers or rheometers with cone-plate geometry.

The expression "polyvinyl alcohol" as indicated above is understood to mean a polymer comprising -CH₂CH(OH)- units.

The polyvinyl alcohols are generally produced by hydrolysis of polyvinyl acetate. Usually, the reaction takes place in the presence of methanol (alcoho lysis). The reaction is customarily acid-catalysed or base-catalysed. The degree of hydrolysis of commerical products is variable, often around 87% but there are also products with a degree of hydrolysis of 100.

Copolymers with monomers other than vinyl acetate also exist, such as ethylene/vinyl alcohol copolymers.

The polyvinyl alcohol polymers as thickening polymers are preferably chosen from homopolymers or copolymers with vinyl acetate, the latter corresponding in particular to a partial hydrolysis of polyvinyl acetate. Use may be made, for example, of the products from the Celvol range sold by the company CELANESE under the names Celvol 540, Celvol 350,

Celvol 325, Celvol 165, Celvol 125 Celvol 540 S, Celvol 840, Celvol 443. The composition according to the present invention advantageously comprises from 0.05 to 20%, preferably from 0. 1 to 10%> by weight o f one or more po lyvinyl alcohols relative to the total weight of the composition.

Advantageously, in the cosmetic composition according to the invention, the polyvinyl alcohol(s) are chosen from homopolymers or copolymers. More advantageously still, the copolymer(s) are copolymers with vinyl acetate.

Preferably, the cosmetically acceptable medium is aqueous.

The cosmetic composition according to the invention may also comprise one or more organic so lvents, preferably in an amount between 0.05 and 40%>, very preferably between 1 and 20%> by weight, relative to the total weight of the composition.

This organic so lvent may be a C₂ to C₄ lower alcoho l, in particular ethanol, polyo ls and po lyo l ethers such as propylene glycol, polyethylene glycol or glycerol.

The compositions according to the invention may also contain other cosmetically acceptable adjuvants, such as for example ionic or nonionic surfactants, additional thickeners other than the polyvinyl alcoho ls used in the compositions according to the present application, ethoxylated or non-ethoxylated fatty alcoho ls, co-thickeners, penetrants, fragrances, dyes, plasticizers, buffers, and various customary adjuvants such as waxes, volatile or non-vo latile silicones that are cyclic or linear or branched, and are organomodified especially alkoxylated or modified by amine groups or are unmodified, for example silicone gums, ceramides, pseudoceramides, plant, mineral or synthetic oils, vitamins or provitamins such as panthenol, opacifiers, reducing agents, emulsifiers, preservatives, mineral fillers, pearlescent agents, flakes, sunscreens, proteins, anionic, nonionic, cationic or amphoteric fixing polymers, moisturisers, emo llients, demulcents, anti-fo aming agents, antiperspirants, free-radical scavengers, bactericides, sequestrants, anti- dandruff agents, antioxidants, basifying agents, acidifying agents, and any other additive conventionally used in cosmetic compositions intended to be applied to the hair.

The surfactants that can be used in the composition according to the present invention may be anionic, nonionic, amphoteric or cationic surfactants, or mixtures thereof.

The term "anionic surfactant" means a surfactant comprising, as ionic or ionizable groups, only anionic groups . These anionic groups are preferably chosen from the following groups : C0₂H, C0₂ ^", S O₃H, S O₃ ^", O S O3H, O S O3 ^", H2PO3 , HPO3 ^" ,P0₃ ^2", H2PO2 , HPO2 , HPCV, P0₂ ^", POH, PO .

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkyl sulphonates, alkylamide sulphonates, alkylaryl sulphonates, alpha-o lefin sulphonates, paraffin sulphonates, alkyl sulphosuccinates, alkyl ether sulphosuccinates, alkylamide sulphosuccinates, alkyl sulphoacetates, acyl sarcosinates, acyl glutamates, alkyl sulphosuccinamates, acyl isethionates and N-acyltaurates, salts o f alkyl monoesters o f polyglycoside-polycarboxylic acids, acyl lactylates, D-galactoside- uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts ; and the corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group .

These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts o f C₆ -24 alkyl monoesters of polyglycoside- polycarboxylic acids may be chosen from C₆ -24 alkyl polyglycoside citrates, C₆ -24 alkyl polyglycoside tartrates and C₆ -24 alkyl polyglycoside sulphosuccinates.

When the anionic surfactant(s) (ii) are in salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably the sodium salt, the ammonium salts, the amine salts and in particular amino alcohol salts or the alkaline-earth metal salts such as the magnesium salt.

Examples o f amino alcoho l salts that may especially be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl- 1 -propanol salts, 2-amino- 2-methyl- 1 ,3 -propanedio l salts and tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.

Among the anionic surfactants, it is preferred, according to the invention, to use alkyl sulphate salts and alkyl ether sulphate salts and mixtures thereof.

Nonionic surfactants are themselves also compounds that are well known per se (see especially in this regard the "Handbook of Surfactants" by M .R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp . 1 16- 178) . Thus, they may be chosen especially from (non-limiting list) alcohols, alpha-diols and alkylphenols, these compounds being po lyethoxylated, polypropoxylated or polyglycerolated and containing a fatty chain comprising, for example, 8 to 1 8 carbon atoms, it being possible for the number of ethylene oxide or propylene oxide groups to range especially from 2 to 50 and it being possible for the number o f glycero l groups to range especially from 2 to 30. Mention may also be made o f copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and of propylene oxide with fatty alcoho ls; po lyethoxylated fatty amides preferably having from 2 to 30 mo l o f ethylene oxide, polyglycerolated fatty amides containing on average 1 to 5 , and in particular 1 .5 to 4 glycerol groups, ethoxylated fatty acid esters of sorbitan containing from 2 to 30 mo l o f ethylene oxide, fatty acid esters of sucrose, fatty acid esters of polyethylene glyco l, alkylpo lyglycosides, N-alkylglucamine derivatives, amine oxides such as (C i o- C i 4)alkylamine oxides or N-acylaminopropylmorpholine oxides . It will be noted that alkylpolyglycosides constitute nonionic surfactants that are particularly suitable within the context of the present invention.

The amphoteric or zwitterionic surfactant(s) that can be used in the present invention may especially be optionally quaternized, secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulphonate, sulphate, phosphate or phosphonate group . In particular, mention may be made of (C₈- C2o)alkylbetaines, sulphobetaines, (C 8 - C20 alkyl)amido(C3 -8 alkyl)betaines or (C 8 - C20 alkyl)amido(C6-Cs alkyl)sulphobetaines . Among the optionally quaternized, secondary or tertiary aliphatic amine derivatives that can be used, as defined above, mention may also be made o f the compounds having the respective structures (A l ) and (A2) below :

Ra-CONHCH₂CH₂- N⁺(Rb)(Rc)(CH₂COO^~) (A l ) in which:

Ra represents a C 10-C₃₀ alkyl or alkenyl group derived from an acid

Ra-COOH, preferably present in hydrolysed coconut oil, a heptyl, nonyl or undecyl group,

Rb represents a beta-hydroxyethyl group , and

Rc represents a carboxymethyl group;

-CONHCH₂CH₂-N(B)(B') (A2) in which:

B represents -CH₂CH₂OX^*,

B' represents -(CH₂)_ZY' , with z = 1 or 2, X^* represents the group -CH₂-COOH, CH₂-COOZ ' , -CH₂CH₂- COOH, -CH₂CH₂-COOZ ' , or a hydrogen atom,

Y^* represents -COOH, -COOZ ' , the group -CH₂-CHOH-S0₃H or -CH₂-CHOH-S0₃Z ' ,

Z ' represents an ion derived from an alkali metal or alkaline- earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine.

Ra ' represents a C i o-C₃o alkyl or alkenyl or alkenyl group of an acid Ra' -COOH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially a C _{1 7} alkyl group, and its iso form, or an unsaturated C _{1 7} group .

These compounds are classified in the CTFA dictionary, 5th edition, 1993 , under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made o f the cocoamphodiacetate sold by the company Rhodia under the trade name Mirano l® C2M Concentrate.

The composition according to the invention may also comprise one or more cationic surfactants that are well known per se, such as optionally polyoxyalkylenated, primary, secondary or tertiary fatty amine salts; quaternary ammonium salts such as tetraalkylammonium, alky lamido alky ltria Iky lammonium, trialkylbenzyl ammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazo line derivatives; or amine oxides of cationic nature.

The nonionic, amphoteric and cationic surfactants described above may be used alone or as mixtures and the amount thereof is between 0.01 % and 30%> by weight, preferably between 0.05 %> and 20%> by weight and better still between 0. 1 % and 10%> by weight, relative to the total weight of the composition.

The additional gelling agents and/or thickeners other than the polyvinyl alcohols of the invention and that are suitable for the compositions o f the invention are well known in the art and may be chosen from po ly(oxyalkylene) glycols, poly(oxyalkylene) glycol esters, alginates, bio saccharides, starch derivatives, natural gums such as xanthan gum, guar gum, carob bean gum, scleroglucans, derivatives o f chitin and o f chitosan, carrageenans, clays, and mixtures thereof.

By way of example of gelling agents, especially that are in the aqueous phase, mention may be made o f Fucogel^® 1000 PP so ld by the company So labia, Satiagel^® KSO so ld by Degussa and Keltro l^® so ld by the company Kelco .

The additional gelling agents in general represent from 0.05 to 15 %, preferably from 0.5 to 1 0% by weight of the composition.

The silicones that may be used as additives in the cosmetic compositions o f the present invention are vo latile or non- vo latile, cyclic, linear or branched silicones, optionally modified with organic groups, having a viscosity from 5 >< 10^"6 to 2.5 m²/s at 25 °C and preferably l x l O^"5 to 1 m²/s .

The silicones that can be used in accordance with the invention may be so luble or inso luble in the composition and in particular may be polyorganosiloxanes that are insoluble in the composition o f the invention. They may be in the form o f oils, waxes, resins or gums .

Organopolysiloxanes are defined in greater detail in Walter Noll ' s "Chemistry and Techno logy of Silicones" ( 1968), Academic Press. They may be vo latile or non- vo latile.

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

(i) cyclic silicones containing from 3 to 7 and preferably 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone^® 7207 by Union Carbide or Silbione^® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone^® 7158 by Union Carbide, and Silbione® 70045 V5 by Rhodia, and mixtures thereof.

Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone^® FZ 3109 sold by the company Union Carbide, of formula: — D" - D" D"— D'—

CH₃ ' ' CH₃

withD": — Si-O— with D" : -Si-O—

CH₃ C₈H₁₇

Mention may also be made of mixtures of cyclic silicones with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1'- bis(2,2,2',2',3,3 '-hexatrimethylsilyloxy)neopentane;

(ii) linear volatile silicones containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5 x 10^"6 m²/s at 25°C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers "Volatile Silicone Fluids for Cosmetics".

Non-volatile silicones, and more particularly polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes, silicone gums and resins, polyorganosiloxanes modified with organofunctional groups, and mixtures thereof, are preferably used.

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

Among these polyalkylsiloxanes, mention may be made, in a non- limiting manner, of the following commercial products:

- the Silbione® oils of the 47 and 70047 series or the Mirasil® oils sold by Rhodia, for instance the oil 70047 V 500000;

- the oils of the Mirasil® series sold by the company Rhodia;

- the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60000 mm²/s;

- the Viscasil® oils from General Electric and certain oils of the

SF series (SF 96, SF 18) from General Electric.

Mention may also be made of polymethylsiloxanes containing dimethylsilanol end groups, known by the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.

In this category of polyalkylsiloxanes, mention may also be made of the products sold under the names "Abil Wax® 9800 and 9801" by the company Goldschmidt, which are poly(Ci-C₂o) alkylsiloxanes.

The polyalkylarylsiloxanes are chosen particularly from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity of from lxlO^"5 to 5x10^"

² m²/s at 25°C.

Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:

- the Silbione^® oils of the 70641 series from Rhodia;

- the oils of the Rhodorsil^® 70633 and 763 series from Rhodia;

- the Dow Corning 556 Cosmetic Grade Fluid oil from Dow Corning;

- the silicones of the PK series from Bayer, such as the product

PK20;

- the silicones of the PN and PH series from Bayer, such as the products PN1000 and PH1000;

- certain oils of the SF series from General Electric, such as SF 1023 , SF 1 1 54, SF 1250 and SF 1265.

The silicone gums that can be used in accordance with the invention are, in particular, po lyorganosiloxanes having high number- average mo lecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a so lvent. This so lvent can be chosen from vo latile silicones, po lydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane and tridecane, or mixtures thereo f.

Mention may be made more particularly o f the fo llowing products :

polydimethylsiloxane gums,

- polydimethylsiloxane/methylvinylsiloxane gums,

- polydimethylsiloxane/diphenylsiloxane gums,

- polydimethylsiloxane/phenylmethylsiloxane gums,

- polydimethylsiloxane/diphenylsiloxane/methylvinylsiloxane gums.

Products that can be used more particularly in accordance with the invention are mixtures such as :

- mixtures formed from a po lydimethylsiloxane hydroxylated at the end of the chain, or dimethiconol (CTFA) and from a cyclic polydimethylsiloxane also called cyclomethicone (CTFA), such as the product Q2 1401 sold by the company Dow Corning;

- mixtures formed from a po lydimethylsiloxane gum with a cyclic silicone, such as the product SF 1214 Silicone Fluid from the company General Electric; this product is an SF 30 gum corresponding to a dimethicone, having a number-average mo lecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethy Icy clop entasiloxane;

- mixtures of two PDMSs with 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 a mixture of a gum SE 30 defined above with a viscosity o f 20 m²/s and o f an oil SF 96 with a viscosity o f 5 x 10^"6 m²/s . This product preferably comprises 15% o f gum SE 30 and 85% o f an oil SF 96.

The organopolysiloxane resins that can be used in accordance with the invention are crosslinked siloxane systems containing the fo llowing units :

R₂Si0₂/2 , Rs SiO i/2 , RSi0_3/2 and Si0_4/2

in which R represents a hydrocarbon-based group containing 1 to 16 carbon atoms or a phenyl group . Among these products, the ones that are particularly preferred are those in which R denotes a C i -C₄ lower alkyl group, more particularly methyl, or a phenyl group .

Among these resins, mention may be made o f the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid S S 4230 and S S 4267 by the company General Electric, which are silicones of dimethyl/trimethylsiloxane structure.

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

The organomodified silicones that can 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 .

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

- polyethyleneoxy and/or polypropyleneoxy groups optionally containing C₆-C₂₄ alkyl groups, such as the products known as dimethicone copo lyo l so ld by the company Dow Corning under the name DC 1248 or the oils Silwet® L 722, L 7500, L 77, L 71 1 from the company Union Carbide and the (C i ₂)alkylmethicone copolyo l so ld by the company Dow Corning under the name Q2 5200;

- substituted or unsubstituted amine groups, such as the products so ld 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 or Dow Corning 2-8299 by the company Dow Corning or the product sold under the name Belsil ADM LOG 1 by the company Wacker. The substituted amine groups are, in particular, C 1 - C 4 aminoalkyl groups;

- thio l groups such as the products sold under the names GP 72A and GP 71 from Genesee;

- alkoxylated groups such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones and Abil Wax® 2428 , 2434 and 2440 by the company Go ldschmidt;

hydroxylated groups such as the po lyorganosiloxanes containing a hydroxyalkyl functional group, described in French patent application FR-A-8 5 16 334;

alkoxyalkyl groups such as, for example, the polyorganosiloxanes described in patent US-A-4 957 732;

- anionic groups o f carboxylic type, such as, for example, in the products described in patent EP 1 86 507 from the company Chisso Corporation, or of alkylcarboxylic type, such as those present in the product X-22-3701 E from the company Shin-Etsu; 2-hydroxyalkyl sulphonate; 2-hydroxyalkyl thio sulphate such as the products sold by the company Go ldschmidt under the names Abil^® S201 and Abil^® S255 ;

hydroxyacrylamino groups, for instance the polyorganosiloxanes described in patent application EP 342 834. Mention may be made, for example, of the product Q2-8413 from the company Dow Corning.

The silicones as described above may be used, alone or as a mixture, in an amount of between 0.01 % and 20% by weight and preferably between 0. 1 % and 5 % by weight.

The compositions o f the invention may also comprise non- silicone fatty substances such as mineral, plant, animal and synthetic oils, waxes, fatty esters, ethoxylated or non-ethoxylated fatty alcoho ls, and fatty acids . As oils that may be used in the composition o f the invention, examples that may be mentioned include :

hydrocarbon-based oils o f animal origin, such as perhydrosqualene;

- hydrocarbon-based oils of plant origin, such as liquid fatty acid triglycerides containing from 4 to 10 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, maize oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stearineries Dubois or those sold under the names Miglyo l^® 8 10, 8 12 and 8 1 8 by the company Dynamit Nobel, jojoba oil and shea butter oil;

- linear or branched hydrocarbons of mineral or synthetic origin, such as vo latile or non-vo latile liquid paraffins, and derivatives thereof, petroleum j elly, po lydecenes, hydrogenated polyisobutene such as Parleam®; isoparaffins, for instance isohexadecane and isodecane;

- partially hydrocarbon-based and/or silicone-based fluoro oils, for instance those described in document JP-A-2-295 912; fluoro oils that may also be mentioned include perfluoromethylcyclopentane and perfluoro- 1 ,3 -dimethylcyclohexane, sold under the names Flutec^® PC I and Flutec^® PC3 by the company BNFL Fluorochemicals; perfluoro- 1 ,2- dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050^® and PF 5060^® by the company 3M, or bromoperfluorooctyl so ld under the name Foralkyl^® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4- trifluoromethyl perfluoromorpholine sold under the name PF 5052^® by the company 3M;

The wax(es) are selected in particular from carnauba wax, candelilla wax, esparto grass wax, paraffin wax, ozokerite, plant waxes such as o live wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax o f blackcurrant blo ssom so ld by the company Bertin (France), animal waxes, for instance beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy raw materials that may be used according to the invention are especially marine waxes such as the product sold by the company Sophim under the reference M82, and po lyethylene waxes or polyo lefin waxes in general.

The saturated or unsaturated fatty acids are more particularly chosen from myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, lino leic acid, lino lenic acid and isostearic acid.

The fatty esters are especially carboxylic acid esters, in particular mono-, di-, tri- , or tetracarboxylic esters.

The carboxylic acid esters are especially esters of saturated or unsaturated, linear or branched C i -C₂₆ aliphatic acids and of saturated or unsaturated, linear or branched C i -C₂₆ aliphatic alcoho ls, the total carbon number o f the esters being greater than or equal to 10.

Among the monoesters, mention may be made o f dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C _{1 2}- C i 5 alkyl lactate; isostearyl lactate; lauryl lactate; lino leyl lactate; o leyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricino leate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Esters of C₄-C₂₂ dicarboxylic or tricarboxylic acids and of C i -C₂₂ alcoho ls and esters o f monocarboxylic, dicarboxylic or tricarboxylic acids and of C₂-C₂₆ dihydroxy, trihydroxy, tetrahydroxy or pentahydroxy alcoho ls may also be used. Mention may especially be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dio ctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricino leate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glyco l dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glyco l dioctanoate and neopentyl glyco l diheptanoate. The esters mentioned above being different from the esters of formula (I) .

Among the esters mentioned above, it is preferred to use ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.

As fatty alcoho ls, mention may be made of linear or branched, saturated or unsaturated fatty alcoho ls containing from 8 to 26 carbon atoms, for instance cetyl alcoho l, stearyl alcohol and the mixture thereo f (cetylstearyl alcoho l), octyldodecanol, 2-butyloctano l, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcoho l or lino leyl alcoho l.

The fatty substances in general represent from 0. 1 to 50%; preferably from 1 to 30%, and more preferably still from 2 to 20% by weight of the total composition.

As indicated previously, the compositions may comprise fixing polymers other than the polymers used according to the invention. The expression " fixing polymer" is understood within the meaning o f the present invention to mean any polymer that makes it possible to give a shape to the hair or to hold the hair in a given shape.

All the anionic, cationic, amphoteric and nonionic fixing polymers and mixtures thereof used in the art may be used in the compositions according to the present application.

The fixing po lymers may be so luble in the cosmetically acceptable medium or inso luble in this same medium and used in this case in the form o f dispersions o f so lid or liquid particles o f po lymer (latex or pseudolatex) .

The anionic fixing polymers generally used are polymers containing groups derived from carboxylic, sulphonic or phosphoric acid, and have a number-average mo lecular mass of between approximately 500 and 5 000 000.

The anionic fixing containing carboxylic groups that are preferred according to the invention are :

A) copolymers of acrylic acid and of acrylamide sold in the form of their sodium salts under the names Reten 421 , 423 or 425 by the company Hercules, the sodium salts of polyhydroxycarboxylic acids;

B) copolymers of acrylic or methacrylic acid with a monoethylenic monomer such as ethylene, styrene, vinyl esters, acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glyco l such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1 222 944 and German patent application 2 330 956 , the copolymers of this type comprising an optionally N-alkylated and/or hydroxyalkylated acrylamide unit in their chain as described in particular in Luxembourg patent application 75370 and 75371 or sold under the name Quadramer by the company American Cyanamid. Mention may also be made of the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers such as Ultrahold Strong so ld by the company BASF . Mention may also be made o f copolymers of acrylic acid and of C 1 - C4 alkyl methacrylate and terpolymers of vinylpyrro lidone, of acrylic acid and of methacrylate of C 1 - C20 alkyl, for example lauryl methacrylate, such as the product sold by the company ISP under the name Acrylidone^® LM and methacrylic acid/ethyl acrylate/tert-butyl acrylate terpolymers such as the product sold under the name Luvimer^® 100 P by the company BASF; Mention may also be made o f methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers as an aqueous dispersion, sold under the name Amerho ld® DR 25 by the company Amercho l.

C) crotonic acid copolymers, such as those comprising vinyl acetate or propionate units in their chain and optionally other monomers such as allyl esters or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid with a long hydrocarbon chain such as those containing at least 5 carbon atoms, it being possible for these polymers optionally to be grafted or crosslinked, or alternatively another vinyl, allyl or methallyl ester monomer of an a- or β-cyclic carboxylic acid. Such po lymers are described, inter alia, in French patents 1 222 944, 1 580 545 , 2 265 782, 2 265 78 1 , 1 564 1 1 0 and 2 439 798. Commercial products that come under this category are the resins 28-29-30, 26- 13 - 14 and 28- 13 - 10 so ld by the company National Starch;

D) copolymers of C 4 - C 8 monounsaturated carboxylic acids or anhydrides chosen from:

- copolymers comprising (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) at least one monomer selected from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid and its esters, the anhydride functions of these copolymers optionally being monoesterified or monoamidated. Such polymers are described, in particular, in US patents 2 047 398 , 2 723 248 and 2 102 1 13 , and GB patent 839 805 . Commercial products are especially those so ld under the names Gantrez^® AN or ES by the company ISP;

- copolymers comprising (i) one or more maleic, citraconic or itaconic anhydride units and (ii) one or more monomers chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, O-o lefin, acrylic or methacrylic ester, acrylic or methacrylic acid or vinylpyrrolidone groups in their chain,

the anhydride functions o f these copolymers optionally being monoesterified or monoamidated. These polymers are described, for example, in French patents 2 350 384 and 2 357 241 by the Applicant;

E) polyacrylamides comprising carboxylate groups .

F) homopolymers and copolymers comprising sulphonic groups such as po lymers comprising vinylsulphonic, styrenesulphonic, naphthalenesulphonic or acrylamidoalkylsulphonic units, different from the branched sulphonic polyesters used according to the invention.

These po lymers can be chosen in particular from:

- polyvinylsulphonic acid salts having a mo lecular weight of approximately between 1000 and 100 000 , and also the copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and their esters, and also acrylamide or its derivatives, vinyl ethers and vinylpyrro lidone;

- polystyrenesulphonic acid salts such as the sodium salts that are so ld for examp le under the names Flexan^® 500 and Flexan^® 130 by National Starch. These compounds are described in patent FR 2 198 719;

- polyacrylamidesulphonic acid salts, such as those mentioned in patent US 4 128 63 1 and more particularly polyacrylamidoethylpropanesulphonic acid sold under the name Cosmedia Polymer HSP 1 1 80 by Henkel.

As another anionic fixing polymer that can be used according to the invention, mention may be made of the branched block anionic polymer so ld under the name Fixate G- 100 by the company Lubrizo l.

According to the invention, the anionic fixing polymers are preferably chosen from copolymers of acrylic acid or of acrylic esters, such as the acrylic acid/ethyl acrylate/N-tert-butylacrylamide terpolymers sold especially under the name Ultrahold^® Strong by the company BASF, copo lymers derived from crotonic acid, such as vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and the crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold especially under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives and acrylic acid and esters thereof, such as the methyl vinyl ether/monoesterified maleic anhydride copolymers sold, for example, under the name Gantrez^® by the company ISP, the copolymers of methacrylic acid and o f methyl methacrylate so ld under the name Eudragit^® L by the company Rohm Pharma, the copo lymers o f methacrylic acid and of ethyl acrylate sold under the name Luvimer^® MAEX or MAE by the company BASF, the vinyl acetate/crotonic acid copolymers sold under the name Luviset CA 66 by the company BASF, the vinyl acetate/crotonic acid copolymers grafted with polyethylene glyco l so ld under the name Aristo flex^® A by the company BASF, and the polymer so ld under the name Fixate G- 100 L by the company Lubrizo l.

The cationic fixing film-forming polymers that can be used according to the present invention are preferably chosen from po lymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the polymer chain or directly attached thereto, and having a mo lecular weight of between 500 and about 5 000 000 and preferably between 1 000 and 3 000 000.

Among these polymers, mention may be made more particularly of the fo llowing cationic po lymers :

( 1 ) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units o f the fo llowing formulae :

in which:

P 3 denotes a hydrogen atom or a CH₃ radical;

A is a linear or branched alkyl group comprising 1 to 6 carbon atoms or a hydroxyalkyl group comprising 1 to 4 carbon atoms;

R₄, R₅ and R₆, which may be identical or different, represent an alkyl group having from 1 to 1 8 carbon atoms or a benzyl radical;

Ri and R₂, which may be identical or different, each represent a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms;

X denotes a methosulphate anion or a halide such as chloride or bromide.

The copolymers o f the family ( 1 ) also contain one or more units derived from comonomers that may be chosen from the family o f acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (C _{1 -4}) alkyl groups, groups derived from acrylic or methacrylic acids or esters thereo f, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

Thus, among these copolymers of the family ( 1 ), mention may be made o f:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulphate or with a dimethyl halide, such as the product sold under the name Herco flo c® by the company Hercules,

copolymers of acrylamide and of methacryloyl- oxyethyltrimethylammonium chloride, described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 1 00 by the company Ciba Geigy,

copolymers of acrylamide and of methacryloyl- oxyethyltrimethylammonium methosulphate, such as the product 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 alternatively the products known as Copolymer® 845 , 958 and 937. These polymers are described in detail in French patents 2 077 143 and 2 393 573 ,

- fatty-chain po lymers containing a vinylpyrrolidone unit, such as the products sold under the name Styleze W20 and Styleze W 10 by the company ISP,

dimethylamino ethyl methacrylate/vinylcaprolactam/vinyl- pyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP, and

quaternized vinylpyrrolidone/dimethylaminopropyl- methacrylamide copolymers, such as the products sold under the name Gafquat® HS 100 by the company ISP;

(2) non-cellulosic cationic po lysaccharides, preferably containing quaternary ammonium, such as those described in US patents 3 589 578 and 4 03 1 307 , such as guar gums containing trialkylammonium cationic groups . Such products are sold in particular under the trade names Jaguar C 13 S , Jaguar C 15 and Jaguar C 17 by the company Meyhall.

(3) Quaternary copolymers of vinylpyrrolidone and of vinylimidazole.

(4) Chitosans or salts thereof; the salts that can be used are, in particular, chitosan acetate, lactate, glutamate, gluconate or pyrrolidonecarboxylate.

Among these compounds, mention may be made o f chitosan having a degree of deacetylation o f 90.5 % by weight, sold under the name Kytan Brut Standard by the company Aber Techno logies, and chitosan pyrrolidonecarboxylate sold under the name Kytamer® PC by the company Amercho l.

(5) Cationic cellulose derivatives such as copolymers of cellulo se or of cellulo se derivatives grafted with a water-so luble monomer comprising a quaternary ammonium, and disclo sed in particular in patent US 4 13 1 576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcellulo ses grafted in particular with a methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The products sold corresponding to this definition are, more particularly, the products sold under the name Celquat L 200 and Celquat H 100 by the company National Starch.

The amphoteric fixing that can be used in accordance with the invention can be selected from polymers comprising units B and C distributed randomly in the polymer chain, where B denotes a unit derived from a monomer comprising at least one basic nitrogen atom and C denotes a unit derived from an acid monomer comprising one or more carboxylic or sulphonic groups, or alternatively B and C can denote groups derived from carboxybetaine or sulphobetaine zwitterionic monomers;

B and C can also denote a cationic po lymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulphonic group connected via a hydrocarbon group or alternatively B and C form part of a chain o f a po lymer containing an (Χ, β-dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups .

The amphoteric fixing corresponding to the definition given above that are more particularly preferred are selected from the fo llowing polymers :

( 1 ) copolymers having acidic vinyl units and basic vinyl units, such as those resulting from the copolymerization of a monomer derived from a vinyl compound bearing a carboxylic group such as, more particularly, acrylic acid, methacrylic acid, maleic acid, a-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamides and acrylamides . Such compounds are described in patent US 3 836 537.

(2) Polymers comprising units derived from:

a) at least one monomer selected from acrylamides and methacrylamides substituted on the nitrogen atom by an alkyl group, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and

c) at least one basic comonomer such as esters containing primary, secondary, tertiary and quaternary amine substituents of acrylic and methacrylic acids and the product of quaternization o f dimethylaminoethyl methacrylate with dimethyl or diethyl sulphate.

The N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are compounds in which the alkyl groups contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butylacrylamide, N-tert- octylacrylamide, N-octylacrylamide, N-decylacrylamide, N- dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, of maleic or fumaric acids or anhydrides.

The preferred basic comonomers are amino ethyl, butylamino ethyl, Ν,Ν ' -dimethylaminoethyl and N-tert-butylamino-ethyl methacrylates.

Use is made particularly o f the copolymers whose CTFA (4th edition, 1991 ) name is octylacrylamide/acrylates/butylamino ethyl methacrylate copolymer, such as the products sold under the name Amphomer^® or Lovocryl^® 47 by the company National Starch.

(3) Crosslinked and acylated polyaminoamides partially or totally deriving from polyaminoamides of general formula: {- CO R₁₀— CO— Z— } (IX) in which R_{1 0} represents a divalent group derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid containing an ethylenic double bond, an ester of a lower alkano l, having 1 to 6 carbon atoms, of these acids, or a group derived from the addition of any one of said acids to a bis(primary) or bis(secondary) amine, and Z denotes a group derived from a bis(primary), mono- or bis(secondary) polyalkylene-polyamine and preferably represents :

a) in proportions o f from 60 to 100 mo l%, the group :

N (CH₂)_X N

H L 2 x H— I— p (X) where x = 2 and p = 2 or 3 , or alternatively x = 3 and p = 2 this group being derived from diethylenetriamine, from triethylenetetraamine or from dipropylenetriamine;

b) in proportions o f from 0 to 40 mo l%, the group (X) above in which x = 2 and p = 1 and which is derived from ethylenediamine, or the group derived from piperazine :

/ \

N N

\ /

c) in proportions of from 0 to 20 mol%, the -NH-(CH₂)₆-NH- group being derived from hexamethylenediamine,

these polyamino amides being crosslinked by addition reaction o f a difunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives, using from 0.025 to 0.35 mo l o f crosslinking agent per amine group of the polyamino amide and acylated by the action of acrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.

The saturated carboxylic acids are preferably selected from acids having 6 to 1 0 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid, acids containing an ethylenic double bond such as, for example, acrylic acid, methacrylic acid and itaconic acid.

The alkane sultones used in the acylation are preferably propane sultone or butane sultone; the salts o f the acylating agents are preferably the sodium or potassium salts.

(4) Polymers comprising zwitterionic units of formula:

in which Rn denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3 , R12 and R13 represent a hydrogen atom, a methyl, ethyl or propyl group, R14 and R1 5 represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R14 and R1 5 does not exceed 10.

The po lymers comprising such units can also comprise units derived from non-zwitterionic monomers such as dimethyl- or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

By way of example, mention may be made o f the copolymers o f methyl methacrylate/methyl dimethylcarboxymethylammonio ethyl methacrylate such as the product sold under the name Diaformer Z301 by the company Sandoz.

(5) Polymers derived from chitosan comprising monomer units corresponding to the following formulae :

the unit (D) being present in proportions of between 0 and 30%, the unit (E) in proportions of between 5% and 50% and the unit (F) in proportions of between 30%> and 90%>, it being understood that, in this unit (F), Ri6 represents a group of formula:

in which, if q=0, R17, Ris and R19, which are identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue that are optionally interrupted by one or more nitrogen atoms and/or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio or sulphonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the groups R17, Ris and R19 being, in this case, a hydrogen atom;

or, if q=l, R17, Ris and R19 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) Polymers with units corresponding to the general formula (XII) are described, for example, in French patent 1 400 366: †20

(CH

COOH CO

1 (XII)

N-R₂₁

N-R.3

¾2

in which R₂o represents a hydrogen atom, a CH₃0, CH₃CH₂0 or phenyl group, R₂i denotes a hydrogen atom or a lower alkyl group such as methyl or ethyl, R₂₂ denotes a hydrogen atom or a Ci-C₆ lower alkyl group such as methyl or ethyl, R₂₃ denotes a Ci-C₆ lower alkyl group such as methyl or ethyl or a group corresponding to the formula: -R₂₄- N(R₂₂)₂, R₂₄ representing a -CH₂-CH₂- , -CH₂-CH₂-CH₂- or -CH₂- CH(CH₃)- group, and R₂₂ having the abovementioned meanings.

(7) Polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name "Evalsan" by the company Jan Dekker.

(8) Amphoteric polymers of the type -D-X-D-X chosen from: a) Polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula:

-D-X-D-X-D- (ΧΙΠ)

where D denotes a group

/ \

N N

\ /

and X denotes the symbol E or E', E or E', which may be identical or different, denote a divalent group that is an alkylene group with a straight or branched chain containing up to 7 carbon atoms in the main chain, which is unsubstituted or substituted by hydroxyl groups and which can comprise, in addition to the oxygen, nitrogen and sulphur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulphur atoms being present in the form o f ether, thioether, sulphoxide, sulphone, sulphonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups.

b) Po lymers of formula:

-D-X-D-X- (XIV)

where D denotes a group

/ \

N N

\ /

and X denotes the symbol E or E ' and at least once E ' ; E having the meaning given above and E ' is a divalent group that is an alkylene group with a straight or branched chain having up to 7 carbon atoms in the main chain, which is unsubstituted or substituted with one or more hydroxyl groups and containing one or more nitrogen atoms, the nitrogen atom being substituted with an alkyl chain that is optionally interrupted by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betainized by reaction with chloroacetic acid or sodium chloroacetate.

(9) (Ci -C₅)alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an N,N- dialkylaminoalkylamine such as Ν,Ν-dimethylaminopropylamine or by semiesterification with an Ν,Ν-dialkylaminoalkanol. These copolymers can also comprise other vinyl comonomers such as vinylcapro lactam.

Among the amphoteric fixing po lymers mentioned above, the ones that are most particularly preferred according to the invention are those of family (3), such as the copo lymers whose CTFA name is octylacrylamide/acrylates/butylamino ethyl methacrylate copolymer, such as the products sold under the names Amphomer^®, Amphomer^® LV 71 or Lovocryl 47 by the company National Starch and those of family (4) such as the methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate copolymers, sold, for example, under the name Diaformer Z301 by the company Sandoz.

The nonionic fixing that may be used according to the present invention are selected, for example, from:

- polyalkyloxazo lines;

- vinyl acetate homopolymers;

- vinyl acetate copolymers, for instance copolymers of vinyl acetate and of acrylic ester; copolymers of vinyl acetate and of ethylene, or copolymers of vinyl acetate and of maleic ester, for example o f dibutyl maleate;

- homopolymers and copolymers of acrylic esters, for instance copolymers of alkyl acrylates and of alkyl methacrylates, such as the products sold by the company Rohm & Haas under the names Primal^® AC-261 K and Eudragit^® NE 30 D , by the company BASF under the name 8845 , or by the company Hoechst under the name Appretan^® N92 12;

- acrylonitrile copolymers and copolymers of a nonionic monomer selected, for example, from butadiene and alkyl

(meth)acrylates; mention may be made of the products so ld under the name CJ 0601 B by the company Rohm & Haas;

- styrene homopolymers;

- styrene copolymers, for instance copolymers o f styrene and o f an alkyl (meth)acrylate, such as the products Mowilith^® LDM 69 1 1 ,

Mowilith^® DM 61 1 and Mowilith^® LDM 6070 so ld by the company Hoechst, and the products Rhodopas^® SD 215 and Rhodopas^® D S 91 0 so ld by the company Rhone-Poulenc; copolymers of styrene, of alkyl methacrylate and o f alkyl acrylate; copolymers of styrene and of butadiene; or copolymers of styrene, of butadiene and of vinylpyridine;

- polyamides;

vinyllactam homopolymers such as vinylpyrrolidone homopolymers and such as the polyvinylcaprolactam so ld under the name Luvisko l^® Plus by the company BASF; and

vinyllactam copolymers such as a poly(vinylpyrrolidone/vinyllactam) copolymer sold under the trade name Luvitec^® VPC 55K65W by the company BASF, poly(vinylpyrrolidone/vinyl acetate) copolymers, such as those sold under the name PVPVA^® S630L by the company ISP, Luviskol^® VA 73 , VA 64, VA 55 , VA 37 and VA 28 by the company BASF; and poly(vinylpyrrolidone/vinyl acetate/vinyl propionate) terpolymers, for instance the product sold under the name Luviskol^® VAP 343 by the company BASF .

The alkyl groups of the nonionic po lymers mentioned above preferably have from 1 to 6 carbon atoms.

According to the invention, it is also possible to use fixing polymers o f grafted silicone type comprising a po lysiloxane portion and a portion consisting o f a non-silicone organic chain, one of the two portions constituting the main chain o f the po lymer, and the other being grafted onto said main chain.

These polymers are described, for example, in patent applications EP-A-0 4 12 704, EP-A-0 4 12 707, EP-A-0 640 105 and WO 95/00578 , EP-A-0 582 1 52 and WO 93/23009 and patents US 4 693 935 , US 4 728 571 and US 4 972 037.

These po lymers may be amphoteric, anionic or nonionic, and are preferably anionic or nonionic.

Such polymers are, for example, copolymers that can be obtained by free radical po lymerization from the monomer mixture formed from: a) 50 to 90 % by weight of tert-butyl acrylate;

b) 0 to 40 % by weight of acrylic acid;

c) 5 to 40 % by weight of a silicone macromer of formula:

in which v is a number ranging from 5 to 700, the weight percentages being calculated relative to the total weight of the monomers.

Other examples of grafted silicone polymers are, in particular, polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, mixed po lymer units o f the poly(meth)acrylic acid type and o f the po lyalkyl (meth)acrylate type and polydimethylsiloxanes (PDMSs) onto which are grafted, via a thiopropylene-type connecting chain, polymer units of the po lyisobutyl (meth)acrylate type.

Another type o f silicone fixing po lymer that may be mentioned is the product Luviflex^® Silk so ld by the company BASF .

As fixing it is also possible to use functionalized or non- functionalized, cationic, nonionic, anionic or amphoteric, silicone or non-silicone po lyurethanes, or mixtures thereof.

The po lyurethanes particularly intended by the present invention are those disclosed in patent applications EP 0 75 1 162 , EP 0 637 600, EP 0 648 485 and FR 2 743 297, of which the Applicant is the Proprietor, and patent applications EP 0 656 021 and WO 94/035 1 0 from the company BASF and EP 0 619 1 1 1 from the company National Starch.

As po lyurethanes that are particularly suitable for the present invention, mention may be made of the products sold under the names Luviset Pur^® and Luviset^® Si Pur by the company BASF .

The concentration o f fixing po lymer(s) used in the compositions according to the present invention is between 0. 1 % and 20% and preferably between 0.5 % and 10% by weight relative to the total weight of the composition.

A person skilled in the art should know how to add the additives without disturbing the properties of the compositions of the invention.

Preferably, the compositions are in the form o f gels. Preferably, the compositions have a viscosity greater than 500 cps at a temperature of 25 °C and at a shear rate of 1 s^{" 1} .

When the composition according to the invention is packaged in an aerosol device, it comprises at least one propellant, which may be chosen from vo latile hydrocarbons, such as N-butane, propane, isobutane, pentane, halogenated hydrocarbons and mixtures thereof. It is also possible to use carbon dioxide, nitrous oxide, dimethyl ether (DME), nitrogen or compressed air as the propellant. Mixtures o f propellants can also be used. Preferably, dimethyl ether is used.

Advantageously, the propellant is present at a concentration between 5 and 90% by weight relative to the total weight of the composition in the aeroso l device and, more particularly, at a concentration between 10 and 60% .

The composition according to the invention may especially be used as a leave-in application on the hair.

Another subj ect of the invention is a method for shaping the hair, comprising the application o f a cosmetic composition according to the invention. In particular, the invention relates to a styling method comprising the application o f a composition according to the invention to the hair, optional rinsing of the hair, then the shaping and drying o f the hair.

The examp les that fo llow illustrate the invention without limiting the scope thereof. Examples

The fo llowing compositions were produced:

The concentrations are expressed as grams of active material per 100 g of composition.

Examples of formulations (Styling mousses):

These compositions are easily distributed over the hair and fix said hair with good shape retention.

Claims

1 . Cosmetic composition characterized in that it comprises, in a cosmetically acceptable medium:

(i) one or more branched sulphonic po lyesters; and

(ii) one or more po lyvinyl alcoho ls.

2. Cosmetic composition according to Claim 1 , in which the branched sulphonic polyester is obtained by po lycondensation o f:

(a) at least one dicarboxylic acid that does not bear a sulphonic functional group,

(b) at least one dio l or a mixture o f a dio l and of a diamine, (c) at least one monomer comprising two identical or different reactive functional groups chosen from hydroxyl, amino and carboxyl groups, and that bears, in addition, at least one sulphonic functional group, and

(d) at least one monomer comprising at least three identical or different reactive functional groups chosen from hydroxyl, amino and carboxyl groups.

3. Cosmetic composition according to Claim 2, in which the branched sulphonic polyester comprises units (e) derived from monomers comprising two different reactive functional groups chosen from hydroxy carboxylic acids and amino carboxylic acids or mixtures thereo f .

4. Cosmetic composition according to any one of the preceding claims, comprising from 0.2 to 15 %, preferably from 0.5 to 1 0% by weight of one or more branched sulphonic polyesters relative to the total weight of the composition.

5. Cosmetic composition according to any one of the preceding claims in which the po lyvinyl alcoho l or alcoho ls are chosen from homopolymers or copolymers.

6. Cosmetic composition according to the preceding claim, in which the copolymer or copolymers are copolymers with vinyl acetate.

7. Cosmetic composition according to any one of the preceding claims, comprising from 0.05 to 20%, preferably from 0. 1 to 10% by weight of one or more polyvinyl alcohols relative to the total weight of the composition.

8. Cosmetic composition according to any one of the preceding claims, comprising one or more surfactants chosen from anionic, nonionic, amphoteric or cationic surfactants .

9. Cosmetic composition according to any one of the preceding claims, comprising one or more gelling agents and/or additional thickeners chosen from poly(oxyalkylene) glycols, poly(oxyalkylene) glyco l esters, alginates, bio saccharides, starch derivatives, natural gums such as xanthan gum, guar gum, carob bean gum, scleroglucans, derivatives o f chitin and o f chitosan, carrageenans, clays, and mixtures thereo f.

10. Cosmetic composition according to any one of the preceding claims, comprising one or more compounds chosen from silicones and non-silicone fatty substances chosen from mineral, plant, animal and synthetic oils, waxes, fatty esters, ethoxylated or non- ethoxylated fatty alcoho ls, and fatty acids .

1 1 . Cosmetic composition according to any one of the preceding claims, comprising one or more fixing polymers chosen from anionic, nonionic, amphoteric or cationic fixing polymers .

12. Use o f the cosmetic composition according to any one o f the preceding claims, for styling, especially for styling or shaping keratin materials, preferably human keratin materials and in particular the hair.

13. Styling method that comprises the application of a composition according to any one o f Claims 1 to 1 1 to the hair, optional rinsing of the hair, then shaping and drying of the hair.