WO2012137165A2

WO2012137165A2 - A hair treatment method

Info

Publication number: WO2012137165A2
Application number: PCT/IB2012/051692
Authority: WO
Inventors: Stefania Nuzzo; Gabin Vic; Fabrice OSOLIN; Maryse Chaisy
Original assignee: L'oreal
Priority date: 2011-04-08
Filing date: 2012-04-05
Publication date: 2012-10-11
Also published as: EP2694009A2; FR2973661A1; US20140096786A1; WO2012137165A3; BR112013023142A2

Abstract

The present invention provides a method of treating hair, the method comprising the following steps:. applying a composition to the hair, the composition comprising one or more active ingredients selected from the following: - hair conditioning agents; - reducing agents; - organic or inorganic bases; - hair dyes; - abrasive solid particles; and - moisturizing agents; and. combing the hair using a motor-driven combing device (10) comprising spikes that are driven in an oscillating motion.

Description

A HAIR TREATMENT METHOD

The present invention relates to methods, devices and kits for treating hair.

Tools for cleaning or massaging the hair are known from US 6 283 930 B, JP 2002-363039 A, JP 2005-046190 A, CN 2010 44658 Y and JP 11070019 A.

European application EP 1 825 842 Al describes a massage device for massaging the scalp when washing the hair, for example, and envisages using it at the same time as shampoo is used.

The application US 2009/0182249 Al discloses a device for massaging the scalp, comprising a reservoir that can accommodate a liquid such as a shampoo or a lotion for stimulating hair growth. Various devices for massaging the scalp are also disclosed in the

publications EP 1 972 317 Al, EP 1 964 537 Al, and

EP 2 080 500 Al.

There is a need for a method and for a treatment kit that can be used to improve the efficacy of the active ingredients in hair treatments.

In first exemplary embodiments the invention

provides a cosmetic hair treatment method comprising the steps consisting in:

• applying a composition to the hair, the

composition comprising one or more active ingredients selected from the following:

o hair conditioning agents;

o reducing agents;

o organic or inorganic bases;

o hair dyes;

o abrasive solid particles; and

o moisturizing agents; and

• combing the hair using a motor-driven combing device comprising spikes that are driven in an

oscillating motion.

Hair combing using a motor-driven device can be carried out after applying the composition of the invention to the hair, preferably in the presence of the composition on the hair.

Hair combing using a motor-driven device may be carried out before applying the composition of the invention to the hair, in particular after wetting the hair or after applying a composition not including any active ingredient of the invention. By way of example, combing may be carried out less than 60 minutes before applying the composition containing the active ingredient of the invention.

Applying the method to frizzy or curly hair in association with the composition containing the active ingredient results in a very distinct reduction in volume and density, in better disentangling, and in a smoother feel .

Preferably, the combing device is characterized in that it includes a flexible diaphragm carrying spikes and a drive mechanism that enables the diaphragm to deform periodically in order to generate movement of the spikes.

The drive mechanism preferably includes a connecting rod that is driven in oscillating motion, which

connecting rod is connected at one end to a member that is driven in rotation by an electric motor and is

connected directly or indirectly at its other end to the flexible diaphragm, in particular in a central region thereof .

The frequency of oscillation of the diaphragm preferably lies in the range 0.5 Hz [Hertz] to 200 Hz, better preferably in the range 1 Hz to 20 Hz, the limits of the ranges being included in the ranges.

The envelope surface defined by the free ends of the spikes may be a surface that is concave towards the scalp, with a radius of curvature that varies as a function of the deformations of the diaphragm.

During oscillation of the diaphragm, at least some of the spikes rub against the hair. Performance is improved by rubbing these spikes on the hair in combination with using the composition. The invention enables a superior effect to be achieved than that obtained manually. he travel axis of the flexible

diaphragm, i.e. the axis of the oscillating movement, may be substantially perpendicular to the scalp during combing, at least while combing the base of hair.

Preferably, the spikes are made out of a

thermoplastic material.

In other exemplary embodiments the invention

provides a cosmetic hair treatment method comprising the steps consisting in:

• applying a composition to the hair, the

o hair conditioning agents;

o reducing agents;

o organic or inorganic bases;

o hair dyes;

o abrasive solid particles; and

o moisturizing agents; and

• combing the hair for a period of 1 minute to

5 minutes using a motor-driven combing device comprising spikes that are driven in an oscillating motion.

In other exemplary embodiments the invention also provides a motor-driven combing device for carrying out one of the above methods.

The invention also provides a motor-driven combing device comprising: a flexible diaphragm carrying spikes adapted to come into contact with the hair; a drive mechanism enabling the diaphragm to deform periodically in order to generate movement of the spikes in contact with the hair; and a reservoir containing a composition for application, in the form of a pre-filled removable cartridge . Active ingredients

The composition of the invention applied to the hair may contain at least one of the following active

ingredients .

The active ingredient or ingredients may be applied alone or in combination with other ingredients. When applied in combination, the active ingredient may

represent up to 50% by weight of the total composition weight, preferably up to 20% by weight of the total composition weight.

The active ingredient or ingredients may represent more than 0.001%, preferably more than 0.1 ~6 , more

preferably more than 0.2%; and more particularly more than 0.5% by weight relative to the total composition weight .

Hair dyes

The term "hair dye" as used in the present invention means synthetic direct dyes, natural dyes, and precursors of oxidation dyes.

These hair dyes may be non-ionic or ionic, in particular cationic or anionic.

The precursor or precursors of the oxidation dyes present in the composition of the present invention may be selected from oxidation bases and coupling agents in conventional use in oxidation dyeing.

The oxidation base or bases may be selected from para-phenylenediamines , bis-phenylalkylenediamines , para- aminophenols , bis-para-aminophenols , ortho-aminophenols , ortho-phenylenediamines , heterocyclic bases, and their addition salts.

Examples of para-phenylenediamines that may be mentioned are para-phenylenediamine, para-toluenediamine, 2-chloro para-phenylenediamine, 2,3-dimethyl para- phenylenediamine, 2, 6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,5-dimethyl para- phenylenediamine, N, -dimethyl para-phenylenediamine, Ν,Ν-diethyl para-phenylenediamine, Ν,Ν-dipropyl para- phenylenediamine, 4-amino Ν,Ν-diethyl 3-methyl aniline, N, -bis- ( β-hydroxyethyl ) para-phenylenediamine, 4-N,N- bis- ( β-hydroxyethyl ) amino 2-methyl aniline,

4-N, -bis- ( β-hydroxyethyl) amino 2-chloro aniline,

2- -hydroxyethyl para-phenylenediamine, 2-fluoro para- phenylenediamine, 2-isopropyl para-phenylenediamine, N- ( β-hydroxypropyl ) para-phenylenediamine,

2-hydroxymethyl para-phenylenediamine, N, N-dimethyl 3- methyl para-phenylenediamine, N,N- (ethyl, β-hydroxyethyl ) para-phenylenediamine, N- ( β , γ-dihydroxypropyl) para- phenylenediamine, N- ( 4 ' -aminophenyl ) para- phenylenediamine, N-phenyl para-phenylenediamine,

2^-hydroxyethyloxy para-phenylenediamine, 2- β - acetylaminoethyloxy para-phenylenediamine,

N- ( β-methoxyethyl ) para-phenylene-diamine, 4-aminophenyl pyrrolidine, 2-thienyl para-phenylenediamine,

2- β-hydroxyethylamino 5-amino toluene, 3-hydroxy l-(4'- aminophenyl) pyrrolidine, and their addition salts.

Particularly preferred examples of the above- mentioned para-phenylenediamines are para- phenylenediamine, para-toluenediamine, 2-isopropyl para- phenylenediamine, 2^-hydroxyethyl para-phenylenediamine, 2^-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- ( β - hydroxyethyl ) para-phenylenediamine, 2-chloro para- phenylenediamine, 2^-acetylaminoethyloxy para- phenylenediamine, and their addition salts.

Examples of bis-phenylalkylenediamines that may be mentioned are N, N ' -bis- ( β-hydroxyethyl ) N, N ' -bis- ( 4 ' - aminophenyl) 1 , 3-diamino propanol, N,N'-bis-^- hydroxyethyl ) N, N ' -bis- ( 4 ' -aminophenyl ) ethylenediamine, N, N ' -bis- (4-aminophenyl) tetramethylenediamine,

N, N ' -bis- ( β-hydroxyethyl ) N, N ' -bis- (4-aminophenyl) tetramethylenediamine, N, N ' -bis- (4 -methyl-aminophenyl) tetramethylenediamine, N, N ' -bis- (ethyl ) N, N ' -bis- ( 4 ' - amino, 3 ' -methylphenyl ) ethylenediamine, 1, 8-bis- (2, 5- diamino phenoxy) -3, 6-dioxaoctane, and their addition salts .

More particular examples of para-aminophenols that may be mentioned are para-aminophenol , 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4-amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino

2-aminomethyl phenol, 4-amino 2- ( β-hydroxyethyl

aminomethyl) phenol, 4-amino 2-fluoro phenol, and their addition salts.

Examples of ortho-aminophenols that may be mentioned are 2-aminophenol, 2-amino 5-methyl phenol, 2-amino

6-methyl phenol, 5-acetamido 2-aminophenol, and their addition salts.

Examples of heterocyclic bases that may be mentioned are pyridine derivatives, pyrimidine derivatives and pyrazolic derivatives.

Examples of pyridine derivatives that may be

mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as

2,5-diamino pyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino 6-methoxy pyridine, 2- ( β - methoxyethyl ) amino 3-amino 6-methoxy pyridine, 3,4- diamino pyridine, and their addition salts.

Other pyridinic oxidation bases that may be used in the present invention are 3-amino pyrazolo- [ 1 , 5-a] - pyridine oxidation bases, or their addition salts, as described in patent application FR 2 801 308, for

example. Examples that may be mentioned are

pyrazolo [ 1 , 5-a] pyridin-3-ylamine ; 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine ; 2-morpholin-4-yl-pyrazolo [ 1 , 5- a] pyridin-3-ylamine ; 3-amino-pyrazolo [1, 5-a]pyridin-2- carboxylic acid; 2-methoxy-pyrazolo [ 1 , 5-a] pyridine-3- ylamino ; (3-amino-pyrazolo [ 1 , 5-a] pyridine-7 -yl ) -methanol ; 2- (3-amino-pyrazolo [ 1 , 5-a] pyridine-5-yl ) -ethanol ; 2- ( 3- amino-pyrazolo [ 1 , 5-a] pyridine-7 -yl ) -ethanol ; (3-amino- pyrazolo [1, 5-a]pyridine-2-yl) -methanol ; 3 , 6-diamino- pyrazolo [ 1 , 5-a] pyridine ; 3 , 4-diamino-pyrazolo [1,5- a]pyridine; pyrazolo [ 1 , 5-a] pyridine-3 , 7-diamine ; 7- morpholin-4 -yl-pyrazolo [ 1 , 5-a] pyridin-3-ylamine ;

pyrazolo [1, 5-a]pyridine-3, 5-diamine ; 5-morpholin-4-yl- pyrazolo [1, 5-a] pyridin-3-ylamine ; 2- [ (3-amino- pyrazolo [1, 5-a]pyridin-5-yl) - (2-hydroxyethyl ) -amino ] - ethanol ; 2- [ (3-amino-pyrazolo [1, 5-a]pyridin-7-yl) - (2- hydroxyethyl ) -amino] -ethanol; 3-amino-pyrazolo [1, 5- a] pyridine-5-ol ; 3-amino-pyrazolo [ 1 , 5-a] pyridine-4-ol ; 3- amino-pyrazolo [ 1 , 5-a] pyridine- 6-ol ; 3-amino-pyrazolo [1,5- a] pyridine-7-ol ; as well as their addition salts.

Examples of pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 23 59 399; JP 88-169571; JP 05-63124;

EP 0 770 375 or patent application WO 96/15765 such as 2, 4, 5, 6-tetra-aminopyrimidine, 4-hydroxy 2,5,6- triaminopyrimidine, 2-hydroxy 4, 5, 6-triaminopyrimidine, 2, 4-dihydroxy 5, 6-diaminopyrimidine,

2 , 5 , 6-triaminopyrimidine and pyrazolo-pyrimidine

derivatives such as those mentioned in patent application FR-A-2 750 048; in which some that may be mentioned are pyrazolo- [1, 5-a] -pyrimidine-3 , 7-diamine; 2, 5-dimethyl pyrazolo- [1, 5-a] -pyrimidine-3, 7-diamine; pyrazolo- [1, 5- a] -pyrimidine-3, 5-diamine; 2,7-dimethyl pyrazolo- [ 1 , 5-a] - pyrimidine-3 , 5-diamine ; 3-amino pyrazolo- [ 1 , 5-a] - pyrimidin-7-ol ; 3-amino pyrazolo- [ 1 , 5-a] -pyrimidin-5-ol ; 2- (3-amino pyrazolo- [1, 5-a] -pyrimidin-7-ylamino) -ethanol, 2- (7-amino pyrazolo- [1, 5-a] -pyrimidin-3-ylamino) -ethanol, 2- [ (3-amino-pyrazolo [1, 5-a] pyrimidin-7-yl) - (2-hydroxy^¬ ethyl) -amino] -ethanol, 2- [ (7-amino-pyrazolo [1, 5- a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol, 5, 6- dimethyl pyrazolo- [1, 5-a] -pyrimidine-3, 7-diamine,

2,6-dimethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7-diamine, 2, 5, N7, N7-tetramethyl pyrazolo- [ 1 , 5-a] -pyrimidine-3 , 7- diamine, 3-amino-5-methyl-7-imidazolylpropylamino

pyrazolo- [ 1 , 5-a] -pyrimidine, and their addition salts, and their tautomeric forms when a tautomeric equilibrium exists .

Examples of pyrazolic derivatives that may be mentioned are the compounds described in patents

DE 38 43 892, DE 41 33 957 and patent applications

WO 94/08969, WO 94/08970, FR-A-2 733 749 and

DE 195 43 988, such as 4,5-diamino 1- (β-hydroxyethyl) pyrazole, 4,5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4 ' -chlorobenzyl) pyrazole, 4,5- diamino 1,3-dimethyl pyrazole, 4,5-diamino 3-methyl 1- phenyl pyrazole, 4,5-diamino 1-methyl 3-phenyl pyrazole, 4-amino 1,3-dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5- diamino 3-methyl pyrazole, 4,5-diamino 3-tert-butyl 1- methyl pyrazole, 4,5-diamino 1-tert-butyl 3-methyl pyrazole, 4,5-diamino 1- ( β-hydroxyethyl) 3-methyl

pyrazole, 4,5-diamino 1-ethyl 3-methyl pyrazole, 4,5- diamino 1-ethyl 3- ( 4 ' -methoxyphenyl ) pyrazole, 4,5- diamino 1-ethyl 3-hydroxymethyl pyrazole, 4,5-diamino 3- hydroxymethyl 1-methyl pyrazole, 4,5-diamino

3-hydroxymethyl 1-isopropyl pyrazole, 4,5-diamino 3- methyl 1-isopropyl pyrazole, 4-amino 5-(2'- aminoethyl ) amino 1,3-dimethyl pyrazole, 3 , 4 , 5-triamino pyrazole, 1-methyl 3 , 4 , 5-triamino pyrazole, 3,5-diamino 1-methyl 4-methylamino pyrazole, 3,5-diamino

4- ( β-hydroxyethyl) amino 1-methyl pyrazole, 2,3- diamino- 6, 7-dihydro-lH, 5H-pyrazolo[l,2-a]pyrazol-l-one, and their addition salts.

The coupling agent or agents present in the

composition of the present invention may be selected from meta-phenylenediamines , meta-aminophenols , meta- diphenols, naphthalenic coupling agents, heterocyclic coupling agents, and their addition salts.

Examples that may be mentioned are 3-aminophenol , 2- methyl 5-aminophenol, 2-methyl 5- ( β-hydroxyethylamino) phenol, 2-chloro 6-methyl 3-aminophenol, 1 , 3-dihydroxy benzene, 1 , 3-dihydroxy 2-methyl benzene, 4-chloro 1,3- dihydroxy benzene, 2,4-diamino 1- ( β-hydroxyethyloxy) benzene, 2-amino 4- ( β-hydroxyethylamino) 1- methoxybenzene, 1 , 3-diaminobenzene, 1, 3-bis- (2, 4- diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1- dimethylaminobenzene, sesamol, l^-hydroxyethylamino-3, 4- methylenedioxybenzene, a-naphthol, 2-methyl-l-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6- hydroxy

benzomorpholine, 3, 5-diamino-2, 6-dimethoxy pyridine, 1-N- (β-hydroxyethyl) amino-3, 4-methylene dioxybenzene, 2,6- bis- ( β-hydroxyethylamino) toluene, and their addition salts .

In general, addition salts of oxidation bases and coupling agents that may be used in the context of the invention are in particular selected from addition salts with an acid such as hydrochlorides, hydrobromides , sulfates, citrates, succinates, tartrates, lactates, (C1-C4) alkyl sulfonates, and in particular

methylsulfonates , tosylates, benzenesulfonates ,

phosphates, and acetates, and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines, or alkanolamines .

The term "natural dyes" means any dye or dye

precursor that occurs naturally and that is produced either by extraction (and possibly purification) from a plant matrix, or by chemical synthesis.

In contrast, the term "synthetic dyes" means any dye that does not occur naturally.

Examples of suitable synthetic direct dyes that may be mentioned are azo direct dyes; methine dyes; carbonyl dyes; azine dyes; nitro (hetero) aryl dyes; tri- (hetero)aryl methane dyes; used alone or as a mixture.

More particularly, azo dyes include an -N=N- function in which both nitrogen atoms are not

simultaneously engaged in a cycle. However, it is also possible for one of the two nitrogen atoms of the -N=N- concatenation to be engaged in a cycle. Dyes of the methine family are more particularly compounds comprising at least one concatenation selected from >C=C< and -N=C< in which both atoms are not

simultaneously engaged in one cycle. However, it should be pointed out that one of the atoms of the

concatenations, nitrogen or carbon, may be engaged in a cycle. More particularly, dyes of this family derive from compounds of the true methane type (comprising one or more of the above-mentioned -C=C- concatenations) ; of the azomethine type (including at least one or more -C=N- concatenations ) with, for example, azacarbocyanins and their isomers, or diazacarbocyanins and their isomers, tetraazacarbocyanins ; of the mono- and di- arylmethane type; indoamines (or diphenylamines) ; indophenols ;

indoanilines .

Examples of dyes of the carbonyl family that may be mentioned are dyes selected from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone,

anthranthrone, pyranthrone, pyrazolanthrone,

pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso) violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigoid, thioindigo, naphthalimide, anthrapyrimidine,

diketopyrrolopyrrole, and coumarin.

Particular examples of dyes of the azine family that may be mentioned are azine, xanthene, thioxanthene, fluorindine, acridine, (di)oxazine, (di) thiazine, and pyronine .

More particular nitro (hetero) aromatic dyes are nitrobenzene direct dyes or nitropyridine dyes.

Regarding porphyrin or phthalocyanin dyes, it is possible to use cationic or non-cationic compounds, optionally including one or more metals or metallic ions such as alkali and alkaline-earth metals, zinc, or silicon, for example. Particularly suitable examples of direct dyes that may be mentioned are nitrated dyes of the benzene series; azo direct dyes; methine dyes; azomethine dyes, more particularly with diazacarbocyanins and their isomers and tetraazacarbocyanins (tetraazapentamethines) ; quinone direct dyes and in particular anthraquinone,

naphthoquinone or benzoquinone dyes; azine direct dyes; xanthene dyes; triarylmethane dyes; indoamine dyes;

indigoid dyes; and phthalocyanins and porphyrins; used alone or as a mixture.

Preferably, the direct dyes are selected from nitro dyes of the benzene series; azo dyes; azomethines with diazacarbocyanins and their isomers, tetraazacarbocyanins (tetraazapentamethines); anthraquinone direct dyes; and triarylmethane direct dyes; used alone or as a mixture.

Still more preferably, said direct dyes are selected from nitro dyes of the benzene series; azo direct dyes; azomethines with diazacarbocyanins and their isomers, and tetraazacarbocyanins (tetraazapentamethines) ; alone or as a mixture.

Non-limiting examples of nitrobenzene direct dyes that may be used in accordance with the invention that may be mentioned are the following compounds:

• 1, 4-diamino-2-nitrobenzene;

• l-amino-2 nitro-4-β- hydroxyethylaminobenzene ;

• l-amino-2 nitro-4-bis (β-hydroxyethyl) - aminobenzene ;

• 1, 4-bis ( β-hydroxyethylamino) -2-nitrobenzene;

• l^-hydroxyethylamino-2-nitro-4-bis- (β- hydroxyethylamino) -benzene;

• Ι-β-hydroxyethylamino-2 -nitro-4 -aminobenzene ;

• l^-hydroxyethylamino-2-nitro-4- (ethyl) (β- hydroxyethyl ) -aminobenzene;

• l-amino-3-methyl-4^-hydroxyethylamino- 6- nitrobenzene ;

• l-amino-2 -nitro-4^-hydroxyethylamino-5- chlorobenzene ; • 1, 2-diamino-4-nitrobenzene;

• l-amino-2^-hydroxyethylamino-5-nitrobenzene ;

• 1, 2-bis- ( β-hydroxyethylamino) -4-nitrobenzene;

• l-amino-2-tris- (hydroxymethyl ) -methylamino-5- nitrobenzene ;

• 1 -hydroxy-2 -amino-5-nitrobenzene ;

• 1 -hydroxy-2 -amino-4 -nitrobenzene ;

• l-hydroxy-3-nitro-4-aminobenzene ;

• l-hydroxy-2-amino-4 , 6-dinitrobenzene ;

• l^-hydroxyethyloxy-2^-hydroxyethylamino-5- nitrobenzene ;

• 1 -methoxy-2^-hydroxyethylamino-5-nitrobenzene ;

• l^-hydroxyethyloxy-3-methylamino-4 -nitrobenzene ;

• l^DY-dihydroxypropyloxy-3-methylamino-4- nitrobenzene ;

• l^-hydroxyethylamino-4^, Y-dihydroxypropyloxy-2- nitrobenzene ;

• l^DY-dihydroxypropylamino-4-trifluoromethyl-2 - nitrobenzene ;

• l-β-hydroxyethylamino-4-trifluoromethyl-2- nitrobenzene ;

• 1 - β-hydroxyethylamino-3-methy1-2 -nitrobenzene ;

• l^-aminoethylamino-5-methoxy-2 -nitrobenzene ;

• 1 -hydroxy-2 -chloro- 6-ethylamino-4 -nitrobenzene ;

• 1 -hydroxy-2 -chloro- 6-amino-4 -nitrobenzene ;

• l-hydroxy-6-bis- ( β-hydroxyethyl ) -amino-3- nitrobenzene ;

• l-β-hydroxyethylamino-2-nitrobenzene; and

• l-hydroxy-4^-hydroxyethylamino-3-nitrobenzene . Examples of azo, azomethine, methine direct dyes that may be used in accordance with the invention and that may be mentioned are the cationic dyes described in patent applications WO 95/15144, WO 95/01772, and

EP 7 149 54; FR 2 189 006, FR 2 285 851, FR 2 140 205, EP 1 378 544, and EP 1 674 073.

As an example, the synthetic direct dye or dyes may be selected from cationic monochromophoric direct dyes of the azo; methine; azomethine type with diazacarbocya and their isomers, tetraazacarbocyanins ; and

anthraquinones ; used alone or as a mixture.

Thus, cationic direct dyes with the following formulae may in parti ned:

in which:

^• D represents a nitrogen atom or the group -CH;

^• Ri and R₂, which may be identical or different, represent a hydrogen atom; a C₁-C4 alkyl radical possibly substituted with a -CN, -OH or -NH₂ radical or form a heterocycle, optionally oxygen-containing or nitrogen- containing, with a carbon atom of the benzene ring, possibly substituted with one or more C₁-C4 alkyl

radicals; or a 4 ' -aminophenyl radical;

^• R3 and R'3, which may be identical or different, represent a hydrogen atom or halogen atom selected from chlorine, bromine, iodine and fluorine, or a cyano, C₁-C4 alkyl, C₁-C4 alkoxy, or acetyloxy radical;

^• X - represents an anion, preferably selected from the chloride, methyl sulfate, and acetate;

^• A represents a group selected from the following struct

in which R₄ represents a C₁-C4 alkyl radical, possibly substituted with a hydr

in which: ^• R₅ represents a hydrogen atom, a C₁-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine, or fluorine;

^• R6 represents a hydrogen atom, a C₁-C4 alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle that optionally contains oxygen and/or is substituted with one or more C₁-C4 alkyl groups;

^• R₇ represents a hydrogen atom or halogen atom such as bromine, chlorine, iodine, or fluorine;

^• Di and D₂, which may be identical or different, represent a nitrogen atom or the group -CH;

^• m = 0 or 1 ;

^• X- represents a cosmetically acceptable anion preferably selected from chloride, methyl sulfate and acetate ;

^• E represents a group selected from the following structures :

in which R' represents a C₁-C4 alkyl radical;

^• when m = 0 and Di represents a nitrogen atom, E may also designate a group with the following

structure :

in which R' represents a C₁-C4 alkyl radical.

More particular examples of the above-mentioned compounds are as follows:

X-

(A2)

X- representing a cosmetically acceptable anion or mixture of anions.

Other dyes that may be used in accordance with the invention that may also be mentioned from azo direct dyes include the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition:

• Disperse Red 17;

• Disperse Red 13;

• Basic Red 22;

• Basic Red 76;

• Basic Yellow 57;

• Basic Brown 16;

• Basic Brown 17;

• Disperse Green 9; • Disperse Black 9;

• Solvent Black 3;

• Disperse Blue 148;

• Disperse Violet 63; and

• Solvent Orange 7.

1- (4 ' -aminodiphenylazo) -2-methyl-4 bis- (β-hydroxyethyl ) aminobenzene ( INCI name: HC Yellow 7) may also be mentioned .

Examples of direct quinone dyes that may be mentioned are the following dyes:

• Disperse Red 15;

• Solvent Violet 13;

• Solvent Blue 14;

• Disperse Violet 1;

• Disperse Violet 4;

• Disperse Blue 1;

• Disperse Violet 8;

• Disperse Blue 3;

• Disperse Red 11;

• Disperse Blue 7;

• Disperse Blue 14;

• Basic Blue 22;

• Disperse Violet 15;

• Disperse Blue 377;

• Disperse Blue 60; and

• Basic Blue 99;

as well as the following compounds:

• l-N-methylmorpholiniumpropylamino-4- hydroxyanthraquinone ;

• l-aminopropylamino-4-methylaminoanthraquinone ;

• 1-aminopropylaminoanthraquinone ;

• 5-β-hydroxyethyl-l , 4-diaminoanthraquinone;

• 2-aminoethylaminoanthraquinone; and

• 1 , 4 -bis- ( βγ-dihydroxypropylamino) -anthraquinone . The coumarin Disperse Yellow 82 may also be mentioned . Examples of azine dyes that may be mentioned are the following compounds:

• Basic Blue 17;

• Basic Red 2; and

• Solvent Orange 15.

Examples of triarylmethane dyes that may be used in accordance with the invention and that may be mentioned are the following compounds:

• Basic Green 1;

• Basic Violet 3;

• Basic Violet 14;

• Basic Blue 7; and

• Basic Blue 26.

Examples of indoamine dyes that may be used in accordance with the invention and that may be mentioned are the following compounds:

• 2^-hydroxyethylamino-5- [bis- (β-4 ' - hydroxyethyl) amino] anilino-1, 4-benzoquinone;

• 2^-hydroxyethylamino-5- (2 ' -methoxy-4 ' - amino) anilino-1, 4-benzoquinone;

• 3-N (2 ' -chloro-4 ' -hydroxy) phenyl-acetylamino- 6- methoxy-1 , 4-benzoquinone imine;

• 3- (3 ' -chloro-4 ' -methylamino) phenyl-ureido- 6- methyl-1 , 4-benzoquinone imine; and

• 3- [4 ' -N- (ethylcarbamylmethyl ) -amino] -phenyl- ureido-6-methyl-l, 4-benzoquinone imine .

Preferably, the direct cationic dyes are selected from direct dyes of the following types: azo; methine; azomethine with diazacarbocyanins and their isomers, tetraazacarbocyanins (tetraazapentamethines) ;

anthraquinone ; used alone or as a mixture.

Examples of direct anionic dyes that may in

particular be mentioned are those described in the COLOR INDEX INTERNATIONAL 3rd edition listed under ACID and in particular :

• Disperse Red 17;

• Acid Yellow 9; Acid Black 1;

Acid Yellow 36;

Acid Orange 7;

Acid Red 33;

Acid Red 35;

Acid Yellow 23;

Acid Orange 24;

Acid Violet 43;

Acid Blue 62;

Acid Blue 9;

Acid Violet 49; and

Acid Blue 7.

Particular natural dye or dyes that may be used to carry out the invention are preferably selected from lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, laccaic acid, purpurogallin, anthragallol , protocatechaldehyde, indigo, isatin, curcumin,

spinusolin, chlorophylls, chlorophyllins , orceins, hematein, hematoxylin, brazilin, brazilein, carthame dyes (such as carthamin, for example) , flavonoids (with morin, apigenidin, santal, for example) , anthocyans (of the apigeninidin type) , carotenoids, tannins, sorghum, and cochineal carmine, or mixtures thereof.

It is also possible to use extracts or decoctions containing natural dyes, in particular henna-based extracts .

Preferably, the natural dye or dyes are selected from lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, laccaic acid, purpurogallin,

protocatechaldehyde, indigo, isatin, curcumin,

spinulosin, apigenidin, chlorophyllin, sorghum, orceins, cochineal carmine, hematein, hematoxylin, braziline, and brazilein, and mixtures thereof.

These dyes may optionally be used in the presence of mordants (for example salts of zinc, manganese, aluminum, iron etc . ) . Reducing agents

The composition may contain at least one reducing agent capable of reducing disulfide bonds in the hair.

It is possible to use a reducing agent of the phosphine or sulfite or alkaline bisulfite type.

Advantageously, a thiol reducing agent is used.

Preferably, the thiol or thiols used as reducing agents in the reducing composition are selected from aminothiols such as cysteine and its derivatives, such as N-acetylcysteine, cysteamine and its derivatives,

preferably its C1-C4 acylated derivatives such as N-acetyl cysteamine and N-propionyl cysteamine, and non-amino- containing thiols such as thiolactic acid and its esters, such as glycerol monothiolactate, thioglycolic acid and its esters, such as glycerol or glycol monothioglycolate, and thioglycerol .

When the thiol has at least one carboxylic acid function, if appropriate it is possible to use said thiol in the form of one or more of its salts, such as alkali metal or ammonium salts. It is thus possible to use thioglycolate ammonium as the thiol. If the thiol has an amino group, it would be possible to use said thiol in the form of one or more of its salts such as aminothiol halides. Thus, the thiol used in the context of the present invention may be L-cysteine hydrochloride.

Aminothiols that may be used in the reducing

composition used in accordance with the invention and that may also be mentioned are N-mercapto-alkylamides of sugars, such as N- (mercapto-2-ethyl) gluconamide,

pantheteine, N- (mercaptoalkyl ) co-hydroxyalkylamides such as those described in patent application EP-A-354 835 and N-mono- or N, -dialkylmercapto 4-butyramides such as those described in patent application EP-A-368 763, aminomercaptoalkylamides such as those described in patent application EP-A-432 000 and alkylaminomercapto alkylamides such as those described in patent application EP-A-514 282. Examples of non-aminated thiols used in the invention that may also be mentioned are 2- hydroxypropyl thioglycolate (2/3) and 2-hydroxy-l- methylethyl thioglycolate (67/33) described in patent application FR-A-2 679 448, β-mercaptopropionic acid and its derivatives, and thiomalic acid.

It is possible to use a thiol-containing reducing agent, in particular thioglycolic acid or cysteine.

Organic or inorganic bases

For straightening, it is also possible to use strong bases such as alkali or alkaline-earth metal hydroxides, transition metal hydroxides or organic hydroxides. By way of example, examples of hydroxides that may be mentioned are sodium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide, manganese hydroxide, zinc hydroxide, and guanidinium hydroxide. Preferred hydroxides are sodium hydroxide, calcium hydroxide, lithium hydroxide and guanidinium hydroxide.

Conditioning agents

The conditioning agent may be selected from the group comprising non-silicone cationic polymers, non- silicone cationic surfactants, silicones, in particular organosiloxanes , linear or branched C₈- C30 hydrocarbons, linear or branched C8-C30 fatty alcohols, esters of C8- C30 fatty acids and C₁- C30 monoalcohols or polyols including esters of C8- C30 fatty acids and C8- C30 fatty alcohols, esters of C₁-C7 acids or dibasic acids and C₈- C30 fatty alcohols, ceramides or ceramide analogs, and mixtures of these compounds.

The term "cationic non-silicone polymer" means a polymer having no silicon atoms in its structure, charged positively when it is contained in the composition of the invention. This polymer may carry one or more permanent positive charges or contain one or more cationizable functions in the composition of the invention. The cationic polymer or polymers that may be used as conditioning agents of the present invention are

preferably selected from polymers comprising primary, secondary, tertiary, and/or quaternary groups forming part of the polymer chain or directly bonded thereto, and having a molecular weight (MW) in the range 500 to approximately 5,000,000, preferably in the range 1000 to 3, 000,000.

When the conditioning agent is a cationic polymer, it is preferably selected from those containing motifs comprising primary, secondary, tertiary, and/or

quaternary amine groups that may either form part of the main polymer chain or be carried by a lateral substituent bonded directly thereto.

More particular examples of cationic polymers that may be mentioned are polymers of the polyamine,

polyaminoamide, and quaternary polyammonium type. These are known products. They are described, for example, in French patents numbers 2 505 348 and 2 542 997.

Some of these polymers that may be mentioned are: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the motifs with the following formulae:

(ID

in which:

^• R3 and R4, which may be identical or different, represent hydrogen or an alkyl group containing 1 to 6 carbon atoms, preferably methyl or ethyl;

^• R₅, which may be identical or different, designate a hydrogen atom or a C¾ radical;

^• A, which may be identical or different, represent a linear or branched alkyl group containing 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group containing 1 to 4 carbon atoms;

^• R6, R7, Rs, which may be identical or different, represent an alkyl group containing 1 to 18 carbon atoms or a benzyl radical, preferably an alkyl group containing 1 to 6 carbon atoms; and

^• X designates an anion derived from an organic or inorganic acid such as a methosulfate anion or a halide such as chloride or bromide.

The copolymers of family (1) may further contain one or more motifs deriving from co-monomers that may be selected from the family of acrylamides, methacrylamides, acrylamides, diacetone acrylamides, and acrylamides and methacrylamides substituted on the nitrogen with lower (C₁-C4) alkyls, acrylic or methacrylic acids or their esters, vinyllactams such as vinylpyrrolidone or

vinylcaprolactam, and vinyl esters.

Thus, copolymers of family (1) that may be mentioned include : • copolymers of acrylamide and dimethylaminoethyl methacrylate quaternized with dimethyl sulfate or with a dimethyl halide such as that sold under the trade name HERCOFLOC by the supplier HERCULES;

• copolymers of acrylamide and

methacryloyloxyethyltrimethyl ammonium chloride

described, for example, in patent application

EP-A-080 976 and sold under the trade name BINA QUAT P 100 by the supplier CIBA GEIGY;

• the copolymer of acrylamide and

methacryloyloxyethyltrimethyl ammonium methosulfate sold under the trade name RETEN by the supplier HERCULES;

• quaternized or non-quaternized vinylpyrrolidone /dialkylaminoalkyl acrylate or methacrylate copolymers such as the products sold under the trade name "GAFQUAT" by the supplier ISP such as, for example, "GAFQUAT 734" or "GAFQUAT 755", or the products designated as

"COPOLYMER 845, 958, and 937". These polymers are described in detail in French patents 2 077 143 and

2 393 573;

• dimethyl amino ethyl methacrylate

/vinylcaprolactam /vinylpyrrolidone terpolymers such as the product sold under the trade name GAFFIX VC 713 by the supplier ISP;

• vinylpyrrolidone /methacrylamidopropyl

dimethylamine copolymers, in particular as sold under the trade name STYLEZE CC 10 by ISP.

• and vinylpyrrolidone /quaternized dimethylamino propyl methacrylamide copolymers such as the product sold under the trade name "GAFQUAT HS 100" by the supplier ISP; and

• cross-linked polymers of methacryloyloxy

(Ci-C₄)alkyl (C₁-C₄) trialkyl ammonium salts such as the polymers obtained by homopolymerization of

dimethylaminoethylmethacrylate quaternized by methyl chloride, or by copolymerization of acrylamide with dimethylaminoethylmethacrylate quaternized by methyl chloride, the homo- or copolymerization being followed by cross-linking with a compound containing an olefinically unsaturated bond, in particular methylene bis-acrylamide . More particularly, an acrylamide /methacryloyloxyethyl trimethylammonium chloride cross-linked polymer (20/80 by weight) may be used in the form of a dispersion

containing 50% by weight of said copolymer in mineral oil. This dispersion is sold under the name "SALCARE® SC 92" by the supplier CIBA. It is also possible to use a cross-linked homopolymer of methacryloyloxyethyl

trimethylammonium chloride, for example in dispersion in mineral oil or in a liquid ester. These dispersions are provided under the names "SALCARE® SC 95" and "SALCARE® SC 96" by the supplier CIBA;

(2) polymers constituted by piperazinyl motifs and divalent alkylene or hydroxyalkylene radicals with straight or branched chains, possibly interrupted by oxygen, sulfur or nitrogen atoms or aromatic or

heterocyclic cycles as well as the oxidation and/or quaternization products of said polymers. Such polymers are in particular described in French patents 2 162 025 and 2 280 361;

(3) polyaminoamides that are soluble in water prepared, in particular, by polycondensation of an acid compound with a polyamine; these polyaminoamides may be cross-linked 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 an oligomer resulting from the reaction of a bifunctional compound that is reactive towards a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide, an epihalohydrin, a diepoxide or a bis- unsaturated derivative; the cross-linking agent is used in proportions of 0.025 to 0.35 moles per amine group of the polyaminoamide ; these polyaminoamides may be

alkylated or, if they comprise one or more tertiary amine functions, they may be quaternized. Such polymers are in particular described in French patents 2 252 840 and 2 368 508;

(4) derivatives of polyaminoamides resulting from condensation of polyalkylene polyamines with

polycarboxylic acids followed by alkylation with

functional agents. Examples that may be mentioned are adipic acid-dialkylaminohydroxyalkyldialkylene triamine polymers in which the alkyl radical contains 1 to 4 carbon atoms and preferably designates methyl, ethyl or propyl. Such polymers are described in particular in French patent 1 583 363;

More particular examples of these derivatives that may be mentioned are adipic acid /dimethylamino- hydroxypropyl /diethylene triamine polymers provided under the trade name "Cartaretine F, F4, or F8" by the supplier Sandoz.

(5) polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid selected from diglycolic acid and saturated aliphatic dicarboxylic acids containing 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is in the range 0.8: 1 to 1.4; the resulting polyaminoamide is reacted with epichlorhydrin in a molar ratio of epichlorhydrin to the second amine group of the polyaminoamide in the range 0.5:1 to 1.8:1. Such polymers are described in particular in American patents US 3 227 615 and US 2 961 347;

Polymers of this type are in particular sold under the trade name "Hercosett 57" by the supplier Hercules Inc. or under the trade name "PD 170" or "Delsette 101" by the supplier Hercules for an adipic acid /epoxypropyl /diethylene-triamine copolymer.

(6) alkyl diallyl amine or dialkyl diallyl ammonium cyclopolymers such as homopolymers or copolymers comprising motifs with formulae (V) or (V) as the

principal constituent of the chain:

in which formulae k and t equal 0 or 1, the sum k + t being equal to 1; R12 designates a hydrogen atom or a methyl radical; Ri o and Rn, independently of each other, designate an alkyl group containing 1 to 6 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably contains 1 to 5 carbon atoms, a lower ( C1-C4) amidoalkyl group, or Ri o and Rn may, together with the nitrogen atom to which they are attached, designate heterocyclic groups such as piperidinyl or morpholinyl ; and Y- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, or phosphate. These polymers are in particular described in French patent 2 080 759 and in its certificate of addition 2 190 406;

^• Ri o and Rn , independently of each other, preferably designate an alkyl group containing 1 to 4 carbon atoms and more particularly 1 carbon atom;

More particular examples of polymers as defined above that may be mentioned are the dimethyldiallyl ammonium chloride homopolymer sold under the trade name "Merquat 100" by the supplier NALCO (and its homologs with low mass average molecular weights) and copolymers of diallyldimethylammonium chloride and acrylamide sold under the trade name "MERQUAT 550".

(7) the quaternary diammonium polymer containing recurring motifs with formula: R 13 R 15

in which formula (VII) :

^• Ri₃, Ri₄, Ri₅, and Ri₆, which may be identical or different, represent aliphatic, alicyclic, or

arylaliphatic radicals containing 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or R₁₃, R_i4, R_i5 and R16, together or separately, constitute, together with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen or R₁₃, R_i4, R_i5 and Ri₆ represent a linear or branched C₁-C6 alkyl radical substituted with a nitrile, ester, acyl, amide or -CO-O-R17-D or -CO-NH-R₁₇-D group where R₁₇ is an alkylene and D is a quaternary ammonium group;

Ai and Bi represent polymethylene groups containing

2 to 20 carbon atoms that may be linear or branched, saturated or unsaturated, and may contain, linked to or interposed in the main chain, one or more aromatic rings, one or more oxygen or sulfur atoms or sulfoxide,

sulfone, disulfide, amino, alkylamino, hydroxyl,

quaternary ammonium, ureido, amide or ester groups; and

^• X- designates an anion derived from an organic or inorganic acid;

^• Ai, Ri₃, and R15 may, with the two nitrogen atoms to which they are attached, form a piperazine cycle;

further, if Ai designates a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, Bi may also designate a group (CH₂) _n ^_CO-D-OC- (CH₂) _p- ;

where n and p are integers in the range approximately 2 to 20; and

D designates: a) a glycol residue with formula: -0-Z-0-, where Z designates a linear or branched hydrocarbon radical or a group having one of the following formulae:

• (CH₂-CH₂-0)_x-CH₂-CH₂-

• [CH₂-CH(CH₃) -0]_y-CH₂-CH(CH₃) - where x and y designate an integer in the range 1 to 4, representing a predetermined, unique degree of

polymerization or any nucleic from 1 to 4 representing a mean degree of polymerization;

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

c) a bis-primary diamine residue with formula:

-NH-Y-NH-, where Y designates a linear or branched hydrocarbon radical, or the bivalent radical

CH₂—CH₂—S-S-CH₂—CH₂— ;

d) a ureylene group with formula: -NH-C0-NH-; and X- is preferably an anion such as chloride or bromide .

These polymers have a number average molecular mass that is generally in the range 1000 to 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 in US patents Nos.

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.

More particularly, polymers constituted by recurring motifs with the following formula may be used:

in which Ri g , Ri g , R₂ o and R₂ i , which may be identical or different, designate an alkyl or hydroxyalkyl radical containing approximately 1 to 4 carbon atoms, r and s are integers in the range approximately 2 to 20 and, X- is an anion derived from an organic or inorganic acid.

A particularly preferred compound with formula

(VIII) is that in which Ri g , Ri g , R2₀ and R2₁, represent a methyl radical and r = 3, s = 6 and X = CI, known as Hexadimethrine chloride using the INCI nomenclature

(CTFA) .

(8) quaternary polyammonium polymers constituted by motifs with formula (IX) :

^22 R₂₄

— N+ - (CH₂)_t - NH - CO - (CH₂)_u - CO - NH - (CH₂)_v - N+ - A—

^R23 (IX) _x_ R₂₅

in which formula:

^• R22, R23, R2₄ and R25, which may be identical or different, represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl , β-hydroxypropyl or

-CH2CH2 (OCH₂CH₂)_POH radical;

where :

^• p is equal to 0 or to an integer in the range 1 to 6, provided that R22, R23, R24, and R25 do not

simultaneously represent a hydrogen atom;

^• t and u, which may be identical or different, are integers in the range 1 to 6;

^• v is equal to 0 or an integer in the range 1 to

34;

^• X- designates an anion such as a halide;

^• A designates a radical of a dihalide or,

preferably, represents -CH2-CH2-O-CH2-CH2- .

Such compounds are described in particular in patent application EP-A-122 324.

Examples of the above that may be mentioned include the products "Mirapol® A 15", "Mirapol® AD1 " , "Mirapol® AZ1" and "Mirapol® 175" provided by the supplier Miranol;

(9) Quaternary vinylpyrrolidone and vinylimidazole polymers such as the products provided under the trade names Luviquat® FC 905, FC 550, and FC 370 by the

supplier B.A.S.F, for example;

(10) Cationic polysaccharides, in particular

celluloses and cationic galactomannan gums.

More particular examples of cationic polysaccharides that may be mentioned are derivatives of cellulose ethers comprising quaternary ammonium groups, cationic

copolymers of cellulose or cellulose derivatives grafted with a hydrosoluble quaternary ammonium monomer and cationic galactomannan gums.

Derivatives of cellulose ethers comprising

quaternary ammonium groups have been described in French patent 1 492 597. These polymers are also defined in the CTFA dictionary as quaternary ammonium

hydroxyethylcellulose compounds that have reacted with an epoxide substituted with a trimethylammonium group.

Cationic cellulose copolymers or cellulose

derivatives grafted with a hydrosoluble quaternary ammonium monomer are described in particular in the patent US 4 131 576, such as hydroxyalkyl celluloses, for example hydroxymethyl-, hydroxyethyl- or hydroxypropyl- celluloses grafted in particular with a methacryloylethyl trimethylammonium salt, methacrylamidopropyl

trimethylammonium salt, or dimethyl-diallylammonium salt.

Cationic galactomannan gums are described more particularly in patents US 3 589 578 and 4 031 307, in particular guar gums containing cationic trialkylammonium groups. As an example, guar gums modified by a salt (for example chloride) of 2 , 3-epoxypropyl trimethylammonium may be used.

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 containing vinylpyridine or vinylpyridinium motifs, condensates of polyamines and epichlorhydrin, quaternary polyureylenes , and chitin derivatives. Particular examples of cationic proteins or protein hydrolysates are chemically modified polypeptides carrying quaternary ammonium groups at the chain end or grafted thereto. Their molecular mass may, for example, be from 1500 to 10,000, in particular from approximately 2000 to 5000. Particular examples of these compounds that may be mentioned are as follows:

Preferably, these polypeptides are of vegetable origin .

The following may in particular be mentioned:

• hydrolysates of wheat, soya, or rice protein modified by cocodimonium hydroxypropyl groups;

• hydrolysates of protein, soya, jojoba, oats, or rice wheat modified by hydroxypropyl trimonium groups;

• hydrolysates of wheat, soya, or jojoba protein modified by laurdimonium hydroxypropyl groups; and

• hydrolysates of jojoba, soya, or rice protein modified by steardimonium hydroxypropyl groups.

Examples of these products that may be mentioned include the products provided by the supplier COGNIS under the trade name GLUADIN WQ, by the supplier CRODA under the trade names HYDROTRITICUM WQ PE or CROQUAT SOYA.

Preferred examples of cationic polymers that could be used in the context of the present invention are cationic cyclopolymers , in particular homopolymers or copolymers of dimethyldiallylammonium chloride, sold under the trade names "MERQUAT 100", "MERQUAT 550" and "MERQUAT S" by the supplier NALCO, quaternary

vinylpyrrolidone and vinylimidazole polymers and cationic polysaccharides, and mixtures thereof.

Non-silicone cationic surfactants

The conditioning agent or agents that may be used in accordance with the invention may be selected from non- silicone cationic surfactants. The term "non-silicone cationic surfactant" means a surfactant having no silicon atoms in its structure and positively charged when it is contained in the

composition of the invention. This surfactant may carry one or more permanent positive charges or contain one or more cationizable functions in the composition of the invention .

The cationic surfactant or surfactants suitable for use as conditioning agents in the context of the present invention are preferably selected from primary,

secondary, or tertiary fatty amines, possibly

polyoxyalkylenated, or their salts, quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one C8-C30 hydrocarbon chain. Examples of fatty amines that may be used in accordance with the invention that may be mentioned are stearyl amidopropyl dimethylamine and distearylamine .

Examples of quaternary ammonium salts that may in particular be mentioned are as follows:

• those with the following general formula (XII) :

(XII) in which the radicals Rs to Rn, which may be identical or different, represent a linear or branched aliphatic radical containing 1 to 30 carbon atoms or an aromatic radical such as aryl or alkylaryl, at least one of radicals Rs to Rn designating a radical containing 8 to 30 carbon atoms, preferably 12 to 24 carbon atoms. The aliphatic radicals may comprise heteroatoms such as oxygen, nitrogen, sulfur or the halogens. Examples of aliphatic radicals are selected from C1-C30 alkyl, C1-C30 alkoxy, ( C2-C6) polyoxyalkylene, C1-C30 alkylamide,

( C12 - C22 ) alkyl ( C2-C6) amidoalkyl, ( C12 - C22 ) alkyl acetate, and C₁-C30 hydroxyalkyl ; X- is an anion selected from the group formed by halides, phosphates, acetates, lactates, (C₂-C6) alkyl sulfates, and alkyl- or alkylaryl- sulfonates .

Preferred examples of quaternary ammonium salts with formula (XII) are tetraalkylammonium chlorides such as, for example, dialkyldimethylammonium or

alkyltrimethylammonium chlorides in which the alkyl radical comprises approximately 12 to 22 carbon atoms, in particular behenyltrimethylammonium,

distearyldimethy1ammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides or,

alternateively, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl- (myristyl acetate) - ammonium chloride such that sold under the trade name CERAPHYL® 70 by the supplier VAN DYK;

• quaternary ammonium salts of imidazoline such as, for example, those with the following formula (XIII) :

in which R₁₂ represents an alkenyl or alkyl radical containing 8 to 30 carbon atoms, for example fatty acid derivatives from tallow, R₁₃ represents a hydrogen atom, a C₁-C₄ alkyl radical or an alkenyl or alkyl radical

containing 8 to 30 carbon atoms, R14 represents a C₁-C₄ alkyl radical, R15 represents a hydrogen atom, a C₁-C₄ alkyl radical, X- is an anion selected from the group formed by halides, phosphates, acetates, lactates, alkylsulfates , alkyl- or alkylaryl-sulfonates .

Preferably, R₁₂ and R₁₃ designate a mixture of alkenyl or alkyl radicals containing 12 to 21 carbon atoms, for example fatty acid derivatives from tallow, R_i4 designates a methyl radical, R15 designates a hydrogen atom. An example of such a product is that sold under the trade name REWOQUAT® W 75 by the supplier REWO;

• quaternary di- or triammonium salts, in particular with formula (XIV) :

R₁₆ 2X- (XIV)

in which Ri6 designates an alkyl radical containing approximately 16 to 30 carbon atoms optionally

hydroxylated and/or interrupted by one or more oxygen atoms, Ri7 is selected from hydrogen or an alkyl radical containing 1 to 4 carbon atoms or a (Ri6a) (Ri7a) (Ri8a)N- ( CH₂ ) ₃ - group, Ri ea , Ri7a, Ri8a, Ri s , Ri g , R2o,and R₂ i , which may be identical or different, being selected from hydrogen or an alkyl radical containing 1 to 4 carbon atoms, and X- is an anion selected from the group formed by halides, acetates, phosphates, nitrates and

methylsulfates . Examples of such compounds are Finquat CT-P promoted by the supplier FINETEX (Quaternium 89), Finquat CT promoted by the supplier FINETEX (Quaternium 75) ;

• quaternary ammonium salts containing at least one ester function, such as those with the following formula (XV) :

in which:

^• R22 is selected from C1-C6 alkyl radicals and C1-C6 hydroxyalkyl or dihydroxyalkyl radicals;

^• R2₃ is selected from:

O II

R₂6 C

• the radical • radicals R2₇, which are linear or branched, saturated or unsaturated C₁-C22 hydrocarbon radicals;

• the hydrogen atom;

^• R2₅ is selected from:

O II

R-28—C—

• the radical

• radicals R2₉, which are linear or branched, saturated or unsaturated C₁-C6 hydrocarbon radicals;

• the hydrogen atom;

^• R2₄, R26_/ and R28_/ which may be identical or

different, are selected from linear or branched,

saturated or unsaturated C7-C2₁ hydrocarbon radicals;

^• r, s, and t, which may be identical or different, are integers from 2 to 6;

^• y is an integer from 1 to 10;

^• x and z, which may be identical or different, are integers from 0 to 10;

^• X- is a simple or complex organic or inorganic anion ;

^• provided that the sum x + y + z is equal to 1 to 15, that when x is equal to 0 then R2₃ designates R2₇ and that when z is equal to 0 then R2₅ designates R2₉.

The R22 alkyl radicals may be linear or branched, more particularly linear.

Preferably, R22 designates a methyl, ethyl,

hydroxyethyl , or dihydroxypropyl radical, and more particularly a methyl or ethyl radical.

Advantageously, the sum x + y + z is equal to a value in the range 1 to 10.

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

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

Advantageously, R2₄, R26, and R28, which may be identical or different, are selected from linear or branched, saturated, or unsaturated C₁₁-C2₁ hydrocarbon radicals, and more particularly from linear or branched, saturated or unsaturated alkyl and alkenyl C₁₁-C2₁

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, still more particularly equal to 2.

The anion X- is preferably a halide (chloride, bromide or iodide) or an alkylsulfate, more particularly methylsulfate . However, it is possible to use the methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as the acetate or lactate, or any other anion compatible with the ammonium possessing an ester function.

Still more particularly, the anion X- is the

chloride or the methylsulfate .

More particularly, in the composition of the

invention, ammonium salts with formula (XV) are used in which :

• R22 designates 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 selected from:

O II

R₂₆—C—

• the radical

• methyl, ethyl, or C14- C22 hydrocarbon radicals;

• the hydrogen atom;

• R25 is selected from:

O II

R₂g—C—

• the radical

• the hydrogen atom;

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

unsaturated C13-C17 alkyl and alkenyl radicals.

Advantageously, the hydrocarbon radicals are linear.

Examples that may be mentioned are compounds with formula (XV) such as salts (in particular chloride or methylsulfate) of diacyloxyethyl-dimethylammonium, of diacyloxyethyl-hydroxyethyl-methylammonium, of

monoacyloxyethyl-dihydroxyethyl-methylammonium, of triacyloxyethyl-methylammonium, or of monoacyloxyethyl- hydroxyethyl-dimethylammonium, and mixtures thereof. The acyl radicals preferably contain 14 to 18 carbon atoms and more particularly originate from a vegetable oil such as palm oil or sunflower oil. When the compound contains several acyl radicals, they may be identical or

different .

Said products are obtained, for example, by direct esterification of triethanolamine, of

triisopropanolamine, of alkyldiethanolamine, or of alkyldiisopropanolamine optionally oxyalkylenated on C10-C30 fatty acids or on C10-C30 fatty acid mixtures of animal or vegetable origin, or by transesterification of their methyl esters. This esterification is followed by quaternization using an alkylation agent such as an alkyl halide (preferably methyl or ethyl) , a dialkyl sulfate (preferably methyl or ethyl) , methyl methanesulfonate, methyl para-toluenesulfonate, or glycol, or glycerol chlorhydrin .

By way of example, such compounds are sold under the trade names DEHYQUART® by the supplier HENKEL,

STEPANQUAT® by the supplier STEPAN, NOXAMIUM® by the supplier CECA, or REWOQUAT® WE 18 by the supplier REWO- WITCO.

The composition of the invention may, for example, contain a mixture of quaternary ammonium mono-, di- and trimester salts with a majority by weight of diester salts . It is also possible to use ammonium salts containing at least one ester function as described in patents US-A-4 874 554 and US-A-4 137 180.

Particularly preferred cationic surfactant ( s ) that may be used in the invention are selected from compounds with formula (XII) or with formula (XV) .

Preferred examples of cationic surfactants that may be present in the composition of the invention include cetyl trimethyl ammonium, behenyl trimethyl ammonium, dipalmitoylethyl hydroxyethyl methyl ammonium,

distearoylethyl hydroxyethyl methyl ammonium, methyl (C9-C19) alkyl , (C10-C20) alkyl amidoethylimidazolium, and stearamidopropyldimethylamine salts, a salt of

stearamidopropyl dimethylammonium, and mixtures thereof.

Silicones

Non-limiting examples of silicones that may be used as conditioning agents of the present invention that may be mentioned are:

I. Volatile silicones:

These have a boiling point in the range 60°C to 260°C. This type of silicone includes:

(i) cyclic silicones containing 3 to 7 silicon atoms, and preferably 4 to 5.

It may, for example, be the octamethylcyclo- tetrasiloxane sold under the name "VOLATILE SILICONE 7207®" by the supplier UNION CARBIDE or "SILBIONE

70045 V2®" by the supplier RHONE POULENC, the

decamethylcyclopentasiloxane sold under the name

"VOLATILE SILICONE 7158®" by the supplier UNION CARBIDE, "SILBIONE 70045 V5®" by the supplier RHONE POULENC, and also their mixtures. Cyclopolymers of the

dimethylsiloxane /methylalkylsiloxane type, such as "SILICONE VOLATILE FZ 3109®" sold by the supplier UNION CARBIDE, which is a dimethylsiloxane /methyloctylsiloxane cyclocopolymer, may also be mentioned; (ii) linear volatile silicones containing 2 to 9 silicon atoms and having a viscosity of 5><10^~6 m²/s [square meters per second] or less at 25°C.

It may, for example, be the hexamethyldisiloxane sold under the trade name "SILBIONE 70041 V0,65®" by the supplier 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, pp. 27-32.

II. Non-volatile silicones

These are principally constituted by

polyalkylsiloxanes , polyarylsiloxanes ,

polyalkylarylsiloxanes and organomodified polysiloxanes , and also their mixtures. They may be in the form of oils, gums or resins.

Examples of polyalkylsiloxanes that may be mentioned are principally linear polydimethylsiloxanes with a viscosity of more than 5><10^~6 m²/s, and preferably less than 2.6 m²/s, i.e.:

• with terminal trimethylsilyl groups, non-limiting examples of which are "SILBIONE®" oils from the 70047 series sold by the supplier RHONE POULENC, Wacker Belsil DM 60000 oil from WACKER, or certain "VISCASIL®" liquids from the supplier GENERAL ELECTRIC;

• with terminal trihydroxysilyl groups, such as oils from the "48 V®" series from the supplier RHONE POULENC.

In this class of polyalkylsiloxanes, mention can also be made of polyalkylsiloxanes provided by the supplier GOLDSCHMIDT under the trade names "ABILWAX

9800®" and "ABILWAX 9801®", which are

poly(Ci-C2o) alkylsiloxanes .

Examples of polyalkylarylsiloxanes that may be mentioned are polydimethylphenylsiloxanes , linear and/or branched polydimethyldiphenylsiloxanes with a viscosity of 10^~5 to 5xl0^~2 m²/s such as, for example:

• "RHODORSIL®" oil 763 from RHONE POULENC; • "SILBIONE®" oils from the 70641 series from RHONE POULENC, such as "SILBIONE 70641 V30®" and "SILBIONE 70641 V200®" oils;

• the product "DC 556®" Cosmetic Grad Fluid from DOW CORNING;

• silicones from the series PK de BAYER, such as "PK20®";

• silicones from the series PN, PH de BAYER, such as "PN 1000®" and "PH 1000®"; and

• certain oils from the SF series from GENERAL

ELECTRIC, such as "SF 1250®", "SF 1265®", "SF 1154®", "SF 1023®" .

The silicone gums of the present invention are polydiorganosiloxanes with a high number average

molecular mass in the range 200,000 to 1,000,000, used alone or as a mixture in a solvent selected from volatile silicones, polydimethylsiloxane oils (PDMS) ,

polyphenylmethylsiloxanes (PPMS) oils, isoparaffins , methylene chloride, pentane, dodecane, tridecane,

tetradecane, or mixtures thereof.

Examples that may be mentioned are compounds

containing the following structures:

• poly [ (dimethylsiloxane) / (methylvinylsiloxane) ] gums ;

• poly [ (dimethylsiloxane) / (diphenylsiloxane) ] gums;

• poly [ (dihydrogeno dimethylsiloxane)

/ (divinylsiloxane) ] gums;

• poly[ (dimethylsiloxane) / (phenylmethylsiloxane) ] gums ;

• poly [ (dimethylsiloxane) /(diphenylsiloxane)

/ (methylvinylsiloxane) ] gums.

Mirasil DM 300 000 from Rhodia may be mentioned. The following non-limiting examples may also be mentioned :

1) mixtures formed from a polydimethylsiloxane hydroxylated at the chain end (DIMETHICONOL in the CTFA nomenclature) , and a cyclic polydimethylsiloxane (CYCLOMETHICONE in the CTFA nomenclature) , such as the products "Q2 1401®" or DOW CORNING 1501 FLUID provided by the supplier 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 "SE 30 ®" gum with a MW of 500000 (number average) dissolved in "SF 1202 SILICONE FLUID®" (decamethylcyclopentasiloxane) ;

3) mixtures of two PDMS with different viscosities, in particular a PDMS gum and a PDMS oil, such as the products "SF 1236®" and "CF 1241®" from the supplier GENERAL ELECTRIC. The product "SF 1236®" is a mixture of a "SE 30®" gum as defined above with a viscosity of

20 m²/s and a "SF 96®" oil with a viscosity of 5><10⁶ m²/s (15% of "SE 30®" gum and 85% of "SF 96®" oil) .

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

The organopolysiloxane resins that may be used in accordance with the invention are cross-linked siloxane systems comprising the units: R₂Si0₂/2, RSi0₃/2 and Si0₄/2 in which R represents a hydrocarbon group containing 1 to 6 carbon atoms or a phenyl group. Particularly preferred examples of these products are those in which R

designates a lower alkyl radical or a phenyl radical.

Examples of these resins that may be mentioned are the product sold under the trade name "DOW CORNING 593®" or those sold under the trade names "SILICONE FLUID SS 4230" and "SILICONE FLUID SS 4267" by the supplier

GENERAL ELECTRIC and that are dimethyl

/trimethylpolysiloxanes .

The organomodified silicones of the present

invention are silicones as defined above, comprising in their general structure one or more organo-functional groups bonded directly to the siloxane chain or bound via a hydrocarbon radical.

Examples that may be mentioned are silicones

comprising : a) perfluorinated groups such as trifluoroalkyls such as, for example, those provided by the supplier GENERAL ELECTRIC under the trade names "FF.150

FLUOROSILICONE FLUID®" or by the supplier SHIN ETSU under the trade names "X-22-819®", "X-22-82®", "X-22-821®" and "X-22-822®";

b) hydroxyacylamino groups such as, for example, those described in patent application EP 0 342 834 and in particular the silicone sold by the supplier DOW CORNING under the trade name "Q2-8413®";

c) thiol groups such as in the silicones "X 2-8360®" from the supplier DOW CORNING or "GP 72A®" and "GP 71®" from GENESEE;

d) non-quaternized amino groups, such 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, such as the products

described in patent EP 186 507 from CHISSO CORPORATION; f) hydroxyl groups such as polyorganosiloxanes with a C₂-C₁₈ hydroxyalkyl function described, for example, in patent application FR 85/16334; more particularly mention may be made of the product supplied by Dow Corning under the name DC 190;

g) alkoxy groups such as those in the silicone copolymer "F 755®" from SWS SILICONES and the products "ABILWAX 2428®", "ABILWAX 2434®", "ABILWAX 2440®" from the supplier GOLDSCHMIDT;

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

i) quaternary ammonium groups such as in the

products "X2 81 08®" and "X2 81 09®", the product "ABIL K 3270®" from the supplier GOLDSCHMIDT; j) amphoteric or betaine groups, such as those in the product provided by the supplier GOLDSCHMIDT under the trade name "ABIL B 9950®";

k) bisulfite groups such as in the products provided by the supplier GOLDSCHMIDT under the trade names "ABIL S 201®" and "ABIL S 255®"; and

1) polyethyleneoxy and/or polypropyleneoxy groups optionally comprising C6-C24 alkyl groups, such as

products known as dimethicone copolyol provided by the supplier DOW CORNING under the trade name DC 1248 or

SILWET L 722, L 7500, L 77, L 711 oils from the supplier UNION CARBIDE and the (C12) alkyl methicone copolyol

provided by the supplier DOW CORNING under the trade name Q2 5200;

In accordance with the invention, it is also

possible to use silicones comprising a polysiloxane

portion and a portion constituted by an organic non- silicone chain, one of the two portions constituting the main chain of the polymer, the other being grafted onto said principal chain. These polymers are, for example, described 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 in US patents Nos. 4 693 935,

4 728 571, and 4 972 037. These polymers are preferably anionic or non-ionic.

Examples of such polymers are copolymers that can be obtained by radical polymerization from a mixture of

monomers constituted by:

a) 50% to 90% by weight of tertiobutyl acrylate;

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

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

(XVIII)

with v being a number from 5 to 700; the percentages by weight are calculated relative to the total monomer weight .

Other particular examples of graft silicone polymers are polydimethylsiloxanes (PDMS) onto which mixed polymer motifs are grafted, via a linker of the thiopropylene type, which mixed polymer motifs are of the

poly (meth) acrylic and alkyl poly (meth) acrylate types, and polydimethylsiloxanes (PDMS) , onto which polymer motifs of the poly isobutyl (meth) acrylate type are grafted via a thiopropylene type linker.

In accordance with the invention, all of the

silicones may also be used in the form of emulsions, nanoemulsions or microemulsions .

Particularly preferred polyorganosiloxanes of the invention are:

• non-volatile silicones selected from the

polydialkylsiloxane family with terminal trimethylsilyl groups, such as oils with a viscosity in the range

0.2 m²/s to 2.5 m²/s at 25°C, for example oils from the DC200 series from DOW CORNING, in particular that with a viscosity of 60,000 Cst, from the SILBIONE 70047 series, more particularly 70,047 V 500,000 oil provided by the supplier RHODIA CHIMIE, polydialkylsiloxanes with

terminal dimethylsilanol groups such as dimethiconol or polyalkylarylsiloxanes such as SILBIONE 70641 V 200 oil provided by the supplier RHODIA CHIMIE; and

• polysiloxanes with amine groups such as

aminodimethicones or trimethylsilylamodimethicone .

The viscosities of the silicones may in particular be determined using the standard ASTM D445-97

(viscometry) .

Hydrocarbons

When the conditioning agent of the composition of the invention is a hydrocarbon, it is a linear or

branched C8-C300 hydrocarbon. Particular examples of hydrocarbons that are liquid at ambient temperature that fall within this definition that can be mentioned are isododecane, isohexadecane and its isomers (such as 2 , 2 , 4 , 4 , 6, 6-heptamethylnonane) , isoeicosane, isotetracosane, isomers of said compounds, n-dodecane, n-nonane, n-undecane, n-tridecane, n- pentadecane, vaseline oil and mixtures of said

hydrocarbons .

Preferably, vaseline oil, isododecane or one of its isomers is used in the invention.

Fatty alcohols

When the conditioning agent is a fatty alcohol, it is of the linear or branched, saturated or unsaturated C8-C30 type. Examples of these that may be mentioned are 2-butyl octanol, lauric alcohol, oleic alcohol, isocetyl alcohol, isostearic alcohol, behenyl alcohol, stearyl alcohol, cetyl alcohol, and mixtures thereof.

Fatty esters

When the conditioning agent is a fatty ester, it may either be an ester of a C8-C30 fatty acid and C₁-C30 monoalcohols or polyols including esters of C8-C30 fatty acids and C8-C30 fatty alcohols, or an ester of a C₁-C7 dibasic acid and a C8-C30 fatty alcohol.

Examples of such esters that may be mentioned are ethyl, isopropyl, 2-ethylhexyl and 2-octyldecyl

palmitate, isopropyl, butyl, cetyl and 2-octyldecyl myristate, butyl and hexyl stearate, hexyl and 2- hexyldecyl laurate, isononyl isononanoate, dioctyl malate, dioctyl, myristyl myristate, stearyl myristate, cetyl palmitate, myristyl stearate, stearyl stearate, cetyl stearate, and mixtures thereof.

It is also possible to mention natural or synthetic triglycerides, in particular vegetable oils such as rapeseed oil, avocado oil, olive oil, sunflower oil, argan oil, or grapeseed oil. Ceramides

Ceramides or ceramide analogs, such as

glycoceramides , that can be used as a conditioning agent in the compositions of the invention are known per se and are natural or synthetic molecules that may have the following general formula (XIX) :

R₃CHOH—CH—CH₂OR₂

NH

I (XIX) c=o in which:

• Ri designates a, linear or branched, saturated or unsaturated alkyl radical derived from C14-C30 fatty acids, said radical possibly being substituted with a hydroxyl group in the alpha position, or a hydroxyl group in the omega position esterified by a saturated or unsaturated C16-C30 fatty acid;

• R2 designates a hydrogen atom or a (glycosyl)_n, (galactosyl ) _m or sulfogalactosyl radical, in which n is an integer in the range 1 to 4 and m is an integer in the range 1 to 8; and

• R3 designates a C15-C26 hydrocarbon radical,

saturated or unsaturated in the alpha position, said radical possibly substituted with one or more C₁-C14 alkyl radicals ;

it being understood that with natural ceramides or glycoceramides, R3 may also designate a C15-C26 alpha- hydroxyalkyl radical, the hydroxyl group optionally being esterified by a C16-C30 alpha-hydroxyacid .

Ceramides that are preferred in the context of the present invention are those described by DOWNING in Arch. Dermatol, Vol. 123, 1381-1384, 1987, or those described in French patent FR 2 673 179.

A more particularly preferred ceramide or more particularly preferred ceramides of the invention are compounds for which Ri designates a saturated or

unsaturated alkyl derivative of C16-C22 fatty acids; R2 designates a hydrogen atom; and R₃ designates a saturated Ci₅ linear radical.

Examples of such compounds are:

• N-linoleoyldihydrosphingosine ;

• N-oleoyldihydrosphingosine ;

• N-palmitoyldihydrosphingosine ;

• N-stearoyldihydrosphingosine ;

• N-behenoyldihydrosphingosine ; or

mixtures of these compounds.

Still more preferably, ceramides are used for which Ri designates a saturated or unsaturated alkyl radical derived from fatty acids; R₂ designates a galactosyl or sulfogalactosyl radical; and R₃ designates a -CH=CH- (CH₂)i₂-CH₃ group.

An example that may be mentioned is the product constituted by a mixture of these compounds, sold under the trade name GLYCOCER by the supplier WAITAKI

INTERNATIONAL BIOSCIENCES.

Abrasive solid particles

The term "abrasive solid particles" means particles with a hardness that is greater than or equal to that of hair. As an example, the abrasive solid particles may have a hardness of 3 or more on the Mohs scale, or even 4 or more, for example 5 or more on the Mohs scale.

The solid particles may be selected from natural materials, in particular of mineral or vegetable origin, or from synthetic materials. The abrasive solid

particles may, for example, be selected from the

following materials, although this list is not limiting:

• inorganic and/or metallic particles such as boron nitride in the cubic form (Borazon®) , aluminosilicate, zircon, mixed aluminum oxides such as emery, zinc oxide, aluminum oxides such as aluminas or corundum, titanium oxide, mica titanium oxide, carbides, in particular silicon carbide (carborundum) , or other metallic oxides, metals and metal alloys such as iron shot, steel, in particular pearlite; silicates such as glass, quartz or sand, calcium carbonate (for example bora bora sand or Rose de Brignoles marble) or magnesium carbonate, sodium chloride, pumice stone, amorphous silica, diamond, or ceramics ;

• organic particles such as fruit kernels,

especially apricot, for example Scrubami® apricot, wood cellulose, for example ground bamboo, coconut shell, for example Coconut exfoliator; polyamides, in particular Nylon-6, sugars; polyethylenes ; polypropylenes ; and

• mixed particles combining organic and inorganic compounds, and particles coated with the compounds described above.

The solid particles may have a flattened, spherical, elongate, polyhedral or irregular shape. The solid particles may, for example, originate from powdered pumice stone grains, powdered diamond, powdered fruit kernels, powdered coconut shells, microbeads, for example alumina microbeads, glass microbeads, polyamide

microbeads, in particular Nylon-6, or from fibers, in particular polyamide fibers and hardwood cellulose fibers .

Moisturizing agents

The moisturizing agents are preferably selected from urea, urea derivatives such as hydroxyethylurea, polyols such as glycerin, propyleneglycol or sorbitol,

polyethylene glycols.

Preferably, the composition of the invention

comprises at least one conditioning agent or at least one reducing agent or at least one organic or inorganic base, or at least one hair dye.

Still more preferably, the composition of the invention comprises at least one hair conditioning agent. The cosmetic hair composition used in accordance with the invention may also contain other compounds that are normal in the hair cosmetics field, such as vitamins and pro-vitamins including panthenol, sunscreens, organic or inorganic pigments, which may optionally be colored, pearlizing and opacifying agents, sequestrating agents, plasticizers, solubilizing agents, anti-oxidants ,

hydroxyacids , fragrances, non-ionic, anionic, cationic or amphoteric surfactants, non-ionic, anionic, cationic or amphoteric polymers, short chain alkanols such as ethanol or isopropanol, acidifying agents and preservatives.

The compositions of the invention may be aqueous or anhydrous. They may be in the form of powders, liquids, gels, milks, creams or non-powdery solids. They may optionally be sprayed onto the hair using an aerosol or a pump bottle.

The method of the invention may be implemented in a plurality of variant embodiments.

In first variant exemplary embodiments, the hair is combed using a motor-driven device after applying the composition of the invention to the hair, the composition possibly being present on the hair.

In second variant exemplary embodiments, the hair is combed using a motor-driven device before applying the composition of the invention to the hair. In these variant exemplary embodiments, combing is carried out after wetting the hair or after applying a composition not comprising active ingredients of the invention.

The first variant exemplary embodiments are

preferred. The method according to these variant

exemplary embodiments may also include a subsequent step of applying of a composition with or without active ingredients of the invention.

The treatment may optionally be followed by rinsing.

Finally, the hair is dried or left to dry. The method of the invention may be repeated several times. In general, the method of the invention is applied once or twice.

The invention is particularly suitable for curly or frizzy hair.

The invention can be better understood from the following description of non-limiting examples made with reference to the accompanying drawings in which:

• Figure 1 represents an example of a combing device of the invention;

• Figure 2 represents the device of Figure 1 in diagrammatic section;

• Figure 3 diagrammatically illustrates the

deformation of the diaphragm during operation of the device ;

• Figure 4 illustrates the use of the device

• Figure 5 is a diagrammatic and perspective

representation of a variant embodiment of a combing device; and

• Figures 6A and 6B represent a head of hair

respectively with one side treated in accordance with the invention and the other side treated conventionally.

The motor-driven combing device represented in

Figures 1 and 2 comprise a hand piece 10 that can receive a detachable diaphragm 20 carrying spikes 21.

The combing device may be offered to the user with a charging unit 30 for recharging a battery 18 contained in the hand piece 10.

In the example illustrated, the device is similar to those promoted under the trade name NEO or FLEX by

TWINBIRD and to that described in particular in patent application US 2009/0182249 Al; a section of it is reproduced in Figure 2.

It can be seen in this figure that the hand piece comprises a geared electric motor 11 driving a drive member 12 in rotation on which is articulated a rod 13, connected to the diaphragm 20 by means, for example, of a hook 15 that is engaged in a portion in relief 22 provided on the inner face of the diaphragm 20.

Its periphery may be attached to a rim 16 of the casing of the hand piece 10.

In Figure 2, it can be seen that a block 23 of an elastically, deformable, porous material forming a reservoir may be disposed on the inner face side of the diaphragm, but in a variant embodiment, this material is absent. Openings 25 may allow communication between the outside of the diaphragm 20, between the spikes 21, and the block 23.

As illustrated, the hand piece may include a switch 17 that can start the electric motor 11 that is powered via the battery 18.

The spikes 21 may have different heights, generally being shorter in the central region of the diaphragm and longer at its periphery, to provide the envelope surface touching the free ends of the spikes 21 with a generally concave shape .

As illustrated, the spikes 21 may be distributed into two groups, namely a first group 21a disposed in the central region with spikes that are oriented parallel to the axis X of movement of the portion in relief, and a second group 21b with spikes disposed about the first, the respective longitudinal axes of which extend

obliquely outwardly relative to the axis X.

The spikes 21 may be disposed in concentric rows to the circumference of the diaphragm. Thus, the spikes 21 are not aligned and when the combing device is moved along a lock of hair in a direction perpendicular to or obliquely to its major axis Y, the hair that passes between the spikes 21 follows a non-rectilinear path.

During operation of the device, the rod 13 is driven in an oscillating motion from top to bottom in Figure 2, which causes periodic deformation of the diaphragm 20, the periphery of the diaphragm 20 remaining fixed relative to the hand piece 10 while its central region oscillates along the axis X with a maximum amplitude.

As illustrated in Figure 3, the oscillations of the diaphragm 20 generate a rubbing action of the spikes 21 on the hair that, combined with the use of the

composition of the invention, can achieve results that are superior using the composition alone or the combing device alone.

To use the combing device, as illustrated in

Figure 4, the user may apply the composition to the wetted hair and comb the hair, for example by passing it a few times from the base to the tips.

Example

The protocol was as follows:

a) applying a composition A comprising 1% active ingredient of a polydimethysiloxane, or B comprising 0.5% active ingredient of trimetylcetylammonium chloride to wetted hair, for example of the African or Caucasian type;

b) distribution of the composition using the hands and combing by hand or a comb on a first side of the head, and using the NEO device from the supplier TWINBIRD on the other side of the head, for 2 minutes;

c) rinsing; and

d) drying.

Applying the method, particularly to frizzy or curly hair in association with compositions A or B containing the active ingredient shows, as illustrated in Figures 6A and 6B, better individualization of the hair, resulting in a very clear reduction in volume and density compared with massage using the hands. Better disentangling and a smoother feel was also observed. This effect lasted through several shampooings.

Steps a) and b) could also be repeated after step c) then terminated by steps c) and d) . The scope of the invention also encompasses using a combing device comprising, as illustrated in Figure 5, a removable reservoir 40 containing the composition to be applied during use of the combing device. The reservoir 40 is, for example, pre-filled with composition and is supplied to the operator in the form of a cartridge to be placed in the hand piece 10.

The composition from the reservoir is distributed, for example, by means of a pump actuated by the same motor as that which deforms the diaphragm.

The expression "comprising at least one" should be construed as being equivalent to "comprising one or more" .

Claims

1. A method according

A method of treating hair, the method comprising the following steps:

• applying a composition to the hair, the

o hair conditioning agents;

o reducing agents;

o organic or inorganic bases;

o hair dyes;

o abrasive solid particles; and

o moisturizing agents; and

• combing the hair using a motor-driven combing device (10, 20) comprising a flexible diaphragm (20) carrying spikes adapted to contact the hair, and a drive mechanism (11, 12, 13, 15) enabling the diaphragm to be deformed periodically to generate an oscillating movement of the spikes (21) in contact with the hair.

2. A method according to claim 1, wherein the hair is combed by the motor-driven device after applying some of the composition of the invention to the hair .

3. A method according to claim 1, wherein combing of the hair is combed by the motor-driven device before applying some of the composition of the invention to the hair.

4. A method according to any one of claims 1 to 3, the frequency of oscillation of the diaphragm lying in the range 0.5 Hz to 200 Hz, preferably in the range 1 Hz to 20 Hz, the limits of the ranges being included in the ranges.

5. A method according to any one of claims 1 to 4, the envelope surface defined by the free ends of the spikes being concave towards the scalp with a radius of curvature that varies with the deformations of the diaphragm.

6. A method according to any one of claims 1 to 5, the travel axis (X) of the flexible diaphragm (20) being perpendicular to the scalp during combing, at least while combing the base of hair.

7. A method according to any one of claims 1 to 6, the spikes (21) being formed from a thermoplastic material .

8. A method according to any one of claims 1 to 7, the composition including at least one hair dye selected from synthetic direct dyes, natural dyes, and oxidation dye precursors.

9. A method according to any one of claims 1 to 8, the composition including at least one reducing agent selected from phosphines and alkaline sulfites, or bisulfites and thiols.

10. A method according to any one of claims 1 to 9, the composition including at least one organic or inorganic base selected from alkali or alkaline- earth hydroxides, transition metals, and organic hydroxides .

11. A method according to any one of claims 1 to 10, the composition including at least one

conditioning agent selected from the group

comprising non-silicone cationic polymers, non- silicone cationic surfactants, silicones, in

particular organosiloxanes , linear or branched C8-C30 hydrocarbons, linear or branched C8-C30 fatty

alcohols, esters of C8-C30 fatty acids and C₁-C30 mono alcohols or polyols including esters of C8-C30 fatty acids and C8-C30 fatty alcohols, and C₁-C7 esters of acids or dibasic acids and C8-C30 fatty alcohols, and ceramides or ceramide analogs.

12. A method according to any one of claims 1 to

11, the composition including at least abrasive solid particles selected from natural materials, in particular of mineral or vegetable origin, or synthetic materials.

13. A method according to any one of claims 1 to

12, the composition including at least one

moisturizing agent selected from urea, urea

derivatives such as hydroxyethylurea, polyols such as glycerin, propylene glycol, sorbitol and

polyethylene glycols.

14. A method according to any one of claims 1 to

13, the hair being combed for a period of 1 minute to 5 minutes.

15. A method according to any one of claims 1 to

14, the active ingredient or ingredients

representing more than 0.001%, preferably more than 0.1%, more preferably more than 0.2% and more particularly more than 0.5% by weight relative to the total composition weight, being applied alone or with other ingredients, and when applied with other ingredients, the active ingredient preferably representing up to 50% of the total composition weight, more preferably up to 20% of the total composition weight.