WO2014111579A2

WO2014111579A2 - Hair shaping process in which is applied a particular styling composition, which is rinsed out

Info

Publication number: WO2014111579A2
Application number: PCT/EP2014/051045
Authority: WO
Inventors: Valérie Favreau; Xavier JOSEPH
Original assignee: L'oreal
Priority date: 2013-01-18
Filing date: 2014-01-20
Publication date: 2014-07-24
Also published as: FR3001149A1; FR3001149B1; WO2014111579A3; EP2945598A2

Abstract

The present invention relates to a hair shaping process in which: - a styling composition comprising one or more organic solvents and one or more fixing polymers is applied to hair, the fixing polymer(s) being at least partially soluble in the styling composition and being capable of precipitating on the hair when the styling composition is diluted with an aqueous composition, and then - the hair is rinsed with the aqueous composition so as to precipitate the fixing polymer on the hair.

Description

HAIR SHAPING PROCESS IN WHICH IS APPLIED A PARTICULAR STYLING COMPOSITION, WHICH IS RINSED OUT

The present invention relates to a hair shaping process in which is applied a particular styling composition, which is rinsed out with an aqueous composition, and also to a kit comprising the compositions used in the process.

In the field of hair styling, in particular among hair products intended for shaping and/or holding the hairstyle, hair compositions are generally provided in the form of hair gels, lotions, foams or sprays. Documents FR 2 729 563, EP 754 026, EP 1 532 966 and EP 1 629 827 describe, for example, hair styling compositions.

They are generally applied to wet hair, in particular after it has been washed and superficially dried, for example after a shower and superficial drying. The use of these compositions requires an application time additional to the time spent under the shower.

Moreover, styling compositions generally leave, after hair styling, a tactile feeling of residual products in the hands, in particular a phenomenon of residual tackiness which remains on the hands, which requires that the hands be washed after the application of these compositions. Residual tackiness may also remain on the hair.

There is thus a real need to find a novel styling action which allows rapid styling and a good level of fixing and hold of the hairstyle, while retaining a clean and non- tacky feel of the hair.

One subject of the present invention is thus especially a hair shaping process in which:

- a styling composition comprising one or more organic solvents and one or more fixing polymers is applied to hair, preferably wet hair, the fixing polymer(s) being at least partially soluble in the styling composition and being capable of precipitating on the hair when the styling composition is diluted with an aqueous composition, and then

- the hair is rinsed with the aqueous composition so as to precipitate the fixing polymer on the hair.

The hair shaping process allows quick and easy styling. This process also makes it possible to obtain a good level of fixing, long-lasting hairstyle hold and a clean, non- tacky feel of the hair, with little or no residues. The process according to the invention in particular makes it possible to use the styling composition directly in the shower.

According to another of its aspects, the present invention relates to a kit comprising:

- a washing composition comprising one or more surfactants; and/or

- a care composition comprising at least one conditioning agent, and - a styling composition comprising one or more organic solvents and one or more fixing polymers, the fixing polymer(s) being at least partially soluble in the styling composition and being capable of precipitating on the hair when the styling composition is diluted with an aqueous composition.

The expression "at least one" is equivalent to the expression "one or more". Styling composition The term "styling composition" is understood to mean a composition which makes it possible to give a shape to a head of hair and/or to retain the acquired shape of the head of hair.

Fixing polymer

The styling composition according to the invention comprises at least one fixing polymer.

For the purposes of the invention, the term "fixing polymer" is understood to mean any polymer that is capable, by application to the hair, of giving a shape to the head of hair or of making it possible to retain an already acquired shape.

The fixing polymer(s) used are chosen from ionic, especially anionic, cationic or amphoteric, and nonionic fixing polymers, and mixtures thereof.

Anionic polymers that may be mentioned include polymers comprising groups derived from carboxylic acids, sulfonic acids or phosphoric acids, and having a number-average molecular mass of between 500 and 5 000 000.

The carboxylic groups are provided by unsaturated monocarboxylic or dicarboxylic acid monomers 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 to the neighbouring methylene group when n is greater than 1 via a heteroatom such as oxygen or sulfur, R-i denotes a hydrogen atom or a phenyl or benzyl group, R₂ denotes a hydrogen atom, an alkyl group comprising from 1 to 4 carbon atoms or a carboxyl group, and R₃ denotes a hydrogen atom, an alkyl group comprising from 1 to 4 carbon atoms or a -CH₂-COOH, phenyl or benzyl group.

In formula (I) above, the alkyl group comprising from 1 to 4 carbon atoms may in particular denote methyl and ethyl groups.

The anionic fixing polymers containing carboxylic or sulfonic groups that are preferred are:

A) Copolymers of acrylic or methacrylic acid or salts thereof, including copolymers of acrylic acid and of acrylamide and methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers, in particular Amerhold DR 25 sold by the company Amerchol, and the sodium salts of polyhydroxycarboxylic acids. Mention may also be made of methacrylic acid/ethyl acrylate copolymers, especially in aqueous dispersion, such as Luviflex Soft and Luvimer MAE sold by the company BASF;

B) Copolymers of acrylic or methacrylic acids with a monoethylenic monomer such as ethylene, styrene, vinyl esters and acrylic or methacrylic acid esters, optionally grafted onto a polyalkylene glycol such as polyethylene glycol and optionally crosslinked. Such polymers are described in particular in French patent 1 222 944 and German 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 especially in Luxembourg patent applications 75370 and 75371 . Mention may also be made of copolymers of acrylic acid and of a Ci-C₄ alkyl methacrylate.

As another anionic fixing polymer of this family, mention may also be made of the butyl acrylate/acrylic acid/methacrylic acid branched block anionic polymer sold under the name Fixate G-100 L by the company Lubrizol (I NCI name: AMP-acylates/allyl methacrylate copolymer).

C) Crotonic acid-based copolymers, such as those comprising in their chain vinyl acetate or propionate units and optionally other monomers such as allylic or methallylic esters, vinyl ether or vinyl ester of a saturated, linear or branched carboxylic acid containing a long hydrocarbon-based chain such as those comprising at least 5 carbon atoms, these polymers possibly being grafted and crosslinked, or alternatively a vinyl, allylic or methallylic ester of an a- or β-cyclic carboxylic acid. Such polymers are described, inter alia, in French patents 1 222 944, 1 580 545, 2 265 782, 2 265 781 , 1 564 1 10 and 2 439 798. Commercial products that fall within this category are the resins 28-29-30, 26-13-14 and 28-13-10 sold by the company National Starch.

Crotonic acid-based copolymers that may also be mentioned include crotonic acid/vinyl acetate/vinyl tert-butylbenzoate terpolymers and in particular Mexomer PW supplied by the company Chimex. D) Polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives or acrylic acid and esters thereof; these polymers may be esterified. 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, and especially those sold under the names Gantrez® AN or ES by the company ISP.

Polymers also falling within this category are the copolymers of maleic, citraconic or itaconic anhydrides and of an allylic or methallylic ester optionally comprising an acrylamide or methacrylamide group, an a-olefin, acrylic or methacrylic esters, acrylic or methacrylic acids or vinylpyrrolidone in their chain, the anhydride functions 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) Polymers comprising sulfonic groups. These polymers may be polymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic, acrylamidoalkylsulfonic or sulfoisophthalate units.

These polymers can be chosen in particular from:

- polyvinylsulfonic acid salts with a molecular mass of between about 1000 and 100 000, and also copolymers with an unsaturated comonomer such as acrylic or methacrylic acids and esters thereof, and also acrylamide or derivatives thereof, vinyl ethers and vinylpyrrolidone;

- polystyrenesulfonic acid salts, sodium salts, with a molecular mass of about 500 000 and of about 100 000. These compounds are described in patent FR 2 198 719;

- polyacrylamidesulfonic acid salts such as those mentioned in patent US 4 128 631 .

G) Grafted anionic silicone polymers.

The grafted silicone polymers used are preferably chosen from polymers containing a non-silicone organic backbone grafted with monomers containing a polysiloxane, polymers containing a polysiloxane backbone grafted with non-silicone organic monomers, and mixtures thereof.

H) Anionic polyurethanes, which may comprise silicone grafts and silicones bearing hydrocarbon-based grafts.

Examples of fixing polyurethanes that may especially be mentioned include the dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols copolymer (also known under the name polyurethane-1 , INCI name) sold under the brand name Luviset® Pur by the company BASF, and the dimethylolpropionic acid/isophorone diisocyanate/neopentyl glycol/polyester diols/silicone diamine copolymer (also known under the name polyurethane-6, INCI name) sold under the brand name Luviset® Si PUR A by the company BASF.

Another anionic polyurethane that may also be used is Avalure UR 450.

Polymers containing sulfoisophthalate groups, such as the polymers AQ55 and

AQ48 sold by the company Eastman, may also be used.

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, and methacrylic acid/ethyl acrylate copolymers, especially in aqueous dispersion, such as Luviflex Soft and Luvimer MAE sold by the company BASF. Crotonic acid-based copolymers such as vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers sold under the name Resin 28-29-30 by the company National Starch, polymers derived from maleic, fumaric or itaconic acids or anhydrides with vinyl esters, vinyl ethers, vinyl halides or phenylvinyl derivatives, acrylic acid and esters thereof, such as the methyl vinyl ether/monoesterified maleic anhydride copolymer sold under the name Gantrez® ES 425 by the company ISP, Luviset Si Pur, Mexomer PW, elastomeric or non-elastomeric anionic polyurethanes, and polymers containing sulfoisophthalate groups.

The cationic fixing polymers that can be used according to the present invention are preferably chosen from polymers comprising primary, secondary, tertiary and/or quaternary amine groups forming part of the polymer chain or directly attached thereto, and having a molecular weight of between 500 and approximately 5 000 000 and preferably between 1000 and 3 000 000.

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

(1 ) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulae: R, R,

-

in which:

R₃ denotes a hydrogen atom or a CH₃ group;

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

R₄, R₅ and R₆, which are identical or different, represent an alkyl group containing from 1 to 18 carbon atoms or a benzyl group;

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

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

The copolymers of family (1 ) also contain one or more units deriving from comonomers that may be chosen from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides which are substituted on the nitrogen with C1-C4 alkyl groups, groups derived from acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters.

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

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

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, described, for example, in patent application EP-A-080 976 and sold under the name Bina Quat P 100 by the company Ciba Geigy,

- the copolymer of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, 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 polymers containing a vinylpyrrolidone unit, such as the products sold under the name Styleze W20 and Styleze W10 by the company ISP,

- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP, and

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

(2) cationic guar gums, preferably containing quaternary ammonium, such as those described in US patents 3 589 578 and 4 031 307, such as guar gums containing trialkylammonium cationic groups. Such products are sold in particular under the trade names Jaguar C13 S, Jaguar C 15 and Jaguar C 17 by 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.

These compounds include the chitosan having a degree of deacetylation of 90.5% by weight which is sold under the name Kytan Brut Standard by the company Aber Technologies, and the chitosan pyrrolidone carboxylate which is sold under the name Kytamer® PC by the company Amerchol;

(5) cationic cellulose derivatives such as copolymers of cellulose or of cellulose derivatives grafted with a water-soluble monomer comprising a quaternary ammonium, and described in particular in patent US 4 131 576, such as hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted in particular with a methacryloyloxyethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.

The commercial products 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 polymers that can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed randomly in the polymer chain, in which 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 sulfonic groups, or alternatively B and C can denote groups derived from carboxybetaine or sulfobetaine zwitterionic monomers; B and C can also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups bears a carboxylic or sulfonic group connected via a hydrocarbon group or alternatively B and C form part of a chain of a polymer containing an ethylenedicarboxylic 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 polymers corresponding to the definition given above that are more particularly preferred are chosen from the following polymers:

(1 ) polymers 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, ochloroacrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom, such as, more particularly, dialkylaminoalkyl methacrylates and acrylates, dialkylaminoalkylmethacrylamides and -acrylamides. Such compounds are described in US patent No. 3 836 537.

The vinyl compound may also be a dialkyldiallylammonium salt such as diethyldiallylammonium chloride.

(2) polymers comprising units deriving from:

a) at least one monomer chosen from acrylamides and methacrylamides substituted on the nitrogen with 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 acrylic and methacrylic acid esters containing primary, secondary, tertiary and quaternary amine substituents, and the product of quaternization of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides that are more particularly preferred according to the invention are groups 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 aminoethyl, butylaminoethyl, N,N'-dimethylaminoethyl and N-ie f-butylaminoethyl methacrylates. The copolymers whose CTFA (4th edition, 1991 ) name is Octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the name Amphomer® or Lovocryl® 47 by the company National Starch, are particularly used. (3) crosslinked and alkylated polyamino amides partially or totally derived from polyamino amides of general formula:

-CO- ₄-CO- (II)

in which R₄ represents a divalent group derived from a saturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acid bearing an ethylenic double bond, an ester of an alcohol containing 1 to 6 carbon atoms, of these acids, or a group derived from the addition of any one of the said acids to a bis(primary) amine or bis(secondary) derivative, and Z denotes a group derived from a bis(primary), mono- or bis(secondary) polyalkylene polyamine and preferably represents:

a) in proportions of from 60 to 100 mol%, the group:

^■NH- -(CH₂)_x- ^■NH-

(III) where x = 2 and p = 2 or 3, or alternatively x = 3 and p = 2

this group being derived from diethylenetriamine, triethylenetetramine or dipropylenetriamine;

b) in proportions of from 0 to 40 mol%, the group (III) 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 derived from hexamethylenediamine, these polyamino amines being crosslinked by addition of a difunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides and bis-unsaturated derivatives, using from 0.025 to 0.35 mol of crosslinking agent per amine group of the polyamino amide and alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.

The saturated carboxylic acids are preferably chosen from acids having 6 to 10 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 alkylation are preferably propane sultone or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

(4) polymers comprising zwitterionic units of formula:

in which R₅ 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, R₆ and R₇ represent a hydrogen atom, a methyl, ethyl or propyl group, R₈ and R₉ represent a hydrogen atom or an alkyl group such that the sum of the carbon atoms in R₁₀ and Rn does not exceed 10.

The polymers 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.

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

(V) (VI) (VII) the unit (V) being present in proportions of between 0 and 30%, the unit (VI) in proportions of between 5% and 50% and the unit (VII) in proportions of between 30% and 90%, it being understood that, in this unit (VII), R₁₀ represents a group of formula:

in which, if q = 0, Rn , Ri₂ and Ri₃, which may be 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 with one or more amine, hydroxyl, carboxyl, alkylthio or sulfonic groups, an alkylthio residue in which the alkyl group bears an amino residue, at least one of the groups Ri₇, Ri₈ and Ri₉ being, in this case, a hydrogen atom;

or, if q = 1 , Rn , R₁₂ and Ri₃ each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

(6) polymers derived from the N-carboxyalkylation of chitosan.

(7) polymers of units corresponding to the general formula (IX) described, for example, in French patent 1 400 366:

(IX) in which R₁₄ represents a hydrogen atom, a CH₃0, CH₃CH₂0 or phenyl group, R-I5 denotes a hydrogen atom or a Ci_-4 alkyl group such as methyl or ethyl, R₁₆ denotes a hydrogen atom or a Ci_-4 alkyl group such as methyl or ethyl, R₁₇ denotes a Ci_-4 alkyl group such as methyl or ethyl or a group corresponding to the formula: -Ri₈-N(Ri₆)₂, Ri₈ representing a -CH₂-CH₂-, -CH₂-CH₂-CH₂- or -CH₂-CH(CH₃)- group, R_i6 having the meanings mentioned above, and also the higher homologues of these groups, containing up to 6 carbon atoms.

(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- (X)

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 with hydroxyl groups and which can comprise, in addition, oxygen, nitrogen and sulfur atoms and 1 to 3 aromatic and/or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups, hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and/or urethane groups.

b) Polymers of formula:

-D-X-D-X- (XI)

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) (CrC₅)alkyl vinyl ether/maleic anhydride copolymers partially modified by semiamidation with an Ν,Ν-dialkylaminoalkylamine such as N,N- dimethylaminopropylamine or by semiesterification with an Ν,Ν-dialkanolamine. These copolymers can also comprise other vinyl comonomers such as vinylcaprolactam.

According to one preferred embodiment of the invention, the amphoteric fixing polymers that may be used in the aerosol device according to the invention may be chosen from branched block copolymers comprising:

(a) nonionic units derived from at least one monomer chosen from CrC₂o alkyi (meth)acrylates, N-mono(C₂-Ci₂ alkyl)(meth)acrylamides and N,N-di(C₂-Ci₂ alkyl)(meth)acrylamides,

(b) anionic units derived from at least one monomer chosen from acrylic acid and methacrylic acid, and

(c) polyfunctional units derived from at least one monomer comprising at least two polymerizable unsaturated functional groups,

and preferably having a structure consisting of hydrophobic blocks onto which are fixed, via polyfunctional units (c), a number of more hydrophilic blocks.

Preferably, the amphoteric polymers have at least two glass transition temperatures (Tg), at least one of which is greater than 20°C and the other is less than 20°C.

The preferred amphoteric polymers are polymers comprising units derived from: a) at least one monomer chosen from acrylamides and methacrylamides substituted on the nitrogen with an alkyi group,

Mention may be made in particular of the polymers sold under the name Amphomer by the company National Starch.

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

- polyalkyloxazolines;

- vinyl acetate homopolymers;

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

- homopolymers and copolymers of acrylic esters, for instance copolymers of alkyi acrylates and of alkyi 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^® N9212,

- copolymers of acrylonitrile and a nonionic monomer chosen, for example, from butadiene and alkyi (meth)acrylates, such as the products provided under the name

CJ 0601 B by Rohm & Haas,

- styrene homopolymers;

- styrene copolymers, for instance copolymers of styrene and of an alkyi (meth)acrylate, such as the products Mowilith^® LDM 691 1 , Mowilith^® DM 61 1 and Mowilith^® LDM 6070 sold by the company Hoechst, and the products Rhodopas^® SD 215 and Rhodopas^® DS 910 sold by the company Rhone-Poulenc, copolymers of styrene, of alkyi methacrylate and of alkyi 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 sold under the name Luviskol^® Plus by the company BASF,

- 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, and

- polyvinyl alcohols).

The alkyi groups of the nonionic polymers mentioned above preferably have from

1 to 6 carbon atoms.

Preferably, the fixing polymer is an ionic fixing polymer, preferably an anionic fixing polymer.

More preferably, the fixing polymer is chosen from crotonic acid copolymers.

More preferably, the fixing polymer is chosen from crotonic acid copolymers comprising, in their chain, vinyl acetate or propionate units and optionally other monomers, such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid comprising a long hydrocarbon chain.

Even more preferably, the anionic fixing polymer is a vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer. The fixing polymer is at least partially soluble in the styling composition.

Preferably, the fixing polymer of the invention is soluble in the styling composition at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg; i.e. 1.013 * 10⁵ Pa) at a weight concentration of greater than or equal to 1 %.

Preferably, the fixing polymer of the invention is soluble in the organic solvent(s) at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg; i.e. 1.013 * 10⁵ Pa) at a weight concentration of greater than or equal to 5%. For the purpose of the invention, a "fixing polymer capable of precipitating on the hair when the styling composition is diluted with an aqueous composition", is a fixing polymer which solubility in water and at spontaneous pH is less than 0,1. When the fixing polymer is a fixing polymer having an anionic group, the fixing polymer has a degree of neutralization less than 20% in the composition, that is to say that less than 20% of the anionic sites are neutralized by an alkalinisation agent. Preferably, the polymer is not neutralized, that is to say that the composition used in the process according to the invention does not comprise any alkalinisation agent.

According to a preferred embodiment, the fixing polymer is an anionic fixing polymer having a degree of neutralization less than 20% in the composition, and more preferably an anionic fixing polymer which is not neutralized.

The fixing polymer(s) according to the invention are preferably present in the styling composition in an amount ranging from 0.1 % to 30%, preferably from 0.5% to 20% and more preferably from 1 % to 15% by weight relative to the total weight of the styling composition.

Organic solvent

The styling composition according to the present invention also comprises one or more organic solvents.

According to one embodiment, the organic solvent is chosen from liquid monoalcohols or polyols.

The term "liquid" means a compound that is liquid at 25°C and at atmospheric pressure (760 mmHg or 1.013x10⁵ Pa).

Liquid monoalcohols that will be mentioned in particular include Ci_-4 monoalcohols such as ethanol, isopropanol, tert-butanol or n-butanol. The polyols that may be used in the styling composition according to the invention are compounds consisting of a hydrocarbon-based chain optionally interrupted with one or more oxygen atoms and bearing at least two free hydroxyl groups, and having a molecular weight of less than 1000.

The hydrocarbon-based chain may be linear or branched and saturated or unsaturated.

Preferably, the hydrocarbon-based chain comprises from 3 to 50 carbon atoms and better still from 3 to 20 carbon atoms.

In a variant of the invention, the hydrocarbon-based chain is saturated.^*

Very particularly, the polyols of the invention comprise 2 or 3 free hydroxyl functional groups.

The free hydroxyl functional groups can be carried by contiguous carbon atoms or the carbon atoms carrying them can be separated by one or more other carbon atoms.

Use is preferably made, among these polyols, of 1 ,2-propanediol (or propylene glycol), 1 ,3-propanediol, glycerol, 3-(2-ethylhexyl)oxy-1 ,2-propanediol (or ethylhexyl glycerol), 3-methyl-1 ,3,5-pentanetriol, 1 ,2,4-butanetriol, 1 ,5-pentanediol, 2-methyl-1 ,3- propanediol, 1 ,3-butanediol, 3-methyl-1 ,5-pentanediol, neopentyl glycol (2,2-dimethyl- 1 ,3-propanediol), isoprene glycol (3-methyl-1 ,3-butanediol) and hexylene glycol (2- methyl-2,4-pentanediol), diethylene glycol, dipropylene glycol, tripropylene glycol or polyethylene glycols of formula H(OCH₂CH₂)_nOH with n ranging from 4 to 16.

Preferably, the organic solvent is soluble in water at ordinary temperature (25°C) and liquid at atmospheric pressure (760 mmHg; i.e. 1.013x10⁵ Pa) to a weight concentration of greater than or equal to 4%.

The organic solvent is preferably ethanol.

The organic solvent content preferably ranges from 10% to 98% by weight, preferably from 20% to 98% by weight and better still from 50% to 95% by weight relative to the total weight of the styling composition.

The styling composition may be aqueous or anhydrous.

For the purposes of the invention, a composition is anhydrous when it has a water content of less than 2% by weight and preferably less than 1 % by weight relative to the total weight of the composition.

Preferably, an anhydrous composition contains no water added during the preparation of the composition, the only water present corresponding to the residual water provided by the ingredients mixed. Even more preferably, the anhydrous composition is free of water.

When it is aqueous, it preferably comprises from 5% to 70% by weight of water, even more preferentially from 10% to 60% by weight of water and better still from 10% to 50% by weight of water relative to the total weight of the styling composition.

In one variant, the styling composition is anhydrous.

The styling composition according to the invention may also comprise a hair- conditioning agent.

In the context of the present patent application, the term "hair-conditioning agent" means any agent whose function is to improve the cosmetic properties of the hair, in particular the softness, sheen, disentangling, feel, smoothness or static electricity.

The conditioning agents may be in liquid, semi-solid or solid form, for instance oils, waxes or gums.

The conditioning agents may be chosen from fatty substances such as C₆-Ci₆ hydrocarbons or hydrocarbons containing more than 16 carbon atoms and in particular alkanes, oils of animal origin, oils of plant origin, glycerides or fluoro oils of synthetic origin, fatty alcohols, fatty acid and/or fatty alcohol esters, non-silicone waxes, silicones, fatty amines, fatty acids, cationic polymers, amphoteric polymers, cationic proteins, cationic protein hydrolysates, compounds of ceramide type, cationic surfactants, and also mixtures of these various compounds.

The styling composition according to the invention may also comprise one or more thickeners.

For the purposes of the present invention, the term "thickener" means an agent which, by virtue of its presence in the styling composition, makes it possible to increase the viscosity of the said composition by at least 10 cPs and preferably by at least 200 cPs, at 25°C and at a shear rate of 1 s^' This viscosity may be measured using a cone/plate viscometer (Haake R600 rheometer or the like).

The thickener(s) may be chosen from fatty acid amides obtained from Ci₀-C₃₀ carboxylic acid (monoisopropanolamide, diethanolamide or monoethanolamide of coconut acids, monoethanolamide of ethoxylated carboxylic alkyl ether acid), polymeric thickeners and in particular nonionic cellulose-based polymers (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), starches, gum arabic, gums of microbial origin (scleroglucan gum, xanthan gum), gums of galactomannan type (guar gum, locust bean gum, fenugreek gum, tara gum) and derivatives thereof (guar phosphate, hydroxypropyl guar), glucomannans (konjac gum), crosslinked or non- crosslinked homopolymers and copolymers based on acrylic acid, methacrylic acid or acrylamidopropanesulfonic acid, and associative polymers as described below, and mixtures thereof.

The associative polymer(s) that may be used according to the invention are water-soluble polymers that are capable, in aqueous medium, of reversibly associating with each other or with other molecules.

Their chemical structure comprises hydrophilic zones and hydrophobic zones characterized by at least one fatty chain preferably comprising from 10 to 30 carbon atoms.

The associative polymer(s) that may be used according to the invention may be of anionic, cationic, amphoteric or nonionic type, such as the polymers sold under the names Pemulen TR1 or TR2 by the company Goodrich (INCI: Acrylates/C 10-30 Alkyl Acrylate Crosspolymer), Salcare SC90 by the company Ciba, Aculyn 22, 28, 33, 44 or 46 by the company Rohm & Haas and Elfacos T210 and T212 by the company Akzo.

Among all the mentioned thickeners, the additional thickener(s) are preferably chosen from polymers, and better still from nonionic cellulose-based polymers, especially hydroxypropylcellulose and gum arabic.

The additional thickeners may be present in the styling composition in an amount ranging from 0.01 % to 20% by weight and better still from 0.1 % to 10% by weight relative to the total weight of the styling composition.

The pH of the styling compositions used according to the invention generally ranges from 2 to 1 1 , preferably from 3 to 6.5 and even more preferentially from 4 to 6. Preferentially, the styling composition according to the invention may contain active agents conventionally used in non-lasting hair shaping other than those described previously, and chosen from nonionic surfactants, anionic surfactants, amphoteric surfactants, direct dyes, in particular cationic or natural dyes or oxidation dyes, organic or mineral pigments, UV-screening agents, fillers, especially nacres, Ti0₂, clays, fragrances, peptizers, vitamins, amino acids, preserving agents, pH agents, agents for long-lasting shaping of the hair, especially thiol-based organic reducing agents, non-thiol-based organic reducing agents, etc.

Needless to say, a person skilled in the art will take care to select the optional additional compounds and/or the amount thereof such that the advantageous properties of the compositions used according to the invention are not, or are not substantially, adversely affected by the envisaged addition. Preferably, the styling compositions are in the form of gels. Preferably, the styling compositions have a viscosity of greater than or equal to 4 Pa.s and better still ranging from 4 Pa.s to 500 Pa.s at a temperature of 25°C and at a shear rate of 1 s^"1 (measurable, for example, with a Haake RS600 rheometer).

Washing composition The washing composition that may be used in accordance with the invention comprises one or more surfactants.

The surfactants may be chosen from anionic, nonionic, amphoteric or zwitterionic surfactants, and mixtures thereof.

The nonionic surfactants that may be used in the washing compositions in accordance with the present invention are compounds that are well known per se (see in particular in this respect the Handbook of Surfactants by M.R. Porter, published by Blackie & Son (Glasgow and London), 1991 , pp. 1 16-178). They are especially chosen from polyethoxylated, polypropoxylated or polyglycerolated fatty alcohols, polyethoxylated, polypropoxylated or polyglycerolated a-diols, or polyethoxylated, polypropoxylated or polyglycerolated (Ci_₂o)alkylphenols, the fatty chain comprising, for example, from 10 to 20 carbon atoms and preferably from 16 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups possibly ranging especially from 1 to 150 and the number of glycerol groups possibly ranging especially from 1 to 30.

Mention may also be made of condensates of ethylene oxide and of propylene oxide with fatty alcohols; polyethoxylated fatty amides preferably having from 1 to 100 ethylene oxide units, polyglycerolated fatty amides comprising on average from 1 to 5, and in particular from 1 .5 to 4 glycerol groups, ethoxylated fatty acid esters of sorbitan having from 1 to 50 ethylene oxide units, fatty acid esters of sucrose, fatty acid esters of polyethylene glycol, alkyl polyglycosides, polyethoxylated plant oils preferably containing from 1 to 100 ethylene oxide units, N-(C_6-24 alkyl)glucamine derivatives or amine oxides, such as (Cio-i₄ alkyl)amine oxides or N-(Ci₀-i₄ acyl)aminopropylmorpholine oxides.

The alkyl polyglucosides may be selected, for example, from decyl glucoside ((C₉/C11 alkyl) (1 ,4) polyglucoside), such as the product sold under the name Mydol 10^® by the company Kao Chemicals or the product sold under the name Plantacare 2000 UP^® by the company Henkel and the product sold under the name Oramix NS 10^® by the company SEPPIC; caprylyl/capryl glucoside, such as the product sold under the name Plantacare KE 371 1^® by the company Cognis or Oramix CG 1 10^® by the company SEPPIC; lauryl glucoside, such as the product sold under the name Plantacare 1200 UP^® by the company Henkel or Plantaren 1200 N^® by the company Henkel; coco glucoside, such as the product sold under the name Plantacare 818 UP^® by the company Henkel; caprylyl glucoside, such as the product sold under the name Plantacare 810 UP^® by the company Cognis; and 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 C02H, C02-, S03H, S03-, OS03H, OS03-, -H2P03, -HP03-, -P032-, -H2P02, =HP02, - HP02-, =P02-, =POH and =PO- groups.

Mention may be made, among the anionic surfactants capable of being used in the washing composition used according to the invention, of alkyi sulfates, alkyi ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, oolefinsulfonates, paraffin sulfonates, alkyi sulfosuccinates, alkyi ether sulfosuccinates, alkylamide sulfosuccinates, alkyi sulfoacetates, acyl sarcosinates, acyl glutamates, alkyi ether carboxylates, alkyi sulfosuccinamates, acyl isethionates and N-acyl taurates; monoalkyl esters of polyglycoside-polycarboxylic acids, acyl lactylates, D-galactosideuronic acids, alkyi ether carboxylic acids, alkylaryl ether carboxylic acids, alkylamido ether carboxylic acids; and the corresponding salified forms of all these compounds; the alkyi 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 and better still from 1 to 10 ethylene oxide units.

The salts of C6-C24 alkyi monoesters of polyglycoside-polycarboxylic acids may be chosen from C6-C24 alkyi polyglycoside-citrates, C6-C24 alkyi polyglycoside- tartrates and C6-C24 alkyi polyglycoside-sulfosuccinates.

The acyl lactylates preferably have an acyl group comprising from 8 to 20 carbon atoms.

When the anionic surfactant is in the salt form, it may be chosen from the alkali metal salts, such as the sodium salt or potassium salt, the ammonium salts, the amine salts and in particular the amino alcohol salts, or the alkaline-earth metal salts, such as the magnesium salt.

Mention may be made, as examples of amino alcohol salts, of monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1 -propanol salts, 2- amino-2-methyl-1 ,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.

Use is preferably made of alkali metal or alkaline-earth metal salts, in particular sodium or magnesium salts.

The preferred anionic surfactants are chosen from (C6-24)alkyl sulfates, (C6-

24)alkyl ether sulfates, acyl glutamates and (C6-C24)alkyl ether carboxylates, in particular in the form of alkali metal, ammonium, amino alcohol or alkaline-earth metal salts, or a mixture of these compounds.

In particular, use is preferably made of (C12-20)alkyl sulfates, (C12-20)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, acyl glutamates or (C12- C20)alkyl ether carboxylates, especially in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.

The amphoteric or zwitterionic surfactants capable of being used in the present invention can in particular be derivatives of optionally quaternized secondary or tertiary aliphatic amines comprising at least one anionic group, such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group, and in which the aliphatic group or at least one of the aliphatic groups is a linear or branched chain comprising from 8 to 22 carbon atoms.

Mention may be made in particular of (C₈-C₂o)alkyl betaines, sulfobetaines, (C₈-

C₂o)alkylamido(Ci-C₆)alkyl betaines, such as cocoamidopropyl betaine, or (C₈- C₂o)alkylamido(Ci-C₆)alkyl sulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, mention may also be made of the products of respective structures (A1 ) and (A2) below:

Ra-CONHCH2CH2-N+(Rb)(Rc)(CH2COO-) (A1 )

in which:

Ra represents a C10-C30 alkyl or alkenyl group derived from an acid Ra-COOH preferably present in hydrolysed coconut oil, a heptyl group, a nonyl group or an undecyl group,

Rb represents a β-hydroxyethyl group, and

Rc represents a carboxymethyl group;

Ra'-CONHCH2CH2-N(B)(B') (A2)

in which:

B represents -CH₂CH₂OX',

X' represents the group -CH₂-COOH, CH₂-COOZ', -CH₂CH₂-COOH, -CH₂CH₂- COOZ', or a hydrogen atom, B' represents -(CH₂)_Z-Y\ with z = 1 or 2,

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

Z' represents an ion resulting from an alkali or alkaline-earth metal, such as sodium, potassium or magnesium; an ammonium ion; or an ion resulting from an organic amine and in particular from an amino alcohol, such as monoethanolamine, diethanolamine and triethanolamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, 2-amino-2-methyl-1 -propanol, 2-amino-2-methyl-1 ,3-propanediol and tris(hydroxymethyl)aminomethane,

Ra' represents a C10-C30 alkyl or alkenyl group of an acid Ra'COOH preferably present in hydrolysed coconut oil or hydrolysed linseed oil, an alkyl group, in particular a C17 alkyl group, and its iso form, or an unsaturated C17 group.

The compounds corresponding to formula (A2) are preferred. These compounds are also 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 of the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol^® C2M Concentrate.

Use may also be made of the compounds of formula (A3):

Ra"-NH-CH(Y")-(CH2)n-C(0)-NH-(CH2)n'-N(Rd)(Re) (A3)

in which formula:

· Y" represents the group -C(O)OH, -C(O)OZ", -CH₂-CH(OH)-SO₃H or the group -CH₂-CH(OH)-SO₃-Z";

• Rd and Re, independently of each other, represent a Ci-C₄ alkyl or hydroxyalkyl radical;

• Z" represents a cationic counterion 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 C10-C30 alkyl or alkenyl group derived from an acid, Ra"-C(0)OH preferably present in coconut oil or in hydrolysed linseed oil;

• n and n', independently of each other, denote an integer ranging from 1 to 3. Among the compounds of formula (A3), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.

Preferably, the amphoteric or zwitterionic surfactants are chosen from (C₈- C₂o)alkyl betaines, (C₈-C2o)alkylamido(Ci-C₆)alkyl betaines and (C₈- C₂o)alkylamphodiacetates, and also the sodium salt of diethylaminopropyl laurylaminosuccinamate, and mixtures thereof.

Preferably, the amphoteric or zwitterionic surfactants are chosen, alone or as a mixture, from cocoylamidopropyl betaine, cocoyl betaine and cocoamphodiacetate.

The surfactant(s) of the washing composition are preferably chosen from anionic surfactants and amphoteric surfactants. Even more preferentially, they are chosen from anionic surfactants, preferably from alkyl ether sulfates, alkyl sulfates and acyl isethionates, the anionic surfactants optionally being combined with one or more amphoteric surfactants.

The surfactant(s) are preferably present in the washing composition in an amount ranging from 4% to 50% by weight, preferably from 6% to 40% by weight and more preferentially from 8% to 30% by weight relative to the total weight of the washing composition.

The washing composition used according to the invention may also comprise one or more conditioning agents such as those described and defined previously for the styling composition.

As conditioning agent, the washing composition may preferably comprise a cationic polymer and/or a silicone.

The term "cationic polymer" means any polymer comprising cationic groups and/or groups that can be ionized to cationic groups. Preferably, the cationic polymer is hydrophilic or amphiphilic. The cationic polymers may be chosen from all those already known per se as improving the cosmetic properties of the hair, i.e. especially those described in documents EP 337 354, FR 2 270 846, FR 2 383 660, FR 2 598 61 1 , FR 2 470 596 and FR 2 519 863.

The preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that may either form part of the main polymer chain or may be borne by a side substituent directly connected thereto. The cationic polymers that may be used preferably have a weight-average molar mass (Mw) of between 500 and 5 <10⁶ approximately and preferably between 10³ and 3x10⁶ approximately.

Among the cationic polymers, mention may more particularly be made of polymers of the polyamine, polyaminoamide and polyquaternary ammonium type, such as those described in FR 2 505 348 and FR 2 542 997.

Mention may be made in particular of:

(1 ) Homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulae:

FL FL

CH₂— C- CH₉-C— CH₂— C-

I I

O =C O =C O =C

O O NH

X-

A A A

N R— N⁺ - R₆ N

R₂ FL, R₅ FL, R; 2

in which:

- R3, which may be identical or different, denote a hydrogen atom or a CH₃ radical;

- A, which may be identical or different, represent a linear or branched divalent alkyi group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms, or a hydroxyalkyi group of 1 to 4 carbon atoms;

- R4, R5 and R6, which may be identical or different, represent an alkyi group containing from 1 to 18 carbon atoms or a benzyl radical, preferably an alkyi group containing from 1 to 6 carbon atoms;

- R1 and R2, which may be identical or different, represent a hydrogen atom or an alkyi group containing from 1 to 6 carbon atoms, preferably methyl or ethyl; - X denotes an anion derived from a mineral or organic acid, such as a methosulfate anion or a halide such as chloride or bromide.

The copolymers of family (1 ) may also contain one or more units derived from comonomers that may be selected from the family of acrylamides, methacrylamides, diacetone acrylamides, acrylamides and methacrylamides substituted on the nitrogen with lower (CrC₄) alkyls, acrylic or methacrylic acids or esters thereof, vinyllactams such as vinylpyrrolidone or vinylcaprolactam, and vinyl esters. Among these copolymers of family (1 ), mention may be made of:

- copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide, such as the product sold under the name Hercofloc by the company Hercules,

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium chloride, such as those described in EP 080 976 and those sold under the name Bina

Quat P 100 by the company Ciba Geigy,

- copolymers of acrylamide and of methacryloyloxyethyltrimethylammonium methosulfate, 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, for instance 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,

- dimethylaminoethyl methacrylate/vinylcaprolactam/vinylpyrrolidone terpolymers, such as the product sold under the name Gaffix VC 713 by the company ISP,

- vinylpyrrolidone/methacrylamidopropyldimethylamine copolymers, such as those sold under the name Styleze CC 10 by ISP,

- quaternized vinylpyrrolidone/dimethylaminopropylmethacrylamide copolymers such as the product sold under the name Gafquat HS 100 by the company ISP,

- preferably crosslinked polymers of methacryloyloxy(Ci-C₄)alkyltri(Ci- C₄)alkylammonium salts, such as the polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homopolymerization or copolymerization being followed by crosslinking with an olefinically unsaturated compound, more particularly methylenebisacrylamide. A crosslinked acrylamide/methac loyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of the said copolymer in mineral oil may be used more particularly. This dispersion is sold under the name Salcare® SC 92 by the company Ciba. A crosslinked methacryloyloxyethyltrimethylammonium chloride homopolymer containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester can also be used. These dispersions are sold under the names Salcare® SC 95 and Salcare® SC 96 by the company Ciba. (2) Cationic polysaccharides, especially cationic celluloses and galactomannan gums. Among the cationic polysaccharides, mention may be made more particularly of cellulose ether derivatives comprising quaternary ammonium groups, cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer and cationic galactomannan gums.

The cellulose ether derivatives comprising quaternary ammonium groups are especially described in French patent 1 492 597, and mention may be made of the polymers sold under the name Ucare Polymer "JR" (JR 400 LT, JR 125 and JR 30M) or "LR" (LR 400 or LR 30M) by the company Amerchol. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose that have reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer are described especially in US patent 4 131 576, and mention may be made of hydroxyalkylcelluloses, for instance hydroxymethyl-, hydroxyethyl- or hydroxypropylcelluloses grafted, in particular, with a methacryloylethyltrimethylammonium, methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt. The commercial products corresponding to this definition are more particularly the products sold under the names Celquat L 200 and Celquat H 100 by the company National Starch.

The cationic galactomannan gums are described more particularly in US patents 3 589 578 and 4 031 307, and mention may be made of guar gums comprising cationic trialkylammonium groups. Use is made, for example, of guar gums modified with a 2,3- epoxypropyltrimethylammonium salt (for example, chloride). Such products are especially sold under the names Jaguar C13 S, Jaguar C 15, Jaguar C 17 or Jaguar C162 by the company Rhodia. (3) Polymers formed from piperazinyl units and divalent alkylene or hydroxyalkylene radicals containing straight or branched chains, optionally interrupted with oxygen, sulfur or nitrogen atoms or with aromatic or heterocyclic rings, and also the oxidation and/or quaternization products of these polymers. Such polymers are especially described in FR 2 162 025 and FR 2 280 361 ;

(4) Water-soluble polyaminoamides prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked with an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis- unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or alternatively with an oligomer resulting from the reaction of a difunctional compound which is reactive with a bis-halohydrin, a bis-azetidinium, a bis- haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis-unsaturated derivative; the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mol per amine group of the polyaminoamide; these polyaminoamides can be alkylated or, if they comprise one or more tertiary amine functions, they can be quaternized. Such polymers are described, in particular, in French patents 2 252 840 and 2 368 508;

(5) Polyamino amide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with bifunctional agents. Mention may be made, for example, of adipic acid/dialkylaminohydroxyalkyldialkylenetriamine polymers in which the alkyl radical comprises from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in FR 1 583 363.

Among these derivatives, mention may be made more particularly of the adipic acid/dimethylaminohydroxypropyl/diethylenetriamine polymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.

(6) Polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids containing from 3 to 8 carbon atoms; the mole ratio between the polyalkylene polyamine and the dicarboxylic acid preferably being between 0.8:1 and 1 .4:1 ; the resulting polyamino amide being reacted with epichlorohydrin in a mole ratio of epichlorohydrin relative to the secondary amine group of the polyamino amide preferably of between 0.5:1 and 1 .8:1. Such polymers are especially described in US 3 227 615 and US 2 961 347.

Polymers of this type are sold in particular under the name Hercosett 57 by the company Hercules Inc. or alternatively under the name PD 170 or Delsette 101 by the company Hercules in the case of the adipic acid/epoxypropyl/diethylenetriamine copolymer.

(7) Cyclopolymers of alkyldiallylamine or of dialkyldiallylammonium, such as homopolymers or copolymers containing, as main constituent of the chain, units corresponding to formula (X) or (XI):

(CH₂)k

\ (CH₂)k

-(CH₂)t- CR C(R₁₂)-CH₂-

12

-(CH₂)t- C(R₁₂)-CH₂-

HX / CH, 2 H₂C CH,

(I) N+ γ- (II) N

* ^R1 1 ₁₀

(X) (XI) in which:

- k and t are equal to 0 or 1 , the sum k + t being equal to 1 ;

- R12 denotes a hydrogen atom or a methyl radical;

- R10 and R1 1 , independently of each other, denote an alkyl group containing from 1 to 6 carbon atoms, a hydroxyalkyi group in which the alkyl group contains 1 to 5 carbon atoms, a C1 -C4 amidoalkyl group; or alternatively R10 and R1 1 may denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl or morpholinyl; R10 and R1 1 , independently of each other, preferably denote an alkyl group containing from 1 to 4 carbon atoms;

- Y^" is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate or phosphate.

These polymers are especially described in FR 2 080 759 and FR 2 190 406. Mention may be made more particularly of the dimethyldiallylammonium salt (for example chloride) homopolymer sold for example under the name Merquat 100 by the company Nalco (and homologues thereof of low weight-average molar masses) and the copolymers of diallyldimethylammonium salts (for example chloride) and of acrylamide, sold especially under the name Merquat 550 or Merquat 7SPR. (8) Quaterna rs comprising repeating units of formula: 1

1

(XII)

in which:

- R13, R14, R15 and R16, which may be identical or different, represent aliphatic, alicyclic or arylaliphatic radicals comprising from 1 to 20 carbon atoms, or lower hydroxyalkylaliphatic radicals, or else R13, R14, R15 and R16, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally comprising a second non-nitrogen heteroatom, or else R13, R14, R15 and R16 represent a linear or branched Ci-C₆ alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-0-R17-D or -CO-NH-R17-D group in which R17 is an alkylene and D is a quaternary ammonium group;

- A1 and B1 represent divalent polymethylene groups comprising from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated, and which may contain, linked to or intercalated in the main chain, one or more aromatic rings or one or more oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternary ammonium, ureido, amide or ester groups, and

- X^" denotes an anion derived from a mineral or organic acid;

it being understood that A1 , R13 and R15 can form, with the two nitrogen atoms to which they are attached, a piperazine ring;

in addition, if A1 denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 may also denote a group (CH₂)n-CO-D-OC-(CH2)_n- in which D denotes:

a) a glycol residue of formula -0-Z-0-, in which Z denotes a linear or branched hydrocarbon-based radical, or a group corresponding to one of the following formulae: -(CH₂-CH₂-0)_x-CH₂-CH₂- and -[CH₂-CH(CH₃)-0]_y-CH₂-CH(CH₃)-, where x and y denote an integer from 1 to 4, representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative;

c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon-based radical, or else the divalent radical -CH₂-CH₂-S- S-CH₂-CH₂-; d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X^" is an anion such as chloride or bromide.

These polymers have a number-average molar mass (Mn) generally of between 1000 and 100 000.

Polymers of this type are described in particular in French patents 2 320 330, 2 270 846, 2 316 271 , 2 336 434 and 2 413 907 and US patents 2 273 780, 2 375 853,

2 388 614, 2 454 547, 3 206 462, 2 261 002, 2 271 378, 3 874 870, 4 001 432,

3 929 990, 3 966 904, 4 005 193, 4 025 617, 4 025 627, 4 025 653, 4 026 945 and 4 027 020.

Mention may be made more particularly of polymers that are composed of repeating units corresponding to the formula:

R₁ R 3

N (CH₂)_n- H (CH₂)_p —

X- 2 ^Λ R₄

(XIII)

in which R1 , R2, R3 and R4, which may be identical or different, denote an alkyl or hydroxyalkyi radical containing from 1 to 4 carbon atoms approximately, n and p are integers ranging from 2 to 20 approximately, and X^" is an anion derived from an organic or mineral acid.

A particularly preferred compound of formula (XVI I I) is that for which R1 , R2, R3 and R4 represent a methyl radical and n = 3, p = 6 and X = CI, known as Hexadimethrine chloride according to the INCI (CTFA) nomenclature.

(9) Polyquaternary ammonium polymers comprising units of formula (XIV):

R 18 R 20

— N+ - (CH₂)_r - NH - CO - (CH₂)_q - CO - NH (CH₂)_S - N+ - A—

^R19 (V) R₂₁

x^" (XIV) in which:

- R18, R19, R20 and R21 , which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl, β-hydroxypropyl or - CH2CH2(OCH2CH₂)pOH radical, in which p is equal to 0 or to an integer between 1 and 6, with the proviso that R18, R19, R20 and R21 do not simultaneously represent hydrogen atom,

- r and s, which may be identical or different, are integers between 1 and 6,

- q is equal to 0 or to an integer between 1 and 34,

- X- denotes an anion such as a halide,

- A denotes a dihalide radical or preferably represents -CH2-CH2-O-CH2-CH2-.

Such compounds are described in particular in patent application EP-A-122 324. Examples that may be mentioned include the products Mirapol® A15, Mirapol® AD1 , Mirapol® AZ1 and Mirapol® 175 sold by the company Miranol.

(10) Quaternary polymers of vinylpyrrolidone and of vinylimidazole, for instance the products sold under the names Luviquat® FC 905, FC 550 and FC 370 by the company BASF.

(1 1 ) Polyamines such as Polyquart® H sold by Cognis, referred to under the name Polyethylene glycol (15) tallow polyamine in the CTFA dictionary.

(12) Polymers comprising in their structure:

(a) one or more units corresponding to formula (A) below:

— CH5— CH—

NH₂ (A)

(b) optionally, one or more units corresponding to formula (B) below:

— CH5— CH—

² I (B)

NH— C-H

I I

0

In other words, these polymers may be chosen especially from homopolymers or copolymers comprising one or more units derived from vinylamine and optionally one or more units derived from vinylformamide.

Preferably, these cationic polymers are chosen from polymers comprising, in their structure, from 5 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 95 mol% of units corresponding to formula (B), preferentially from 10 mol% to 100 mol% of units corresponding to formula (A) and from 0 to 90 mol% of units corresponding to formula (B). These polymers may be obtained, for example, by partial hydrolysis of polyvinylformamide. This hydrolysis may be performed in an acidic or basic medium.

The weight-average molecular mass of the said polymer, measured by light scattering, may range from 1000 to 3 000 000 g/mol, preferably from 10 000 to 1 000 000 g/mol and more particularly from 100 000 to 500 000 g/mol.

The cationic charge density of these polymers may range from 2 meq/g to 20 meq/g, preferably from 2.5 to 15 meq/g and more particularly from 3.5 to 10 meq/g.

The polymers comprising units of formula (A) and optionally units of formula (B) are sold especially under the name Lupamin by the company BASF, for instance, and in a non-limiting manner, the products sold under the names Lupamin 9095, Lupamin 5095, Lupamin 1095, Lupamin 9030 and Lupamin 9010.

Other cationic polymers that may be used in the context of the invention are cationic proteins or cationic protein hydrolysates, polyalkyleneimines, in particular polyethyleneimines, polymers comprising vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

Preferably, the cationic polymers are chosen from the polymers of families (1 ), (2), (7) and (10) mentioned above.

Among the cationic polymers mentioned above, the ones that may preferably be used are cationic polysaccharides, especially cationic celluloses and galactomannan gums, and in particular quaternary cellulose ether derivatives such as the products sold under the name "JR 400" by the company Amerchol, cationic cyclopolymers, in particular dimethyldiallylammonium salt (for example chloride) homopolymers or copolymers, sold under the names Merquat 100, Merquat 550 and Merquat S by the company Nalco, and homologues thereof of low weight-average molecular weights, quaternary polymers of vinylpyrrolidone and of vinylimidazole, optionally crosslinked homopolymers or copolymers of methacryloyloxy(Ci-C4)alkyltri(Ci-C4)alkylammonium salts, and mixtures thereof.

Among the silicones that can be used as conditioning agents in accordance with the present invention, mention may be made, without limitation, of the following:

I. Volatile silicones: These silicones have a boiling point of between 60°C and 260°C. Among the silicones of this type that are mentioned are:

(i) cyclic silicones comprising from 3 to 7 and preferably 4 to 5 silicon atoms.

These are, for example, octamethylcyclotetrasiloxane sold under the name

Volatile Silicone 7207® by the company Union Carbide or Silbione 70045 V2® by the company Rhone-Poulenc, decamethylcyclopentasiloxane sold under the name Volatile Silicone 7158® by the company Union Carbide, and Silbione 70045 V5® by the company Rhone-Poulenc, and mixtures thereof. Mention is also made of cyclopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone FZ 3109® sold by the company Union Carbide, which is a dimethylsiloxane/methyloctylsiloxane cyclocopolymer;

(ii) linear volatile silicones containing 2 to 9 silicon atoms an having a viscosity of less than or equal to 5x10^"6 m²/s at 25°C.

These are, for example, the hexamethyldisiloxane sold under the name Silbione

70041 V0.65® by the company Rhone-Poulenc. This type of product is described in the article by Todd & Byers Volatile silicone fluids for cosmetics, Cosmetics and Toiletries, Vol. 91 , Jan 76, pages 27-32.

II. Non-volatile silicones

These silicones are mainly constituted by polyalkylsiloxanes, polyarylsiloxanes, polyalkylarylsiloxanes and organomodified polysiloxanes, and also mixtures thereof. They may be in the form of oils, gums and resins.

Among the polyalkylsiloxanes, mention may be made mainly of linear polydimethylsiloxanes with a viscosity of greater than 5 <10^"6 m²/s, and preferably less than 2.6 m²/s, i.e.:

- containing trimethylsilyl end groups, for instance and without limitation, the Silbione® oils of series 70047 that are sold by the company Rhone-Poulenc, the oil Wacker Belsil DM 60000 from Wacker, or certain Viscasil® products from the company General Electric;

- containing trihydroxysilyl end groups, such as the oils of the 48 V® series from the company Rhone-Poulenc.

In this class of polyalkylsiloxanes, mention may also be made of the polyalkylsiloxanes sold by the company Goldschmidt under the names Abil Wax 9800® and Abil Wax 9801®, which are poly(C1 -20)alkylsiloxanes. Among the polyalkylarylsiloxanes, mention may be made of linear and/or branched polydimethylphenylsiloxanes and polydimethyldiphenylsiloxanes, with a viscosity from 10^"5 to 5x10^"2 m²/s, for instance:

- the oil Rhodorsil® 763 from Rhone-Poulenc,

- the Silbione® oils of the 70641 series from Rhone-Poulenc, such as the oils Silbione 70641 V30® and Silbione 70641 V200®,

- the product DC 556® Cosmetic Grade Fluid from Dow Corning,

- the silicones of the PK series from Bayer, such as 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 1250®, SF 1265®, SF 1 154® and SF 1023®.

The silicone gums in accordance with the present invention are polydiorganosiloxanes with a high number-average molecular weight of between 200 000 and 1 000 000, used alone or as a mixture in a solvent chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, methylene chloride, pentane, dodecane, tridecane and tetradecane, or mixtures thereof.

Mention is made, for example, of compounds having the following structures: - poly[(dimethylsiloxane)/(methylvinylsiloxane)] gums,

- poly[(dimethylsiloxane)/(diphenylsiloxane)] gums,

- poly[(dihydrogenodimethylsiloxane)/(divinylsiloxane)] gums,

- poly[(dimethylsiloxane)/(phenylmethylsiloxane)] gums,

- poly[(dimethylsiloxane)/(diphenylsiloxane)/(methylvinylsiloxane)] gums.

Mention may be made of the gum Mirasil DM 300 000 from the company Rhodia.

Examples that may also be mentioned, in a non-limiting manner, include the following mixtures:

1 ) mixtures formed from a polydimethylsiloxane hydroxylated at the end of the chain (dimethiconol according to the CTFA nomenclature) and from a cyclic polydimethylsiloxane (cyclomethicone according to the CTFA nomenclature), such as the products Q2 1401® or Dow Corning 1501 Fluid sold by the company Dow Corning;

2) mixtures formed from a polydimethylsiloxane gum with a cyclic silicone, such as the product SF 1214 Silicone Fluid® from General Electric, which is a gum SE 30® of MW 500 000 (-Mn) dissolved in SF 1202 Silicone Fluid® (decamethylcyclopentasiloxane); 3) mixtures of two PDMSs of different viscosities, especially of a PDMS gum and a PDMS oil, such as the products SF 1236® and CF 1241 ® from the company General Electric. The product SF 1236® is the mixture of an SE 30® gum defined above, with a viscosity of 20 m²/s, and of an SF 96® oil with a viscosity of 5x10⁶ m²/s (15% SE 30® gum and 85% SF 96® oil).

The product CF 1241® is the mixture of an SE 30® gum (33%) and of a PDMS (67%), with a viscosity of 10^"3 m²/s.

The organopolysiloxane resins that may be used in accordance with the invention are crosslinked siloxane systems containing the following units: R2Si02/2, RSi03/2 and Si04/2 in which R represents a hydrocarbon-based group containing 1 to 6 carbon atoms or a phenyl group. Among these products, those particularly preferred are the ones in which R denotes a lower alkyl radical or a phenyl radical.

Among these resins, mention may be made of the product sold under the name Dow Corning 593® or those sold under the names Silicone Fluid SS 4230 and Silicone Fluid SS 4267 by the company General Electric, which are dimethyl/trimethylpolysiloxanes.

The organomodified silicones in accordance with the present invention are silicones as defined above, comprising in their general structure one or more organofunctional groups directly attached to the siloxane chain or attached via a hydrocarbon-based radical.

Mention is made, for example, of silicones comprising:

a) perfluoro groups such as trifluoroalkyls, for instance those sold by the company General Electric under the names FF.150 Fluorosilicone Fluid® or by the company Shin-Etsu under the names X-22-819®, X-22-82®, X-22-821 ® and X-22-822®;

b) hydroxyacylamino groups, for instance those described in patent application EP 0 342 834 and in particular the silicone sold by the company Dow Corning under the name Q2-8413®;

c) thiol groups, as in the silicones X 2-8360® from the company Dow Corning or GP 72A® and GP 71® from Genesee;

d) non-quaternized amine groups, as in GP 4 Silicone Fluid® from Genesee, GP 7100® from Genesee, Q2 8220® from Dow Corning, AFL 40® from Union Carbide or the silicone known as Amodimethicone in the CTFA dictionary; e) carboxylate groups, for instance the products described in patent EP 186 507 from Chisso Corporation;

f) hydroxylated groups, such as the polyorganosiloxanes containing a C2- C18 hydroxyalkyi function, described, for example, in patent application FR 85/16334;

Mention may be made most particularly of the product sold by Dow Corning under the name DC 190;

g) alkoxylated groups, for instance in the silicone copolymer F 755® from SWS Silicones and the products Abil Wax 2428®, Abil Wax 2434® and Abil Wax 2440® from the company Goldschmidt;

h) (C8-C22)acyloxy(C2-C18)alkyl groups, for instance the polyorganopolysiloxanes described in patent application FR 88/17433;

i) quaternary ammonium groups, as in the products X2 8108® and X2 8109® and the product Abil K3270® from the company Goldschmidt;

j) amphoteric or betaine groups, as in the product sold by the company

Goldschmidt under the name Abil B 9950®;

k) bisulfite groups, as in the products sold by the company Goldschmidt under the names Abil S 201® and Abil S 255®;

I) polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C6-C24 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 and L 71 1 by the company Union Carbide, and the (C12)alkylmethicone copolyol sold by the company Dow Corning under the name Q2 5200.

According to the invention, silicones comprising a polysiloxane portion and a portion formed from a non-silicone organic chain, one of the two portions forming the main chain of the polymer and the other being grafted onto the said main chain, may also be used. These polymers are described, for example, in patent applications EP-A- 412 704, EP-A-412 707, EP-A-640 105 and WO 95/00578, EP-A-582 152 and WO 93/23009 and patents US 4 693 935, US 4 728 571 and US 4 972 037. These polymers are preferably anionic or nonionic.

Such polymers are, for example, copolymers that may be obtained by free-radical polymerization 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:

H c = C - - CH

(XV)

with v being 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 especially polydimethylsiloxanes (PDMS) onto which are grafted, via a connecting unit of thiopropylene type, mixed polymer units of the poly(meth)acrylic acid type and of the polyalkyl (meth)acrylate type and polydimethylsiloxanes (PDMS) onto which are grafted, via a connecting unit of thiopropylene type, polymer units of the polyisobutyl (meth)acrylate type.

According to the invention, all the silicones may also be used in the form of emulsions, nanoemulsions or microemulsions.

The polyorganosiloxanes that are particularly preferred in accordance with the invention are:

- non-volatile silicones chosen from the family of polydialkylsiloxanes containing trimethylsilyl end groups, such as oils with a viscosity of between 0.2 and 2.5 m²/s at 25°C, such as the oils of the series DC200 from Dow Corning, in particular the product with a viscosity of 60 000 cSt, of the series Silbione 70047, and more particularly the oil 70 047 V 500 000 sold by the company Rhodia Chimie, polydialkylsiloxanes containing dimethylsilanol end groups such as dimethiconols, or polyalkylarylsiloxanes such as the oil Silbione 70641 V 200 sold by the company Rhodia Chimie;

- polysiloxanes containing amine groups such as amodimethicones or trimethylsilyl amodimethicones.

The viscosities of the silicones may especially be determined by the standard ASTM D445-97 (viscometry).

Care composition

The care composition that may be used in accordance with the invention comprises one or more conditioning agents such as those described and defined previously which the washing composition may comprise.

The care composition may also comprise one or more cationic surfactants. The cationic surfactant(s) that may be used in the care composition comprise, for example, salts of optionally polyoxyalkylenated primary, secondary or tertiary fatty amines, quaternary ammonium salts, and mixtures thereof.

Examples of quaternary ammonium salts that may especially be mentioned include:

- those corresponding to the general formula (XVI) below:

(XVI) in which the radicals R8 to R1 1 , which may be identical or different, represent a linear or branched aliphatic radical comprising from 1 to 30 carbon atoms or an aromatic radical such as aryl or alkylaryl, at least one of the radicals R8 to R1 1 comprising from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms. The aliphatic radicals may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens.

The aliphatic radicals are chosen, for example, from C1 -C30 alkyl, C1 -C30 alkoxy, polyoxy(C2-C6)alkylene, C1 -C30 alkylamide, (C12-C22)alkylamido(C2-C6)alkyl and C1 -C30 hydroxyalkyl radicals, and X^" is an anion chosen from the group of halides, phosphates, acetates, lactates, (C1 -C4)alkyl sulfates, and (C1 -C4)alkyl- or (C1 - C4)alkylaryl-sulfonates.

Among the quaternary ammonium salts of formula (XVI), preference is firstly given to tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl radical comprises approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium, dicetyldimethylammonium and benzyldimethylstearylammonium chlorides, or else, secondly, to palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, which is sold under the name Ceraphyl® 70 by the company Van Dyk.

- quaternary ammonium salts of imidazoline, for instance those of formula (XVII) below:

(XVII) in which R12 represents an alkyl or alkenyl radical comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow, R13 represents a hydrogen atom, a C1 -C4 alkyl radical or an alkyl or alkenyl radical comprising from 8 to 30 carbon atoms, R14 represents a C1 -C4 alkyl radical, R15 represents a hydrogen atom or a C1 -C4 alkyl radical, X- is an anion chosen from the group of halides, phosphates, acetates, lactates, (C1 -C4)alkyl sulfates and (C1 -C4)alkyl- or (C1 -C4)alkylaryl- sulfonates. Preferably, R12 and R13 denote a mixture of alkenyl or alkyl radicals comprising from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R14 denotes a methyl radical and R15 denotes a hydrogen atom. Such a product is sold, for example, under the name Varisoft W 575 PG N by the company Evonik Goldschmidt; - quaternary diammonium or triammonium salts, particularly of formula (XVIII) below:

R₁₆— N 2X ^~

R

(XVIII) in which R16 denotes an alkyl radical comprising about 16 to 30 carbon atoms, optionally hydroxylated and/or interrupted with one or more oxygen atoms; R17 is chosen from hydrogen, an alkyl radical comprising from 1 to 4 carbon atoms or a group -(CH2)3-N+(R16a)(R17a)(R18a); R16a, R17a, R18a, R18, R19, R20 and R21 , which may be identical or different, are chosen from hydrogen and an alkyl radical comprising from 1 to 4 carbon atoms, and X- is an anion chosen from the group of halides, acetates, phosphates, nitrates, (C1 -C4)alkyl sulfates and (C1 -C4)alkyl- or (C1 - C4)alkylaryl-sulfonates, in particular methyl sulfate and ethyl sulfate. Such compounds are, for example, Finquat CT-P, sold by the company Innospec Active Chemicals (Quaternium 89), and Condicare CT sold by the company Innospec Active Chemicals (Quaternium 75);

- quaternary ammonium salts containing one or more ester functions, such those of formula (XIX) below:

R 24 - — R₂₃ X

(XIX) in which:

R22 is chosen from C1 -C6 alkyl radicals and C1 -C6 hydroxyalkyl or dihydroxyalkyl radicals;

R23 is chosen from:

O II

- the radical R₂₆— C— - linear or branched, saturated or unsaturated C1 -C22 hydrocarbon-based radicals R27,

- a hydrogen atom,

R25 is chosen from:

O II

- the radical R₂₈— C— - saturated or unsaturated, linear or branched C1 -C6 hydrocarbon-based radicals

R29,

- a hydrogen atom,

R24, R26 and R28, which are identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based radicals,

r, s and t, which may be identical or different, are integers ranging from 2 to 6, r1 and t1 , which may be identical or different, are equal to 0 or 1 ,

r2+r1 =2r and t1 +t2=2t,

y is an integer ranging from 1 to 10;

x and z, which may be identical or different, are integers ranging from 0 to 10; X^" is a simple or complex, organic or mineral anion; with the proviso that the sum x + y + z is from 1 to 15, that when x is 0, then R23 denotes R27 and that when z is 0, then R25 denotes R29.

The alkyl radicals R22 may be linear or branched, and more particularly linear. R22 preferably denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.

Advantageously, the sum x + y + z is from 1 to 10.

When R23 is a hydrocarbon-based radical R27, it may be long and may contain from 12 to 22 carbon atoms, or may be short and may contain from 1 to 3 carbon atoms.

When R25 is a hydrocarbon-based radical R29, it preferably contains 1 to 3 carbon atoms.

Advantageously, R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C1 1 -C21 hydrocarbon-based radicals, and more particularly from linear or branched, saturated or unsaturated C1 1 - C21 alkyl and alkenyl radicals.

Preferably, x and z, which may be identical or different, are equal to 0 or 1 .

Advantageously, y is equal to 1 .

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion X- is preferably a halide, preferably chloride, bromide or iodide, a (C1 - C4)alkyl sulfate or a (C1 -C4)alkyl- or (C1 -C4)alkylaryl-sulfonate. However, it is possible to use methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function.

The anion X- is even more particularly chloride, methyl sulfate or ethyl sulfate.

Use is made more particularly, in the care composition according to the invention, of the ammonium salts of formula (XIX) in which:

- R22 denotes a methyl or ethyl radical,

- x and y are equal to 1 ;

- z is equal to 0 or 1 ;

- r, s and t are equal to 2;

- R23 is chosen from:

O II

- the radical R₂₆— C— - methyl, ethyl or C14-C22 hydrocarbon-based radicals; - a hydrogen atom;

- R25 is chosen from:

O II

- the radical R₂g— C—

- a hydrogen atom;

- R24, R26 and R28, which may be identical or different, are selected from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based radicals, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl radicals.

Advantageously, the hydrocarbon-based radicals are linear.

Among the compounds of formula, examples that may be mentioned include salts, especially the chloride or methyl sulfate of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl radicals preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl radicals, these radicals may be identical or different.

Mention may be made more particularly of distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with fatty acids or with mixtures of fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably a methyl or ethyl halide, a dialkyl sulfate, preferably a methyl or ethyl sulfate, methyl methanesulfonate, methyl para- toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

The care composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.

It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180. Use may be made of behenoylhydroxypropyltrimethylammonium chloride, sold by Kao under the name Quartamin BTC 131 .

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Among the cationic surfactants optionally present in the care composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium or dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, sold for example by the company Clariant under the trade name Genamin KDMP or Genamin BTLF or by the company Evonik Goldschmidt under the name Varisoft BT 85, cetyltrimethylammonium chloride sold, for example, under the trade name Dehyquart A OR by the company Cognis or Quartamin 60 W25 by the company Kao or alternatively Genamin CTAC 25 by the company Clariant, dipalmitoylethylhydroxyethylmethylammonium methosulfate, such as the commercial product Dehyquart F 30 sold by the company Cognis, and mixtures thereof.

Preferably, the cationic surfactants are chosen from the compounds of formula (XVI) or (XIX). As other ingredient of the care composition, mention may be made of fatty alcohols.

The term "fatty alcohol" means a long-chain aliphatic alcohol comprising from 8 to 40 carbon atoms and comprising at least one hydroxyl group OH. These fatty alcohols are neither oxyalkylenated nor glycerolated. Preferably, the solid fatty alcohols are of structure R-OH with R denoting a linear or branched alkyl or alkenyl group, optionally substituted with one or more hydroxyl groups, comprising from 8 to 40, better still from 10 to 30, or even from 12 to 24 atoms, and even better still from 14 to 22 carbon atoms.

The fatty alcohols may be liquid or solid. Preferably, the fatty alcohols are not liquid at room temperature (25°C) and at atmospheric pressure (1 .013x 10⁵ Pa; 760 mmHg). Even more preferentially, they are solid under these conditions.

Preferably, R denotes a linear alkyl group, optionally substituted with one or more hydroxyl groups, comprising from 8 to 40, better still from 10 to 30, or even from 12 to 24 atoms, and even better still from 14 to 22 carbon atoms.

The fatty alcohols that may be used may be chosen, alone or as a mixture, from: - lauryl alcohol (1 -dodecanol); - myristyl alcohol (1 -tetradecanol);

- cetyl alcohol (1 -hexadecanol);

- stearyl alcohol (1 -octadecanol);

- arachidyl alcohol (1 -eicosanol);

- behenyl alcohol (1 -docosanol);

- lignoceryl alcohol (1-tetracosanol);

- ceryl alcohol (1-hexacosanol);

- montanyl alcohol (1 -octacosanol);

- myricyl alcohol (1 -triacontanol).

Preferentially, the fatty alcohol is chosen from cetyl alcohol, stearyl alcohol and behenyl alcohol and mixtures thereof such as cetylstearyl alcohol or cetearyl alcohol. The fatty alcohols may be mixtures, which means that several species may coexist in a commercial product, especially of different chain lengths, in the form of a mixture.

Shaping process

According to the invention, the hair shaping process consists in applying to hair, preferably wet hair, a styling composition as described previously and in rinsing the hair with an aqueous composition so as to precipitate the fixing polymer(s) on the hair. The fixing is immediate and results from the rinsing with the aqueous composition.

The aqueous rinsing composition may have a pH ranging from 2 to 11.

Preferably, the aqueous rinsing composition is water, especially the running water of a shower.

Preferably, the hair is rinsed immediately after the styling composition has been applied.

The term "immediately after" means within 5 minutes of applying the styling composition.

According to one embodiment, before the step of applying the styling composition, a washing composition such as that described previously is applied and the hair is then rinsed before applying the styling composition.

According to another embodiment, before the step of applying the styling composition and optionally after the step of rinsing out the washing composition, a care composition such as that described previously is applied and the hair is then rinsed before applying the styling composition.

A step of shaping the hair, especially by hand, may be performed after the step of rinsing out the styling composition. The hair may then optionally be dried, especially using a hairdryer. Alternatively, it may be dried in the open air.

The styling composition according to the invention may thus be applied directly in the shower. It may be rinsed out using the shower water, with running water. The shaping may thus take place after rinsing out the styling composition, which avoids an additional step of rinsing the hands after leaving the shower.

By means of the process of the invention, quick and easy styling is obtained, immediately on leaving the shower, without the need to apply another product after having left the shower.

The invention is illustrated in greater detail in the examples that follow, which are presented as non-limiting illustrations of the invention.

EXAMPLES

The following compositions were prepared. The concentrations are expressed as mass percentages of active materials in the final composition.

Washing composition:

Texapon N 702 sold by BASF

Mirataine BB/FLA sold by Rhodia

Care compositions:

C2 C3

Behentrimonium chloride ^{( )} 3

Cetrimonium chloride ⁽⁴⁾ 3

Cetylstearyl alcohol 5 5

Water qs 100 qs 100 Genamin KDMP sold by Clariant

Genamin CTAC 25

Styling compositions:

(⁵⁾ Resyn 28-2930 sold by Akzo Nobel

Ultrahold Strong sold by BASF

On a panel of 10 testers, successive applications with intermediate rinsing of one or more washing compositions and/or of one or more care compositions, and then of a styling composition followed by rinsing, compared with successive applications without intermediate rinsing and/or final rinsing, show greater fixing and greater hold.

Claims

1. Hair shaping process in which:

- a styling composition comprising one or more organic solvents and one or more fixing polymers is applied to hair, the fixing polymer(s) being at least partially soluble in the styling composition and being capable of precipitating on the hair when the styling composition is diluted with an aqueous composition, and then

2. Hair shaping process in which the step of rinsing the hair is performed immediately after applying the styling composition.

3. Process according to any one of the preceding claims, in which, before the step of applying the styling composition, a washing composition comprising at least one surfactant, preferably an anionic or amphoteric surfactant, is applied, a rinsing step being performed between the application of the washing composition and the application of the styling composition.

4. Process according to any one of the preceding claims, in which, before the step of applying the styling composition and optionally after the step of rinsing out the washing composition, a care composition comprising at least one conditioning agent, is applied, a rinsing step being performed between the application of the care composition and the application of the styling composition.

5. Process according to any one of the preceding claims, in which, after the step of rinsing out the styling composition, the hair is shaped.

6. Process according to any one of the preceding claims, which comprises a step of drying the hair after the step of rinsing out the styling composition and/or the shaping step.

7. Process according to the preceding claim, in which the styling composition is rinsed out under the shower.

8. Process according to any one of the preceding claims, in which the fixing polymer(s) are soluble in the styling composition.

9. Process according to any one of the preceding claims, in which the fixing polymer(s) are soluble in the organic solvent(s) at ordinary temperature (25°C) and at atmospheric pressure (760 mmHg; i.e. 1.013 ^χ 10⁵ Pa) at a weight concentration of greater than or equal to 5%.

10. Process according to any one of the preceding claims, in which the fixing polymer is an ionic, preferably anionic, fixing polymer, the anionic fixing polymer(s) preferably being chosen from copolymers of acrylic and methacrylic acid or salts thereof, crotonic acid copolymers, copolymers of monounsaturated C4-C8 carboxylic acids or anhydrides, polyacrylamides containing carboxylate groups, homopolymers or copolymers containing sulfonic groups, anionic polyurethanes, and anionic grafted silicone polymers.

1 1. Process according to any one of the preceding claims, in which the fixing polymer(s) are chosen from crotonic acid copolymers, and more preferably from crotonic acid copolymers comprising, in their chain, vinyl acetate or propionate units and optionally other monomers, such as allyl or methallyl esters, vinyl ether or vinyl ester of a linear or branched saturated carboxylic acid comprising a long hydrocarbon chain, and even more preferably is a vinyl acetate/crotonic acid/vinyl neodecanoate terpolymer.

12. Process according to any one of the preceding claims, in which the content of fixing polymer ranges from 0.1 % to 30%, preferably from 0.5% to 20% and more preferably from 1 % to 15% by weight relative to the total weight of the styling composition.

13. Process according to any one of the preceding claims, in which the organic solvent(s) are chosen from liquid monoalcohols or polyols such as ethanol, isopropanol; propylene glycol, butylene glycol, glycerol; polyol ethers; and mixtures thereof, the organic solvent(s) preferably being ethanol.

14. Process according to any one of the preceding claims, in which the content of organic solvents in the styling composition ranges from 10% to 98% by weight, preferably from 20% to 98% by weight and better still from 50% to 95% by weight relative to the total weight of the styling composition.

15. Process according to any one of the preceding claims, in which the styling composition has a pH ranging from 2 to 1 1 , preferably from 3 to 6.5 and even more preferentially from 4 to 6.

16. Process according to any one of the claims and Claim 3, in which the washing composition comprises a surfactant chosen from anionic surfactants, amphoteric surfactants and nonionic surfactants, preferably from anionic surfactants, optionally combined with one or more amphoteric surfactants.

17. Process according to any one of the preceding claims, in which the washing composition also comprises a conditioning agent chosen from silicones and cationic polymers.

18. Process according to any one of the preceding claims, in which the care composition comprises a conditioning agent chosen from silicones, cationic polymers and cationic surfactants.

19. Kit comprising:

- a washing composition comprising one or more surfactants; and/or

- a care composition comprising at least one conditioning agent, and

- a styling composition comprising one or more organic solvents and one or more fixing polymers, the fixing polymer(s) being at least partially soluble in the styling composition and being capable of precipitating on the hair when the styling composition is diluted with an aqueous composition.