WO2013045379A1 - Method for the temporary coloured shaping of keratinous fibres - Google Patents

Abstract

The present invention relates to a method for the cosmetic treatment of keratinous fibres in which a composition comprising, in a cosmetically acceptable medium, one or more fixing polymer(s) and one or more colouring agent(s) is sprayed over the keratinous fibres using an airbrush.

Description

METHOD FOR THE TEMPORARY COLOURED SHAPING OF KERATINOUS

FIBRES

The present invention relates to a method for the cosmetic treatment of keratinous fibres, in particular the hair, comprising the spraying of a composition by means of an airbrush. The invention relates in particular to a method for the temporary shaping of the hairstyle.

The temporary shaping of the hairstyle is the last act which allows the hairstylist to enhance the cutting carried out.

The styling products which make possible fixing and modularity used by hairstylists are generally liquid products. They are vaporized by aerosol container or pump-action spray systems. These systems make it possible to dispense the necessary dose in tailor-made fashion but they do not make it possible to obtain very great accuracy, for example making it possible to treat only one lock among others.

Products for the temporary dyeing of the hair can also be used to give an additional visual effect to the hairstyle. Products for the temporary dyeing of the hair are today present either in the solid form, in particular in the form of a mascara, grape, gels, creams, and the like, or in the aerosol form. The former are difficult to distribute and the latter lack the accuracy necessary to produce a subtle colour.

The document JP2003-081762 describes in particular a dyeing composition distributed in the aerosol form.

There thus exists a need to further improve the methods for the temporary shaping of the hairstyle associated with a colouring effect.

There thus more particularly exists a need to easily and accurately shape a hairstyle while modifying its colour.

It is an aim of the present invention precisely to satisfy these needs.

The invention relates, according to one of its aspects, to a method for the cosmetic treatment of keratinous fibres in which a composition comprising, in a cosmetically acceptable medium, one or more fixing polymer(s) and one or more colouring agent(s) is sprayed over the keratinous fibres using an airbrush. The method of the invention makes it possible to accurately deposit, whether in terms of amount or in terms of location, a fixing composition which makes it possible to shape the head of hair. As the composition additionally comprises one or more colouring agent(s), the method of the invention at the same time makes it possible to additionally set off the head of hair via a colour effect.

According to another aspect, the invention relates to a spraying system comprising:

- an airbrush,

- one or more removable containers each containing a composition comprising one or more fixing polymer(s) and one or more colouring agent(s).

According to another aspect, the invention also relates to the use of an airbrush for the coloured shaping of a hairstyle.

In that which follows, the expression "at least one" is equivalent to the expression "one or more".

The term "cosmetically acceptable medium" is understood to mean a medium which is compatible with keratinous substances and in particular the hair.

The cosmetically acceptable medium can comprise water or a mixture of water and one or more organic solvents or a mixture of organic solvents.

The cosmetically acceptable organic solvent(s) can be chosen in particular from lower C₂-C₄ monoalcohols, such as ethanol, isopropanol, tert- butanol or n-butanol; organic solvents which are soluble or dispersible in water, in particular C₃-C₄ ketones, such as acetone and methyl ethyl ketone; propylene carbonate or benzyl alcohol; and their mixtures.

Preferably, the composition is alcoholic or aqueous-alcoholic, the preferred alcohol being ethanol.

The composition used in the method according to the invention comprises one or more fixing polymers.

The term "fixing polymer" is understood to mean any polymer capable of conferring a shape on a head of hair or of retaining a head of hair in a given shape. The fixing polymer can be chosen from cationic, anionic, amphoteric and non-ionic fixing polymers.

Preferably, the fixing polymer is chosen from anionic, amphoteric and non-ionic fixing polymers.

The fixing polymers can be soluble in the aqueous-alcoholic or alcoholic medium or insoluble in this same medium and used in this case in the form of dispersions of solid or liquid polymer particles, such as latices or pseudolatices.

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

The carboxylic groups are provided by unsaturated mono- or dicarboxylic acid monomers, such as those corresponding to the formula (I):

in which n is an integer from 0 to 10, denotes a methylene group, optionally connected to the carbon atom of the unsaturated group or to the adjacent methylene group when n is greater than 1 , via a heteroatom, such as oxygen or sulfur, R₇ denotes a hydrogen atom or a phenyl or benzyl group, R₈ denotes a hydrogen atom or a lower alkyl or carboxyl group, and R₉ denotes a hydrogen atom, a lower alkyl group or a -CH₂-COOH, phenyl or benzyl group.

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

The anionic fixing polymers comprising carboxylic groups which are preferred according to the invention are: A) Copolymers of acrylic or methacrylic acid or their salts and of acrylamide, sold in the form of their sodium salts under the names Reten 421 , 423 or 425 by Hercules;

B) Copolymers of acrylic or methacrylic acid with a monoethylenic monomer, such as ethylene, styrene, vinyl esters or acrylic or methacrylic acid esters, optionally grafted to 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 in particular in Luxembourgian Patent Applications 75370 and 75371 or provided under the name Quadramer by American Cyanamid. Mention may also be made of copolymers of acrylic acid and of Ci-C₄ alkyl methacrylate and terpolymers of vinylpyrrolidone, of acrylic acid and of Ci-C₂o alkyl methacrylate, for example lauryl methacrylate, such as that sold by ISP under the name Acrylidone^® LM, and methacrylic acid/ethyl acrylate/tert-butyl acrylate terpolymers, such as the product sold under the name Luvimer^® 100 P by BASF.

Mention may also be made of methacrylic acid/acrylic acid/ethyl acrylate/methyl methacrylate copolymers as an aqueous dispersion, sold under the name Amerhold^® DR 25 by Amerchol.

C) Crotonic acid copolymers, such as those comprising, in their chain, vinyl acetate or propionate units and optionally other monomers, such as allyl or methallyl esters, vinyl ether or vinyl ester of a saturated and linear or branched carboxylic acid having a long hydrocarbon chain, such as those comprising at least 5 carbon atoms, it being possible for these polymers optionally to be grafted or crosslinked, or alternatively another vinyl, allyl or methallyl ester monomer of an a- or β-cyclic carboxylic acid. Such 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 which come within this category are the resins 28-29-30, 26-13-14 and 28-13-10, sold by National Starch. D) Copolymers of monounsaturated C₄-C₈ carboxylic acids or anhydrides chosen from:

- copolymers comprising (i) one or more maleic, fumaric or itaconic acids or anhydrides and (ii) one or more monomers chosen from vinyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives or acrylic acid and its esters, the anhydride functional groups of these copolymers optionally being monoesterified or monoamidated. Such polymers are described in particular in US Patents 2 047 398, 2 723 248 and 2 102 1 13, and in GB Patent 839 805. Commercial products are in particular those sold under the names Gantrez^® AN or ES by ISP,

- copolymers comprising (i) one or more maleic, citraconic or itaconic anhydride units and (ii) one or more monomers chosen from allyl or methallyl esters optionally comprising one or more acrylamide, methacrylamide, a-olefin, acrylic or methacrylic ester, acrylic or methacrylic acid or vinylpyrrolidone groups in their chain, the anhydride functional groups of these copolymers optionally being monoesterified or monoamidated. These polymers are described, for example, in French Patents 2 350 384 and 2 357 241 of the Applicant Company.

E) Polyacrylamides comprising carboxylate groups.

The homopolymers and copolymers comprising sulfonic groups are polymers comprising vinylsulfonic, styrenesulfonic, naphthalenesulfonic or acrylamidoalkylsulfonic units.

These polymers can be chosen in particular from:

- polyvinylsulfonic acid salts having a molecular weight of between approximately 1000 and 100 000, and also copolymers with an unsaturated comonomer, such as acrylic or methacrylic acids and their esters, and also acrylamide and its derivatives, vinyl ethers and vinylpyrrolidone,

- polystyrenesulfonic acid salts, such as the sodium salts sold, for example, under the names Flexan^® 500 and Flexan^® 130 by National Starch, these compounds being described in Patent FR 2 198 719, - polyacrylamidosulfonic acid salts, such as those mentioned in Patent US 4 128 631 , and more particularly polyacrylamidoethylpropanesulfonic acid, sold under the name Cosmedia Polymer HSP 1 180 by Henkel.

Mention may be made, as other anionic fixing polymer which can be used according to the invention, of the branched block anionic polymer sold under the name Fixate G-100 by Noveon.

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

Preference is more particularly given, among the abovementioned anionic fixing polymers, to the use, in the context of the present invention, of monoesterified methyl vinyl ether/maleic anhydride copolymers, sold under the name Gantrez^® ES 425 by ISP, acrylic acid/ethyl acrylate/N-tert- butylacrylamide terpolymers, sold under the name Ultrahold^® Strong by BASF, copolymers of methacrylic acid and methyl methacrylate, sold under the name Eudragit^® L by Rohm Pharma, 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 National Starch, copolymers of methacrylic acid and ethyl acrylate, sold under the name Luvimer^® MAEX or MAE by BASF, vinyl pyrrol idone/acrylic acid/lauryl methacrylate terpolymers, sold under the name Acrylidone^® LM by ISP, and the polymer sold under the name Fixate G-100 by Noveon.

The amphoteric fixing polymers which can be used in accordance with the invention can be chosen from polymers comprising units B and C distributed randomly in the polymer chain, where B denotes a unit deriving from a monomer comprising one or more basic nitrogen atoms and C denotes a unit deriving from an acid monomer comprising one or more carboxylic or sulfonic groups, or alternatively B and C can denote groups deriving 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 carries a carboxylic or sulfonic group connected via a hydrocarbon group, or alternatively B and C form part of a chain of a polymer comprising an α,β-dicarboxylic ethylene unit in which one of the carboxylic groups has been made to react with a polyamine comprising one or more primary or secondary amine groups.

The amphoteric fixing polymers corresponding to the definition given above which are more particularly preferred are chosen from the following polymers:

(1 ) Copolymers having acidic vinyl units and basic vinyl units, such as those resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group, such as, more particularly, acrylic acid, methacrylic acid, maleic acid or a-chloroacrylic acid, and a basic monomer derived from a substituted vinyl compound comprising one or more basic atoms, such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, and dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in Patent US 3 836 537.

(2) Polymers comprising units deriving:

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

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

The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are compounds in which the alkyl groups comprise 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, Ν,Ν'- dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

Use is made in particular of the copolymers whose CTFA name (4th edition, 1991 ) is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the name Amphomer^® or Lovocryl^® 47 by National Starch.

(3) Crosslinked and acylated polyaminoamides partially or totally deriving from polyaminoamides of general formula (II):

CO— F^— CO Z

(II) in which R ₀ represents a divalent group derived from a saturated dicarboxylic acid, from an aliphatic mono- or dicarboxylic acid comprising an ethylenic double bond, from an ester of a lower alkanol, having from 1 to 6 carbon atoms, of these acids, or from a group deriving from the addition of any one of the said acids to a bis(primary) or bis(secondary) amine, and Z denotes a group deriving from a bis(primary), mono- or bis(secondary) polyalkylene-polyamine and preferably represents:

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

in which x = 2 and p = 2 or 3, or x = 3 and p = 2, this group deriving from diethylenetriamine, triethylenetetramine or dipropylenetriamine,

b) in proportions of from 0 to 40 mol%, the group of formula (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 deriving from hexamethylenediamine, these polyaminoamides being crosslinked by an addition reaction of a bifunctional 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 polyaminoamide, and acylated by the action of acrylic acid, chloroacetic acid or an alkane sultone, or their salts.

The saturated carboxylic acids are preferably chosen from acids having from 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid, terephthalic acid or acids comprising an ethylenic double bond, such as, for example, acrylic acid, methacrylic acid or itaconic acid.

The alkane sultones used in the acylation are preferably propane sultone or butane sultone, the salts of the acylating agents preferably being the sodium or potassium salts. (4) Polymers comprising zwitterionic units of formula (IV):

in which Rn denotes a polymerizable unsaturated group, such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer from 1 to 3, Ri₂ and Ri₃ represent a hydrogen atom or a methyl, ethyl or propyl group, and Ri₄ and Ri₅ represent a hydrogen atom or an alkyl group, such that the sum of the carbon atoms in R ₄ and Ri₅ 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.

Mention may be made, by way of example, of methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate copolymers, such as the product sold under the name Diaformer Z301 by Sandoz.

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

the unit (D) being present in proportions of between 0% and 30%, the unit (E) in proportions of between 5% and 50% and the unit (F) in proportions of between 30% and 90%, it being understood that, in this unit (F), R ₆ represents a group of formula:

in which, if q = 0, R17, Ri₈ and Ri₉, which are identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamino residue or a dialkylamino residue, which are optionally interrupted by one or more nitrogen atoms and/or optionally substituted by one or more amino, hydroxyl, carboxyl, alkylthio or sulfonic groups, or an alkylthio residue in which the alkyl group carries an amino residue, at least one of the groups Ri₇, Ri₈ and R19 being, in this case, a hydrogen atom,

or, if q = 1 , R ₇, R ₈ and R19 each represent a hydrogen atom, and also the salts formed by these compounds with bases or acids.

(6) Polymers corresponding to the general formula (V) are described, for example, in French Patent 1 400 366:

in which R₂₀ represents a hydrogen atom, a -O-CH₃, -O-CH₂-CH₃ or phenyl group, R₂i denotes a hydrogen atom or a lower alkyl group, such as methyl or ethyl, R₂₂ denotes a hydrogen atom or a lower d-C₆ alkyl group, such as methyl or ethyl, R₂₃ denotes a lower d-C₆ alkyl group, such as methyl or ethyl, or a group corresponding to the formula: -R₂₄-N(R₂₂)2, R₂₄ representing a -CH₂-CH₂-, -CH₂-CH₂-CH₂- or -CH₂-CH(CH₃)- group and R₂₂ having the abovementioned meanings.

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

(8) Amphoteric polymers of the -D-X-D-X- type chosen from:

a) polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula (VI): -D-X-D-X-D- (VI) where D denotes a group

and X denotes the symbol E or E', E or E', which are identical or different, denoting a divalent group which is an alkylene group having a straight or branched chain, comprising up to 7 carbon atoms in the main chain, which is unsubstituted or substituted by hydroxyl groups and which can additionally comprise oxygen, nitrogen and sulfur atoms and from 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 (VI'): -D-X-D-X- (VI')

/ \

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' being a divalent group which is an alkylene group comprising a straight or branched chain, having up to 7 carbon atoms in the main chain, which group is unsubstituted or substituted by one or more hydroxyl groups and comprises one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain, optionally interrupted by an oxygen atom and necessarily comprising one or more carboxyl functional groups or one or more hydroxyl functional groups 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 N,N- dialkylaminoalkanol. These copolymers can also comprise other vinyl comonomers, such as vinylcaprolactam.

Mention will be made, among the abovementioned most particularly preferred amphoteric fixing polymers according to the invention, of those of family (3), such as the copolymers whose CTFA name is octylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, such as the products sold under the names Amphomer^®, Amphomer^® LV 71 or Lovocryl^® 47 by National Starch, and those of family (4), such as methyl methacrylate/methyl dimethylcarboxymethylammonioethyl methacrylate copolymers, sold, for example, under the name Diaformer Z301 by Sandoz.

The non-ionic fixing polymers which can be used according to the present invention are chosen, for example, from:

- polyalkyloxazolines;

- vinyl acetate homopolymers;

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

- homopolymers and copolymers of acrylic esters, such as, for example, copolymers of alkyl acrylates and alkyl methacrylates, such as the products provided by Rohm & Haas under the names Primal^® AC-261 K and Eudragit^® NE 30 D, by BASF under the name 8845 or by Hoechst under the name Appretan^® N9212, - copolymers of acrylonitrile and a non-ionic monomer chosen, for example, from butadiene and alkyl (meth)acrylates, such as the products provided under the name CJ 0601 B by Rohm & Haas,

- styrene homopolymers;

- styrene copolymers, such as, for example, copolymers of styrene and alkyl (meth)acrylate, such as the products Mowilith^® LDM 691 1 , Mowilith^® DM 61 1 and Mowilith^® LDM 6070, provided by Hoechst, and the products Rhodopas^® SD 215 and Rhodopas^® DS 910, provided by Rhone-Poulenc, copolymers of styrene, alkyl methacrylate and alkyl acrylate, copolymers of styrene and butadiene, or copolymers of styrene, butadiene and vinylpyridine,

- polyamides,

- vinyllactam homopolymers, such as vinylpyrrolidone homopolymers and polyvinylcaprolactam, sold under the name Luviskol^® Plus by BASF, and

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

The alkyl groups of the abovementioned non-ionic polymers preferably have from 1 to 6 carbon atoms.

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

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

These polymers can be anionic, amphoteric or non-ionic and they are preferably anionic or non-ionic. Such polymers are, for example, copolymers capable of being obtained by radical polymerization starting from the monomer mixture formed:

a) of 50% to 90% by weight of terf-butyl acrylate,

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

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

CH₂ = -CH₃

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

Other examples of grafted silicone polymers are in particular polydimethylsiloxanes (PDMSs) to which mixed polymer units of the poly(meth)acrylic acid type and of the poly(alkyl (meth)acrylate) type are grafted via a thiopropylene-type connecting link and polydimethylsiloxanes (PDMSs) to which polymer units of the poly(isobutyl (meth)acrylate) type are grafted via a thiopropylene-type connecting link.

Mention may be made, as other type of silicone fixing polymers, of the product Luviflex^® Silk sold by BASF.

Use may also be made, as fixing polymers, of functionalized or non- functionalized, silicone or non-silicone, anionic, amphoteric or non-ionic polyurethanes, or their mixtures.

The polyurethanes particularly targeted by the present invention are those described in Applications EP 0 751 162, EP 0 637 600, EP 0 648 485 and FR 2 743 297, of which the Applicant Company is the Proprietor, and in Applications EP 0 656 021 and WO 94/03510 of BASF and EP 0 619 1 1 1 of National Starch.

Mention may be made, as polyurethanes which are particularly well suited to the present invention, of the products sold under the names Luviset PUR^® and Luviset^® Si PUR by BASF. Preferably, the fixing polymer(s) are present in concentrations varying from 0.1 % to 30% by weight, preferably from 0.5% to 15% by weight and better still from 1 % to 10% by weight, with respect to the total weight of the composition.

The composition used in the method according to the invention also comprises one or more colouring agent(s).

The colouring agent(s) can be chosen from direct dyes, coloured polymers or pigments.

The colouring agent can be soluble or insoluble in the cosmetically acceptable medium of the composition.

The term "insoluble in the cosmetically acceptable medium" is understood to mean with a solubility of less than 0.1 % at 25°C and at atmospheric pressure in the cosmetically acceptable medium.

According to one embodiment, the composition comprises one or more direct dyes.

The term "direct dye" is understood to mean natural and/or synthetic dyes, other than oxidation dyes, capable of modifying the colour of keratinous fibres without use of other compounds, such as oxidizing agents.

The direct dye(s) are soluble in the cosmetically acceptable medium.

They can be ionic or non-ionic, preferably cationic or non-ionic.

These direct dyes are chosen, for example, from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

Mention may be made, as examples of suitable direct dyes, of azo direct dyes; (poly)methine dyes, such as cyanines, hemicyanines and styryl dyes; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrins; phthalocyanines and natural direct dyes, alone or as mixtures.

Mention may be made, as direct dye according to the invention, of the following dyes: acridines; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthrones; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis-isoindolines; carboxanilides; coumarins; cyanines, such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids, such as flavanthrones and flavones; fluorindines; formazans; indamines; indanthrones; indigoids and pseudoindigoids; indophenols; indoanilines; isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methines, such as dimethines of stilbene or styryl types; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, in particular nitro(hetero)aromatics; oxadiazoles; oxazines; perylones; perynones; perylenes; phenazines; phenoxazines; phenothiazines; phthalocyanines; polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones; pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines; quinophthalones; squaranes; tetrazoliums; thiazines; thioindigos; thiopyronines; triarylmethanes or xanthenes.

When they are cationic, the direct dye(s) which are soluble in the medium of the compositions of the invention preferably comprise a least one quaternary ammonium chromophore or at least one chromophore carrying a quaternary ammonium or quaternizable group.

According to a specific embodiment of the invention, the direct dyes comprise at least one quaternized cationic chromophore.

Mention may in particular be made, for the cationic azo dyes, of those resulting from the cationic dyes described in the Kirk-Othmer Encyclopedia of Chemical Technology, "Dyes, Azo", J. Wiley & Sons, updated on 19/04/2010.

Mention may be made, among the azo dyes which can be used according to the invention, of the cationic azo dyes described in Patent Applications WO 95/15144, WO 95/01772 and EP 714 954.

According to a preferred embodiment of the invention, the direct dye(s) are chosen from cationic dyes known as "basic dyes". Mention may be made, among the azo dyes described in the Colour Index International, 3rd edition, in particular of the following compounds:

-Basic Red 22

-Basic Red 76

-Basic Yellow 57

-Basic Brown 16

-Basic Brown 17.

Among the cationic quinone dyes, those mentioned in the abovementioned Colour Index International are suitable and, among these, mention may be made, inter alia, of the following dyes:

-Basic Blue 22

-Basic Blue 99.

Among the azine dyes which are suitable, mention may be made of those listed in the Colour Index International, for example of the following dyes:

-Basic Blue 17

-Basic Red 2.

Among the cationic triarylmethane dyes which may be used according to the invention, mention may be made, in addition to those listed in the Colour Index, of the following dyes:

-Basic Green 1

-Basic Violet 3

-Basic Violet 14

-Basic Blue 7

-Basic Blue 26.

Mention may also be made of the cationic dyes described in the documents US 5 888 252, EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954. Mention may also be made of those listed in the encyclopaedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the "Kirk-Othmer Encyclopedia of Chemical Technology", in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons. Preferably, the cationic direct dyes are chosen from those resulting from dyes of azo and hydrazono type.

According to a specific embodiment, the direct dyes are cationic azo dyes described in EP 850 636, FR 2 788 433, EP 920 856, WO 99/48465, FR 2 757 385, EP 850 637, EP 918 053, WO 97/44004, FR 2 570 946, FR 2 285 851 , DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540 423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137 005, WO 01 /66646, US 5 708 151 , WO 95/01772, WO 515 144, GB 1 195 386, US 3 524 842, US 5 879 413, EP 1 062 940, EP 1 133 976, GB 738 585, DE 2 527 638, FR 2 275 462, GB 1974-27645, Acta Histochem. (1978), 61 (1 ), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim., (1970), 40(1 ), 195-202; Ann. Chim. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1 ), 209-21 1 ; Rev. Roum. Chim. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chim. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; MRL Bull. Res. Dev. (1992), 6(2), 21 -7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Dyes Pigm. (1992), 19(1 ), 69-79; Dyes Pigm. (1989), 1 1 (3), 163-72.

Preferably, the cationic direct dye(s) comprise a quaternary ammonium group; more preferentially, the cationic charge is endocyclic.

These cationic radicals are, for example, a cationic radical :

having an exocyclic (di/tri)(Ci-C₈)alkylammonium charge, or

- having an endocyclic charge, such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bipyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthoxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phenazinium, phenoxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium or xanthylium. Mention may be made of the hydrazono cationic dyes of formulae (VII) and (VIII) and the azo cationic dyes of formulae (IX) and (X) below:

Het⁺-C(R_a)=N-N(R_b)-ArQ^" Het⁺-N(R_a)-N=C(R_b)-ArQ^"

(VII) (VIII)

Het⁺-N=N-ArQ^" Ar⁺-N=N-Ar"Q^"

(IX) (X) in which formulae (VII) to (X):

• Het⁺ represents a cationic heteroaryl radical, preferentially having an endocyclic cationic charge, such as imidazolium, indolium or pyridinium, which is optionally substituted, preferentially by at least one (CrC₈)alkyl group, such as methyl;

· Ar⁺ represents an aryl radical, such as phenyl or naphthyl, having an exocyclic cationic charge, preferentially ammonium, particularly tri(Ci- C₈)alkylammonium, such as trimethylammonium;

• Ar represents an aryl group, in particular a phenyl group, which is optionally substituted, preferentially by one or more electron-donating groups, such as i) optionally substituted (CrC₈)alkyl, ii) optionally substituted (CrC₈)alkoxy, iii) (di)(Ci-C₈)(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C C₈)alkylamino, v) optionally substituted N-(Ci-C₈)alkyl-N-aryl(Cr C₈)alkylamino or alternatively Ar represents a julolidine group;

· Ar" represents an optionally substituted (hetero)aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferentially by one or more (Ci-C₈)alkyl, hydroxyl, (di)(Ci-C₈)(alkyl)amino, (Ci-C₈)alkoxy or phenyl groups;

• R_a and R_b, which are identical or different, represent a hydrogen atom or a (C-i-Cs)alkyl group which is optionally substituted, preferentially by a hydroxyl group; • or else the R_a substituent with a substituent of Het⁺ and/or R_b with a substituent of Ar form, together with the atoms which carry them, a (hetero)cycloalkyl; in particular, R_a and R_b represent a hydrogen atom or a (Ci-C₄)alkyl group optionally substituted by a hydroxyl group;

· Q^" represents an organic or inorganic anionic counterion, such as a halide or an alkyl sulfate.

Mention may in particular be made of the azo and hydrazono direct dyes having an endocydic cationic charge of formulae (VII) to (X) as defined above, more particularly, the cationic direct dyes of formulae (II) to (V) having an endocydic cationic charge described in Patent Applications WO 95/15144, WO

95/01772 and EP 714 954, preferentially the following direct dyes:

(IX-1 )

in which formulae (VII-1 ) and (IX-1 ):

- R¹ represents a (Ci-C₄)alkyl group, such as methyl;

- R² and R³, which are identical or different, represent a hydrogen atom or a (Ci-C₄)alkyl group, such as methyl; and

- R⁴ represents a hydrogen atom or an electron-donating group, such as (d- C₈)alkyl which is optionally substituted, (CrC₈)alkoxy which is optionally substituted or (di)(Ci-C₈)(alkyl)amino which is optionally substituted on the alkyl group(s) by a hydroxyl group; in particular, R⁴ is a hydrogen atom,

- Z represents a CH group or a nitrogen atom, preferentially CH,

- Q^" is an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

In particular, the dyes of formulae (VII-1 ) and (IX-1 ) are chosen from Basic Red 51 , Basic Yellow 87 and Basic Orange 31 or their derivatives:

Basic Red 51 Basic Orange 31 Basic Yellow 87 with Q^" an anionic counterion as defined above, in particular a halide, such as chloride, or an alkyl sulfate, such as methyl sulfate or mesityl.

According to a specific embodiment of the invention, the direct dyes are fluorescent, i.e. they comprise at least one fluorescent chromophore as defined above.

Mention may be made, as fluorescent dyes, of the radicals resulting from the following dyes: acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1 H-pyrrolato-kN}borons (BODIPY^®), diketopyrrolopyrroles, fluorindines, (poly)methines (in particular cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamines (such as dansyls), oxadiazoles, oxazines, perylones, perynones, perylenes, polyenes/carotenoids, squaranes, stilbenes and xanthenes.

Mention may also be made of the fluorescent dyes described in the documents EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954 and those listed in the encyclopaedia "The Chemistry of Synthetic Dyes" by K. Venkataraman, 1952, Academic Press, vol. 1 to 7, in the "Kirk-Othmer Encyclopedia of Chemical Technology", in the chapter "Dyes and Dye Intermediates", 1993, Wiley and Sons, and in various chapters of "Ullmann's Encyclopedia of Industrial Chemistry", 7th edition, Wiley and Sons, and in the handbook — "A Guide to Fluorescent Probes and Labeling Technologies", 10th Ed., Molecular Probes/lnvitrogen - Oregon 2005, circulated on the Internet or in the preceding printed editions. Mention may be made, among the natural direct dyes which can be used according to the invention, of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orceins. Use may also be made of extracts or decoctions comprising these natural dyes and in particular henna- based cataplasms or extracts.

According to another embodiment, the composition comprises one or more coloured polymers.

The term "coloured polymer" is understood to mean a polymer which is coloured, that is to say which absorbs light in the visible spectrum, namely at a wavelength preferably of between 300 nm and 750 nm inclusive, and which has the ability to dye keratinous fibres, such as the hair.

The coloured polymer can be anionic, cationic or neutral. The coloured polymer according to the invention comprises:

a) a polymeric backbone to which one or more identical or different chromophores absorbing light in the visible region (300 nm to 750 nm) is grafted, or else

b) a backbone consisting of identical or different polymerized chromophores absorbing light in the visible region, or else

c) a backbone consisting of identical or different polymerized chromophores absorbing light in the visible region to which one or more identical or different chromophores absorbing light in the visible region is grafted. The chromophore(s) preferably result from direct dyes as defined above. According to a preferred embodiment, the coloured polymer is a). More particularly, the polymer a) comprises cationic chromophores.

According to another specific embodiment of the invention, the coloured polymer is b). More particularly, it results from the oxidative polymerization of oxidation bases and/or couplers used in hair dyeing.

The coloured polymer can be a polymer comprising at least one organic dye group. The dye group can be grafted, in particular via a covalent bond, to the polymer chain. The coloured polymer generally comprises less than 10% by weight of colouring material, with respect to the total weight of the polymer. This coloured polymer can be of any chemical nature, in particular polyester, polyamide, polyurethane, polyacrylic, poly(meth)acrylic or polycarbonate, of natural origin, such as cellulose polymers or chitosan, or one of their mixtures, in particular a polyester or polyurethane.

In particular, the coloured polymer can be a copolymer based on at least two separate monomers, at least one of which is an organic dye monomer.

Such coloured polymers are described in particular in Patents or Patent Applications US 5 032 670, US 4 999 418, US 5 106 942, US 5 030 708, US 5 102 980, US 5 043 376, US 5 104 913, US 5 281 659, US 5 194 463, US 4 804 719, WO 92/07913 and EP A 747 036.

Mention may in particular be made, by way of illustration of monomers for known coloured polymers, of anthraquinones, methines, bis-methines, aza- methines, arylidenes, 3H-dibenzo[7,i-j] isoquinolines, 2,5- diarylaminoterephthalic acids and their esters, phthaloylphenothiazines, phthaloylphenoxazines, phthaloylacridones, anthrapyrimidines, anthrapyrazoles, phthalocyanines, quinophthalones, indophenols, perynones, nitroarylamines, benzodifuran, 2H-1 -benzopyran-2-ones, quinophthalones, perylenes, quinacridones, triphenodioxazines, fluoridines, 4-amino-1 ,8- naphthalimides, thioxanthrones, benzanthrones, indanthrones, indigo, thioindigo, xanthene, acridine, azine and oxazine.

This coloured polymers can be soluble or insoluble in the medium. In the latter case, they can be provided in the form of coloured latexes.

A person skilled in the art is, of course, able, from his general knowledge, to choose the monomers in order to adjust the colour effect desired according to the invention.

According to another embodiment, the composition used in the method of the invention can comprise one or more pigments.

The term "pigment" is understood to mean a white or coloured solid particle which is naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which is rendered insoluble by formulation in the form of a lake, if appropriate. More particularly, the pigment has little or no solubility in aqueous/alcoholic media. Mention may be made, as pigment, of organic and inorganic pigments, such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry, "Pigments, Organic", 2005, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 , and ibid, "Pigments, Inorganic, 1 . General", 2009, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheiml 0.1002/14356007.a20_243.pub3,

azo pigments which comprise one or more azo groups A-N=N-B, with A representing an optionally substituted (hetero)aryl, B representing an optionally substituted (hetero)aryl or

A' representing an optionally substituted (hetero)aryl and R representing a hydrogen atom or a (CrC₆)alkyl group, with the A, A' and B groups being (hetero)aryls which do not comprise solubilizing groups, such as -SO₃H or -COOH.

They can in particular be monoazo pigments, including β-naphthols, monoazopyrrolone pigments or benzimidazolone pigments; diazo pigments, such as diazodiarylide pigments and bis(N-acetoacetarylide) pigments, or triazo or tetraazo pigments.

Mention may also be made of azo metal complex pigments.

Other pigments are also advantageous; they are isoindolinone and isoindoline pigments; phthalocyanine pigments; quinacridone pigments; perynone pigments; perylene pigments; anthraquinone pigments, such as hydroxyanthraquinone pigments; aminoanthraquinone pigments, including acylaminoanthraquinones and azoanthraquinone pigments; heterocyclic anthraquinones; polycarboxylic anthraquinone pigments; pyranthrone pigments; anthranthrone pigments; diketopyrrolopyrrole (DPP) pigments; thioindigo pigments; dioxazine pigments; triphenylmethane pigments; quinophthalone pigments; and fluorescent pigments.

When the dyes comprise one or more solubilizing groups, such as -SO₃H or -COOH, these dyes are rendered insoluble and consequently pigments by formation of a lake, i.e. by salification (e.g., Na, Ca, St, Ba, and the like), and divided mainly into β-naphthol and 2-hydroxy-3-naphthoic acid pigments "(BON) pigment lakes". In the context of the present invention, the pigment can be at least partly organic.

According to one embodiment of the invention, the pigment is an organic pigment.

According to another embodiment of the invention, the pigment is an inorganic pigment.

Mention may be made, as illustration of the pigments which can be used in the present invention, of carbon black, titanium oxide, chromium oxide, pigments of D&C or FD&C type and their lakes, and in particular those known under the names D&C Blue No. 4, D&C Brown No. 1 , FD&C Green No. 3, D&C Green No. 5, D&C Green No. 6, FD&C Green No. 8, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10, D&C Orange No. 1 1 , FD&C Red No. 4, D&C Red No. 6, D&C Red No. 7, D&C Red No. 17, D&C Red No. 21 , D&C Red No. 22, D&C Red No. 27, D&C Red No. 28, D&C Red No. 30, D&C Red No. 31 , D&C Red No. 33, D&C Red No. 34, D&C Red No. 36, FD&C Red No. 40, FD&C Red 40 lake, D&C Violet No. 2, Ext. D&C Violet No. 2, FD & C Blue No. 1 , D&C Yellow No. 6, FD&C Yellow No. 6, D&C Yellow No. 7, Ext. D&C Yellow No. 7, D&C Yellow No. 8, D&C Yellow No. 10 or D&C Yellow No. 1 1 , it being understood that, when the said pigment is not naturally insoluble in the hydrophilic and lipophilic phases usually employed in cosmetics, it is used in the form of a corresponding lake, as explained above.

Mention may in particular be made, as examples of lakes, of lakes based on barium, strontium, calcium or aluminium, or alternatively diketopyrrolopyrroles.

Mention may in particular be made, as other examples of pigments which can be used in the present invention, of inorganic pigments, optionally surface- treated and/or coated, and in particular titanium dioxide, zirconium oxide or cerium oxide, and also zinc oxide, iron oxide (black, yellow or red) or chromium oxide, manganese violet, ultramarine blue, chromium hydrate and ferric blue, or alternatively metal powders, such as aluminium powder, copper powder, gold powder and silver powder. Mention may also be made of pigments having an optical effect, such as particles comprising a natural or synthetic and organic or inorganic substrate, for example glass, acrylic resins, polyester, polyurethane, polyethylene terephthalate, ceramics or aluminas, the said substrate being covered or not covered with metal substances, such as aluminium, gold, silver, platinum, copper or bronze, or with metal oxides, such as titanium dioxide, iron oxide or chromium oxide.

They can also be pearlescent agents.

The term "pearlescent agents" should be understood as meaning iridescent pigments which are in particular produced by certain molluscs in their shells or which alternatively are synthesized.

The pearlescent pigments can be chosen from mica covered with titanium dioxide or with bismuth oxychloride, titanium dioxide-coated mica covered with iron oxides, titanium dioxide-coated mica covered in particular with ferric blue or with chromium oxide, titanium dioxide-coated mica covered with an organic pigment of the abovementioned type, and also pearlescent pigments based on bismuth oxychloride. Use may also be made of interference pigments, in particular liquid-crystal or multilayer pigments.

They can also be pigments having a structure which can be, for example, of sericite/brown iron oxide/titanium dioxide/silica type.

They can also be pigments having a structure which can be, for example, of the type consisting of microspheres of silica comprising iron oxide.

Mention may in particular be made, as examples of pigments which are very particularly suitable for use in the present invention, of D&C Red No. 7, titanium oxide, chromium oxide and lakes of the pigments of D&C and FD&C type mentioned above, in particular D&C Red No. 22 lake, Yellow No. 6 lake and FD&C Blue No. 1 lake.

The pigments in accordance with the invention can be provided in the form of a powder or of a pigment paste. They can be coated or uncoated.

The pigments in accordance with the invention can be chosen, for example, from white or coloured pigments, lakes, special effect pigments, such as pearlescent agents or glitter, and their mixtures. Mention may be made, as examples of white or coloured inorganic pigments, of zirconium oxide or cerium oxide, chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue.

Mention may be made, as examples of white or coloured organic pigments, of compounds of the following types: nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, of metal complex type, isoindolinone, isoindoline, quinacridone, perynone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone.

In particular, the white or coloured organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100 and 74160, the yellow pigments codified in the Color Index under the references CI 1 1680, 1 1710, 15985, 19140, 20040, 21 100, 21 108, 47000 and 47005, the green pigments codified in the Color Index under the references CI 61565, 61570 and 74260, the orange pigments codified in the Color Index under the references CI 1 1725, 15510, 45370 and 71 105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915 and 75470, and the pigments obtained by oxidative polymerization of indole or phenol derivatives such as described in Patent FR 2 679 771 .

Use may also be made of pigment pastes of organic pigments, such as the products sold by Hoechst under the names:

- Cosmenyl Yellow IOG: Pigment Yellow 3 (CI 1 1710);

- Cosmenyl Yellow G: Pigment Yellow 1 (CI 1 1680);

- Cosmenyl Orange GR: Pigment Orange 43 (CI 71 105);

- Cosmenyl Red R: Pigment Red 4 (CI 12085);

- Cosmenyl Carmine FB: Pigment Red 5 (CI 12490);

- Cosmenyl Violet RL: Pigment Violet 23 (CI 51319);

- Cosmenyl Blue A2R: Pigment Blue 15.1 (CI 74160); - Cosmenyl Green GG: Pigment Green 7 (CI 74260);

- Cosmenyl Black R: Pigment Black 7 (CI 77266).

The pigments in accordance with the invention can also be in the form of composite pigments, such as described in Patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising:

- an inorganic core,

- at least one binder for fixing the organic pigments to the core, and

- at least one organic pigment at least partially covering the core.

The term "lake" is understood to mean dyes adsorbed onto insoluble particles, the combination thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium. Mention may be made, among the organic dyes, of cochineal carmine.

Mention may be made, as examples of lakes, of the products known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850:1 ), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053) or D & C Blue 1 (CI 42 090).

The term "special effect pigments" is understood to mean pigments which generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain brightness) which is non-uniform and which changes as a function of the conditions of observation (light, temperature, angles of observation, and the like). They consequently contrast with white or coloured pigments which afford a conventional opaque, semi-transparent or transparent uniform hue.

Mention may be made, as examples of special effect pigments, of white pearlescent pigments, such as mica covered with titanium dioxide or with bismuth oxychloride, coloured pearlescent pigments, such as mica covered with titanium dioxide and with iron oxides, mica covered with titanium dioxide and in particular with ferric blue or with chromium oxide, or mica covered with titanium dioxide and with an organic pigment as defined above, and also pearlescent pigments based on bismuth oxychloride.

Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker), interference holographic glitter (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also comprise fluorescent pigments, whether substances which are fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, for example sold by Quantum Dots Corporation.

Quantum dots are luminescent semiconductor nanoparticles capable of emitting, under light excitation, radiation exhibiting a wavelength of between 400 nm and 700 nm. These nanoparticles are known from the literature. In particular, they can be manufactured according to the processes described, for example, in US 6 225 198 or US 5 990 479, in the publications which are cited therein and in the following publications: Dabboussi B.O. et al., "(CdSe)ZnS core-shell quantum dots: synthesis and characterisation of a size series of highly luminescent nanocristallites", Journal of Physical Chemistry B, vol. 101, 1997, pp 9463-9475, and Peng, Xiaogang et al., "Epitaxial growth of highly luminescent CdSe/CdS core/shell nanocrystals with photostability and electronic accessibility", Journal of the American Chemical Society, vol. 119, No. 30, pp 7019-7029.

The pigments in accordance with the invention are preferably coloured pigments.

The variety of the pigments involved makes it possible to obtain a wide palette of colours, and also specific optical effects, such as metallic or interference effects.

The size of a pigment other than the pearlescent agents is generally between 10 nm and 10 μιτι, preferably between 50 nm and 5 μιτι and more preferentially still between 100 nm and 3 μιτι. The size of a pearlescent agent is generally between 1 and 200 μητι, preferably between 5 and 150 μηη and more preferentially still between 15 and 50 μιτι.

Preferably, the colouring agent of the invention is a pigment.

More preferably still, the colouring agent of the invention is a pearlescent agent.

In the compositions of the invention, the colouring agent(s) preferably represent from 0.01 % to 30% by weight, better still from 0.1 % to 20% by weight and even better still from 0.1 % to 10% by weight, with respect to the total weight of the composition.

The composition can also comprise one or more thickening agents other than the fixing polymers of the invention which can be chosen from polymeric thickeners, which are natural or synthetic, anionic, amphoteric, zwitterionic, non-ionic or cationic and associative or non-associative, and non-polymeric thickeners, such as, for example, inorganic thickeners, an electrolyte or a sugar.

Mention may be made, as polymeric thickening agents, for example, of cellulose thickening agents, for example hydroxyethylcellulose, hydroxypropylcellulose and carboxymethylcellulose, guar gum and its derivatives, for example hydroxypropyl guar, sold by Rhodia under the reference Jaguar HP 105, gums of microbial origin, such as xanthan gum and scleroglucan gum, synthetic polymeric thickening agents, such as crosslinked homopolymers of acrylic acid or of acrylamidopropanesulfonic acid, for example Carbomer, or non-ionic, anionic or amphoteric associative polymers, such as the polymers sold under the names Pemulen TR1 or TR2 by Goodrich, Salcare SC90 by Allied Colloids, Aculyn 22, 28, 33, 44 or 46 by Rohm & Haas and Elfacos T210 and T212 by Akzo.

The thickening agents can be inorganic thickeners chosen from organophilic clays.

The organophilic clay can be chosen from montmorillonite, bentonite, hectorite, attapulgite and sepiolite, and their mixtures, which is optionally modified. The clay is preferably a bentonite or a hectorite. These clays can be modified with a chemical compound chosen from quaternary ammoniums, tertiary amines, amine acetates, imidazolines, amine soaps, fatty sulfates, alkylarylsulfonates and amine oxides, and their mixtures.

Mention may be made, as organophilic clays, of quaternium-18 bentonites, such as those sold under the names Bentone 3, Bentone 38 and Bentone 38V by Rheox, Tixogel VP by United Catalyst and Claytone 34, Claytone 40 and Claytone XL by Southern Clay; stearalkonium bentonites, such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst and Claytone AF and Claytone APA by Southern Clay; and quaternium-18/benzalkonium bentonites, such as those sold under the names Claytone HT and Claytone PS by Southern Clay.

The preferred inorganic thickening agents are chosen from hectorites or bentonites which are organomodified.

More particularly, the thickening agent used is a distearyldimethylammonium-modified hectorite sold by Elementis under the reference Bentone 38 CVG.

The composition can comprise pH adjusters. The pH adjusters can be acidifying or basifying agents.

Mention may be made, among the acidifying agents, by way of example, of inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, sulfuric acid or sulfonic acids.

Mention may be made, among the basifying agents, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines, and their derivatives, sodium hydroxide, potassium hydroxide and the compounds of following formula:

in which W is a propylene residue optionally substituted by a hydroxyl group or a Ci-C₄ alkyl radical and R_a, Rb, R_c and R_d, which are identical or different, represent a hydrogen atom or a Ci-C₄ alkyl or Ci-C₄ hydroxyalkyl radical. Preferably, the pH adjusters can be chosen from alkaline agents, such as aqueous ammonia, monoethanolamine, diethanolamine, triethanolamine, 1 ,3- propanediamine or an alkaline hydroxide, such as 2-amino-2-methyl-1 - propanol, or else acidifying agents, such as phosphoric acid or hydrochloric acid.

The composition used in the method of the invention can additionally comprise one or more additives chosen from non-ionic, anionic, cationic and amphoteric surface-active agents, silicones, ceramides and pseudoceramides, vitamins and provitamins, including panthenol, sunscreens, sequestering agents, plasticizing agents, solubilizing agents, stabilizing agents, antioxidants, anti-foaming agents, moisturizing agents, emollients, penetrating agents, conditioning polymers, fragrances and preservatives.

Of course, a person skilled in the art will take care to choose the optional additional compounds and/or their amounts so that the advantageous properties of the compositions used according to the invention are not, or not substantially, detrimentally affected by the envisaged addition.

According to the invention, the composition which has just been described is sprayed over the hair by means of an airbrush.

The invention may be better understood on reading the following detailed description of the airbrush and non-limiting implementational examples thereof and on examining the appended drawing, in which:

Figure 1 represents, diagrammatically and partially, the airbrush and an example of a system for feeding the airbrush with compressed air,

- Figure 2 represents a view in perspective of the airbrush.

Use is made, in order to spray the composition which has just been described, of an airbrush system 1 as illustrated in Figure 1 .

The airbrush system 1 can comprise, as illustrated, an airbrush 2 connected to a source of compressed gas, for example comprising an air compressor 4 connected to the airbrush 2 via a pressure regulator 5, in a way known per se, and a flexible tube 15. The source of compressed gas can also be an interchangeable or rechargeable capsule of compressed gas, for example of compressed air.

The airbrush 2 comprises, in a way known per se, a grasping part which is, for example, defined by the elongated body of the airbrush when the latter exhibits a pen shape or by a handle 10 when the airbrush is of gun type, as illustrated in Figure 2.

The airbrush 2 can carry a container 1 1 comprising the composition to be sprayed, this container 1 1 being provided, for example, in the form of a removable bottle. The airbrush can comprise, as illustrated, in the upper part, a joining device 30 for receiving the container 1 1 .

During the operation of the airbrush 2, the product is sucked up and flows through the airbrush by a withdrawal channel, before being sprayed.

The container 1 1 can be transparent or can be provided with graduations, in order to allow the user to more easily visualize the amount of product available. The volume of product present in the container 1 1 is, for example, between 1 and 5000 ml, preferably from 1 to 1000 ml and more preferably still from 1 to 500 ml.

Preferably, the flexible tube 15 which connects the airbrush to the compressor 4 and in particular to the air regulator 5 exhibits a length of less than or equal to 5 m and its internal diameter is, for example, equal to 4 mm. The flexible tube 15 is preferably equipped with quick-coupling connectors.

The airbrush 2 can be provided to the user with several stoppered and pre-filled containers 1 1 , as illustrated in Figure 1 , for example all containing the same product, so as to allow the user to rapidly replace an empty container with a full container, for example in order to treat different people.

The containers 1 1 can also comprise different products, for example of different composition, targeted at carrying out different treatments, which may or may not be complementary, and the user can choose, from the containers 1 1 , that which corresponds to the treatment to be carried out.

The spraying parameters, in particular the flow rate of the carrier gas

(preferably air) and/or the flow rate of sprayed product, can be adjusted manually by the user at each change in container 1 1 , when this is necessary, or during use, in order to obtain the desired visual effect.

The relative pressure of compressed air on arriving in the airbrush 2 can be between 0.2 and 3 bar, for example being of the order of 0.6 bar.

The nozzle 21 with which the airbrush is equipped is preferably chosen so that the mean size of the droplets of sprayed product is centred on a value of between 10 and 35 μιτι, being, for example, of the order of 23 μιτι (size measured at a distance of 15 cm from the outlet of the nozzle).

The joining device 30 suitable for a container 1 1 in the form of a bottle, comprising a neck provided with a flange and with a stoppering means 120, comprises, in the example illustrated, an attaching connector on the body of the airbrush, for example of quick-coupling type, so as to allow removable attaching to the body of the airbrush.

Of course, it is not departing from the scope of the present invention if the joining device 30 is attached permanently to the rest of the airbrush or is attached in removable fashion using means other than a quick coupling.

When the joining device 30 is in place on the airbrush, the axis of the connector can be vertical or directed obliquely towards the front or the back of the airbrush.

It is also possible to produce the joining device 30 in the form of a part of the body of the airbrush, the joining device 30 not necessarily projecting with respect to the body of the airbrush.

As the container 1 1 is attached in leaktight fashion to the joining device, an air uptake circuit is provided in order to allow air to re-enter the container as the latter is emptied. The container is closed, with the exception of the product- withdrawing and air uptake circuits.

In order to use the airbrush 2, the user places the container 1 1 on the joining device 30.

The container 1 1 is for example equipped, before it is fitted to the airbrush, with a stoppering means 120, such as a nipple or a closing cap, which is then separated from the container. The airbrush 2 can comprise any means for triggering the spraying, for example in the form of an operating element, such as a lever 13, as illustrated in Figure 2, actuated by a finger of the hand of the user holding the airbrush. In this figure, the airbrush is a gravity-fed airbrush. It is not departing from the scope of the invention to use a siphon-fed airbrush. In the latter case, it is sufficient for the joining device 30 to be provided with a system (for example a tube 200, as illustrated by a broken line in Figure 1 ) for bringing the first orifice into communication with the inlet of the airbrush making possible the suction.

Mention may be made, as examples of airbrushes to which the invention can be applied, of that with the reference A4700 from Azteck, that with the reference Kustom micron CM from Iwata and that with the reference Evolution Infinity 2 in 1 from Harder and Steenbeck, these airbrushes being of pen-grip type. Use may also be made of the airbrush with the reference Kustom revolution TR from Iwata or that with the Colani^® reference from Harder and Steenbeck.

Of course, other arrangements than those which have just been described are possible. For example, use may be made of one and the same compressor for several airbrushes, this compressor being, for example, situated outside the room in which the treatment is carried out, so as to reduce noise nuisance.

Preferably, the sprayed spray is circular but various nozzles can be used, so as to have flat sprays or sprays having another shape as a function of the visual effect which it is desired to obtain.

The compressor can be replaced by a supply of compressed air, for example bottled compressed air or a cartridge of compressed or liquefied gas, for example loaded onto the airbrush and handled with the latter during use.

Several containers can be fitted to the airbrush, if appropriate.

Use may be made of one and the same compressor for several airbrushes, this compressor being, for example, situated outside the room in which the treatment is carried out, so as to reduce noise nuisance.

A reservoir carried by the airbrush can be replaced by a reservoir connected to the airbrush by a pipe, the product being sucked up into the airbrush by the negative pressure created by the Venturi effect by the movement of carrier gas through the airbrush. A pump can also be used to bring, to the airbrush, the product to be sprayed.

The use of an airbrush makes it possible to easily modify the operating parameters in order to change the effects brought about, during use, according to the taste of the user; the latter can, for example, adjust the flow rate of the jet of product as a function of the visual effect desired. Furthermore, the volume of the gas (preferably air) which is used as carrier gas is unlimited when the airbrush is connected to a compressor. The product to be sprayed can be easily replaced and different products can be easily used successively with one and the same airbrush.

The invention is illustrated in more detail in the following examples, which are provided by way of illustration and without implied limitation of the invention.

EXAMPLES

The following compositions were prepared, the contents being expressed by weight with respect to the total weight of the composition (as active material):

^* disteardimonium hectorite and propylene carbonate in isododecane

Each of the compositions 1 to 10 was sprayed over a head of hair using a Kustom revolution TR airbrush from Iwata. Very precise coloured shaping was obtained, in just one action. The head of hair is very quickly set off.

Claims

1 - Method for the cosmetic treatment of keratinous fibres in which a composition comprising, in a cosmetically acceptable medium, one or more fixing polymer(s) and one or more colouring agents is sprayed over the keratinous fibres using an airbrush.

2 - Method according to the preceding claim, in which the colouring agent(s) are chosen from direct dyes, coloured polymers or pigments.

3 - Method according to Claim 1 or 2, in which the colouring agent(s) are chosen from neutral, acidic or cationic nitrobenzene direct dyes, neutral, acidic or cationic azo direct dyes, tetraazapentamethine dyes, neutral, acidic or cationic quinone and in particular anthraquinone dyes, azine direct dyes, triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

4 - Method according to Claim 1 or 2, in which the colouring agent(s) are chosen from coloured polymers which are soluble or insoluble in the medium.

5 - Method according to Claim 1 or 2, in which the colouring agent(s) are chosen from coloured pigments, in particular pearlescent agents.

6 - Method according to any one of the preceding claims, in which the colouring agent(s) are present in concentrations varying from 0.01 % to 30% by weight, better still from 0.1 % to 20% by weight and even better still from 0.1 % to 10% by weight, with respect to the total weight of the composition.

7 - Method according to any one of the preceding claims, in which the fixing polymer(s) are chosen from anionic, amphoteric and non-ionic fixing polymers. 8 - Method according to any one of the preceding claims, in which the composition comprises a fixing polymer which is anionic and chosen from copolymers of acrylic or methacrylic acid or their salts and of acrylamide, copolymers of acrylic or methacrylic acid with a monoethylenic monomer, crotonic acid copolymers, copolymers of monounsaturated C₄-C₈ carboxylic acids or anhydrides, polyacrylamides comprising carboxylate groups, homopolymers and copolymers comprising sulfonic groups, monoesterified methyl vinyl ether/maleic anhydride copolymers, acrylic acid/ethyl acrylate/N- tert-butylacrylamide terpolymers, copolymers of methacrylic acid and methyl methacrylate, vinyl acetate/vinyl tert-butylbenzoate/crotonic acid terpolymers and crotonic acid/vinyl acetate/vinyl neododecanoate terpolymers, copolymers of methacrylic acid and ethyl acrylate, butyl acrylate/acrylic acid/methacrylic acid branched block polymers and vinylpyrrolidone/acrylic acid/lauryl methacrylate terpolymers.

9 - Method according to any one of the preceding claims, in which the composition comprises at least one fixing polymer which is non-ionic and chosen from polyalkyloxazolines, vinyl acetate homopolymers, vinyl acetate copolymers, homopolymers and copolymers of acrylic esters, acrylonitrile copolymers, styrene homopolymers, styrene copolymers, polyamides, vinyllactam homopolymers and vinyllactam copolymers.

10 - Method according to any one of the preceding claims, characterized in that the fixing polymer(s) are present in concentrations varying from 0.1 % to 30% by weight, preferably from 0.5% to 15% by weight and better still from 1 % to 10% by weight, with respect to the total weight of the composition.

1 1 - Method according to any one of the preceding claims, in which the composition comprises water. 12 - Method according to any one of the preceding claims, in which the composition comprises at least one organic solvent, the solvent preferably being ethanol.

13 - Spraying system comprising:

- an airbrush,

- one or more removable containers each containing a composition comprising one or more fixing polymer(s) and one or more colouring agent(s) as described in Claims 1 to 12.

14 - Use of an airbrush for the coloured shaping of a hairstyle.