EP2076237A1

EP2076237A1 - Composition for oxidation dyeing keratinous fibres comprising at least one particular ammonium salt derived from 18mea, and a colouring method using the composition

Info

Publication number: EP2076237A1
Application number: EP07821437A
Authority: EP
Inventors: Christelle Demeulenaere; Christine Rondeau
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2006-10-25
Filing date: 2007-10-17
Publication date: 2009-07-08
Also published as: WO2008049767A1

Abstract

The present invention concerns a composition for oxidation dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in a medium appropriate for dyeing, i) at least one oxidation base, ii) at least one coupling agent, iii) at least one particular ammonium salt, iv) at least one ceramide compound or at least one particular quaternary polyammonium compound. The invention also concerns dyeing methods and devices employing said composition. The dye compositions of the invention have improved cosmetic properties; in particular, the feel of the hair after colouring of the keratinous fibre is excellent.

Description

COMPOSITION FOR OXIDATION DYEING KERATINOUS FIBRES COMPRISING AT LEAST ONE PARTICULAR AMMONIUM SALT DERIVED FROM 18MEA, AND A COLOURING METHOD USING THE COMPOSITION

The present invention relates to a composition for oxidation dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in a medium appropriate for dyeing, i) at least one oxidation base; ii) at least one coupling agent; iii) at least one particular ammonium salt; iv) at least one ceramide compound or at least one particular quaternary polyammonium compound.

The invention also relates to a dyeing method employing said composition, and to a multi-compartment device containing the composition.

Dyeing keratinous fibres, in particular human hair, using dye compositions containing precursors of the oxidation dye, generally termed oxidation bases, such as ortho- or paraphenylenediamines, ortho- or paraaminophenols or heterocyclic compounds, is known. Such oxidation bases are colourless or slightly coloured compounds which, when associated with oxidizing agents, can give rise to coloured compounds by an oxidative condensation process. Varying the shades obtained with such oxidation bases by associating them with coupling agents or colour modifiers is also known, these latter being selected from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as indole compounds.

The variety of molecules employed for the oxidation bases and coupling agents means that a rich palette of colours can be obtained.

The "permanent" colour obtained using such oxidation dyes must also satisfy a certain number of requirements. Thus, it must be harmless from a toxicological viewpoint, it must be capable of producing shades of the desired intensity and it must have good staying power when exposed to external agents such as light, poor weather, washing, permanent waves, perspiration and friction.

The colourants must also make it possible to cover white hair, and finally must be as non-selective as possible, i.e. they must be capable of producing as little colour difference as possible throughout the length of a keratinous fibre (uniform colour), which generally has a variable sensitivity (i.e. damage) between its end and its root.

Oxidizing agents which allow oxidative condensation may degrade the properties of treated hair. The hair becomes rough, difficult to disentangle and more brittle. To overcome these disadvantages, French patent FR-A-2 270 846 has proposed the use of certain quaternary polyammonium compounds.

However, we have shown that the polymers mentioned above cannot sufficiently overcome those disadvantages while preserving or improving the properties of the dye. The aim of the present invention is to develop dye compositions with improved cosmetic properties which can also produce strong and chromatic (luminous) shades with low selectivity and good persistence as regards chemical agents (shampoo, perming lotion, etc) or natural agents (light, perspiration, etc).

This aim is achieved in the present invention which provides a composition for oxidation dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in a medium appropriate for dyeing: i) at least one oxidation base; M) at least one coupling agent; Mi) at least one ammonium salt with formula (I):

in which formula (I):

^■ R represents a CH₃CH2-CH(R3)-CH2-(CH₂)m- group, with R₃ representing a linear or branched, saturated or unsaturated alkyl group, and m representing an integer in the range 0 to 30 inclusive; ■ Ri and R₂, which may be identical or different, represent a group selected from i) alkyl; ii) alkenyl; iii) alkoxy; iv) alkenyloxy; and v) aryl; the alkyl or alkenyl group of groups i) to iv) possibly being interrupted by one or more heteroatoms, which may be identical or different, selected from oxygen, sulphur and N(Ra) with Ra representing a hydrogen atom or an alkyl group; ^■ X represents the following aminoalkylene group: -N(R₄)-(CH₂)_P-, with R₄ representing a hydrogen atom or a linear or branched alkyl group, preferably a hydrogen atom, and p representing an integer in the range 1 to 6 inclusive, preferably 3; " Y represents an alkyl or alkoxy group; the alkyl group of the alkyl or alkoxy groups possibly being interrupted by one or more heteroatoms, which may be identical or different, selected from oxygen, sulphur and N(Ra) with Ra as defined above;

^■ Q^" represents the anionic counter-ion associated with the quaternary ammonium;

iv) at least one ceramide type compound or at least one quaternary polyammonium compound with formula (II):

in which formu a (II):

^■ R₄, R₅, R₆ and R_7j which may be identical or different, designate an alkyl or hydroxyalkyl radical containing about 1 to 4 carbon atoms;

^■ n and p are whole numbers from about 2 to 20; and

^■ Q' represents an anionic counter-ion associated with the quaternary ammonium.

The invention also provides a method for oxidation dyeing keratinous fibres, in particular human keratinous fibres such as hair, consisting of applying to the fibres the composition of the invention in the presence of an oxidizing agent for a time sufficient to obtain the desired colour.

The invention also pertains to dyeing devices with a plurality of compartments, or "kits", for oxidation dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising a first compartment which comprises the composition of the invention; and a second compartment comprising at least one oxidizing agent. The composition of the present invention can produce a high quality colour in the keratinous fibres as regards intensity, homogeneity, tenacity and, after colouring, also a particularly agreeable feel to the fibres, especially when dry.

Further, disentangling the fibres is facilitated and the particularly shiny appearance of the keratinous fibres is highly aesthetic.

Within the context of the present invention, unless otherwise indicated:

- an "alkyl radical" is a linear or branched CrCi₆ hydrocarbon radical, preferably Ci-C₄; - an "alkenyl radical" is a linear or branched C2-C16 hydrocarbon radical comprising 1 to 5 double π bonds, which may or may not be conjugated, preferably Ci-C₆ comprising one or two double bonds;

- an "alkoxy radical" is an alkyl-oxy (alkyl-O-) radical wherein the alkyl radical is a linear or branched C_rCi₆ hydrocarbon radical, preferably CrC₆; - an "alkenyloxy radical" is an alkenyl-oxy radical wherein the alkenyl radical is a radical as defined above;

- an "aryl" radical represents a mono- or poly-cyclic group, which may or may not be condensed, comprising 6 to 19 carbon atoms, wherein at least one cycle is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl, xylyl, anthracyl, phenanthryl, indenyl or tetrahydronaphthyl radical; the aryl radical may be substituted with one or more substituents selected from a halogen atom; an alkyl group; an alkoxy group, preferably CrC₄; a hydroxy group: OH; a nitro group: NO2; a nitroso group: NO; a cyano group: CN; a RO-C(O)- or R-C(O)O- group with R representing a CrC₄ alkyl or hydroxy group; a carbamoyl R₂N-C(O)-NR'- group with R, R', which may be identical or different, representing a hydrogen atom or an alkyl group, preferably CrC₄; a sulphamoyl group; a trihalogenoalkyl group, preferably CF₃; an aminoalkoxy group: an amino, alkylamino, and dialkylamino group;

- a "heterocyclic radical" is a non-aromatic monocyclic radical containing 5 to 6 links, comprising 1 to 3 heteroatoms selected from a nitrogen, oxygen and sulphur atom; preferably, the heterocycles are selected from pyridyl, piperazyl, morpholinylpiperidyl and pyrolidynyl groups; - a "counter-ion" is an anion or an anionic group associated with the cationic charge of the ammonium; more particularly, the anionic counter ion is selected from i) halides such as the chloride or bromide; ii) nitrates; iii) sulphonates including CrC₆ alkylsulphonat.es: AIk-S(O)₂O^", such as methylsulphonate or ethylsulphonate; iv) arylsulphonates: Ar-S(O)₂O^" such as benzenesulphonate and toluene sulphonate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulphates: AIk-O-S(O)O^", such as methysulphate or ethyl sulphate; x) arylsulphates: Ar-O-S(O)O^"' such as benzenesulphate or toluenesulphate; xi) alkoxysulphates: AIk-O-S(O)₂O^", such as methoxysulphate or ethoxysulphate; xii) aryloxysulphates:

Ar-O-S(O)₂O^"; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate.

The composition may contain at least one oxidation base. Such a base may be selected from those conventionally known in oxidation dyeing, and examples of those which may be cited are ortho- and para-phenylenediamines, double bases, ortho- and para- aminophenols, the following heterocyclic bases and their addition salts with an acid.

The following may in particular be cited:

- (A) paraphenylenediamines with formula (A) below and their addition salts with an acid or an alkali:

in which formula (A):

Ri represents a hydrogen atom, a Ci-C₄ alkyl radical, Ci-C₄ monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, alkoxy(CrC₄)alkyl(Ci-C₄), CrC₄ alkyl substituted with a nitrogen, phenyl or 4'-aminophenyl group; R₂ represents a hydrogen atom, a Ci-C₄ alkyl radical, CrC₄ monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl, alkoxy(Ci-C₄)alkyl(CrC₄) or CrC₄ alkyl substituted with a nitrogen group;

Ri and R₂ together with the nitrogen atom carrying them may also form a nitrogen- containing heterocycle with 5 or 6 links which may be substituted with one or more alkyl, hydroxy or ureido groups;

R₃ represents a hydrogen atom, a halogen atom such as a chlorine atom, a CrC₄ alkyl radical, sulpho, carboxy, CrC₄ monohydroxyalkyl or d-C₄ hydroxyalkoxy, CrC₄ acetylaminoalkoxy, CrC₄ mesylaminoalkoxy or CrC₄ carbamoylaminoalkoxy,

R₄ represents a hydrogen atom, a halogen atom or a CrC₄ alkyl radical.

Nitrogen-containing groups with formula (A) above which may be cited are the amino, monoalkyl(Ci-C₄)amino, dialkyl(Ci-C₄)amino, trialkyl(Ci-C₄)amino, monohydroxyalkyl(Ci-C₄)amino, imidazolinium and ammonium radicals.

More particular paraphenylenediamines with formula (A) above which may be cited are paraphenylenediamine, paratoluylenediamine 1 -methyl-2,5- diaminobenzene, 2-chloro-paraphenylenediamine, 2,3-dimethyl- paraphenylenediamine, 2,6-dimethyl-paraphenylenediamine, 2,6-diethyl- paraphenylenediamine, 2,5-dimethyl-paraphenylenediamine, N,N-dimethyl- paraphenylenediamine, N,N-diethyl-paraphenylenediamine, N,N-dipropyl- paraphenylenediamine, 4-amino-N,N-diethyl-3-methyl-aniline, N,N-bis-(β- hydroxyethyl)-paraphenylenediamine, 4-N,N-bis-(β-hydroxyethyl)amino-2-methyl- aniline, Ia 4-N,N-bis-(β-hydroxyethyl)-amino 2-chloro-aniline, 2-β-hydroxyethyl- paraphenylenediamine, 2-fluoro-paraphenylenediamine, 2-isopropyl- paraphenylenediamine, N-(β-hydroxypropyl)-paraphenylenediamine,

2-hydroxymethyl-paraphenylenediamine, N,N-dimethyl-3-methyl- paraphenylenediamine, N,N-(ethyl,β-hydroxyethyl)-paraphenylenediamine, N-(β,γ- dihydroxypropyl)-paraphenylenediamine, N-(4'-aminophenyl)- paraphenylenediamine, N-phenyl-paraphenylenediamine, 2-β-hydroxyethyloxy- paraphenylenediamine, 2-β-acetylaminoethyloxy-paraphenylenediamine,

N-(β-methoxyethyl)-paraphenylenediamine, 2-methyl-1 -N-β-hydroxyethyl- paraphenylenediamine, and their addition salts with an acid. More particularly preferred paraphenylenediamines with formula (A) above are paraphenylenediamine, paratoluylenediamine, 2-isopropyl- paraphenylenediamine, 2-β-hydroxyethyl-paraphenylenediamine,

2-β-hydroxyethyloxy-paraphenylenediamine, 2,6-dimethyl-paraphenylene-diamine, Ia 2,6-diethyl-paraphenylenediamine, Ia 2,3-dimethyl-paraphenylenediamine, N,N-bis-(β-hydroxyethyl)-paraphenylenediamine, 2-chloro-paraphenylenediamine, and their addition salts with an acid or a base.

-(B) In the context of the invention, the term "soluble bases" means compounds comprising at least two aromatic nuclei on which amino and/or hydroxyl groups are carried.

Double bases which may be used as oxidation bases in the dye compositions of the invention which may be cited are compounds with formula (B) below, and their addition salts with an acid:

in which formula (B):

- Zi and Z₂, which may be identical or different, represent a hydroxyl radical or -NH₂ radical which may be substituted with a CrC₄ alkyl radical or by a connecting arm Y;

- the connecting arm Y represents a linear or branched alkylene chain containing 1 to 14 carbon atoms which may be interrupted or terminated by one or more nitrogen-containing groups and/or by one or more heteroatoms such as oxygen, sulphur or nitrogen atoms, and is optionally substituted with one or more hydroxyl radicals or C_rC₆ alkoxy radicals;

- R₅ and R₆ represent a hydrogen or halogen atom, a Ci-C₄ alkyl radical, CrC₄ monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, CrC₄ aminoalkyl or a connecting arm Y; - R₇, Re, Rs, Rio, Rn and Ri₂, which may be identical or different, represent a hydrogen atom, a connecting arm Y or a Ci-C₄ alkyl radical; it being understood that the compounds with formula (B) comprise only a single connecting arm Y per molecule.

Nitrogen-containing groups with formula (B) above which may be cited include amino, monoalkyl(Ci-C₄)amino, dialkyl(Ci-C₄)amino, trialkyl(Ci-C₄)amino, monohydroxyalkyl(Ci-C₄)amino, imidazolinium and ammonium radicals.

More particular double bases with formulae (B) above which may be cited include N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4'-aminophenyl)-1 ,3-diamino- propanol, N,N'-bis-(β-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-diaminophenoxy)-3,5-dioxaoctane, and their addition salts with an acid.

Of these double bases with formula (B), N,N'-bis-(β-hydroxyethyl)-N,N'- bis-(4'-aminophenyl)-1 ,3-diamino-propanol, 1 ,8-bis-(2,5-diaminophenoxy)-

3,5-dioxaoctane or one of their addition salts with an acid are particularly preferred.

- (C) para-aminophenols with formula (C) below and their addition salts with an acid:

in which formula (C): R-₁₃ represents a hydrogen atom, a halogen atom such as fluorine, a CrC₄ alkyl,

CrC₄ monohydroxyalkyl, alkoxy(Ci-C₄)alkyl(Ci-C₄), CrC₄ aminoalkyl or CrC₄ hydroxyalkyl(Ci-C₄)aminoalkyl radical.

Ru represents a hydrogen atom or a halogen atom such as fluorine, a CrC₄ alkyl,

CrC₄ monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, C_rC₄ aminoalkyl, C_rC₄ cyanoalkyl or alkoxy(Ci-C₄)alkyl(Ci-C₄) radical. More particular para-aminophenols with formula (C) above which may be cited 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, and their addition salts with an acid;

- (D) particular ortho-aminophenols which may be used as oxidation bases in the context of the present invention are selected from 2-amino-phenol, 2-amino-1 - hydroxy-5-methyl-benzene, 2-amino-1 -hydroxy-6-methyl-benzene, 5-acetamido-2- amino-phenol, and their addition salts with an acid;

-(E) more particular heterocyclic bases which may be used as oxidation bases in the dye compositions of the invention which may be cited are pyridine derivatives, pyrimidine derivatives, pyrazole derivatives and their addition salts with an acid.

More particular pyridine derivatives which may be cited are the compounds described, for example, in British 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 with an acid.

More particular pyrimidine derivatives which may be cited are the compounds described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91 -10659 or International 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 French patent application FR-A-2 750 048. Examples of these which may be cited include 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, and their addition salts with an acid.

More particular pyrazole derivatives which may be cited are the compounds described in DE 3 843 892, DE 4 133 957 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 -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 -(β-hydroxyethyl)- 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, and their addition salts with an acid.

In accordance with the present invention, the oxidation bases preferably represent 0.0001 % to 20% by weight of the total composition weight, more preferably 0.005% to 10% by weight of that weight.

The coupling agents which may be used in the composition with the oxidation base of the invention are those which are conventionally used in oxidation dye compositions, i.e. meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols and heterocyclic coupling agents such as, for example indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3-benzodioxoles, quinolines and their addition salts with an acid.

More particularly, these coupling agents are selected from 1 -(β-hydroxyethyloxy)-2,4-diaminobenzene, 2-methyl-5-amino-phenol, 5-N-(β- hydroxyethyl)amino-2-methyl-phenol, 3-aminophenol or 1 -hydroxy-3-a mi no- benzene, 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2-methyl-benzene, 4-chloro- 1 ,3-dihydroxy-benzene, 2-amino 4-(β-hydroxyethylamino)-1 -methoxy-benzene, 1 ,3-diaminobenzene, 1 ,3-bis-(2,4-diaminophenoxy)-propane, sesamol, 1 -amino-2- methoxy-4,5-methylenedioxy benzene, I'α-naphthol, 6-hydroxy-indole, 4-hydroxy- indole, 4-hydroxy-N-methyl indole, 6-hydroxy-indoline, 2,6-dihydroxy-4-methyl- pyridine, 1-H-3-methyl-pyrazole-5-one, 1-phenyl-3-methyl-pyrazole-5-one, 2- amino-3-hydroxypyridine, 3,6-dimethyl-pyrazolo-[3,2-c]-1 ,2,4-triazole, 2,6- dimethyl-pyrazolo-[1 ,5-b]-1 ,2,4-triazole and their addition salts with an acid.

These coupling agents preferably represent about 0.0001 % to 20% by weight of the total composition weight, more preferably about 0.005% to 10% by weight.

In general, the addition salts with an acid of the oxidation bases and coupling agents are selected from hydrochlorides, hydrobromides, sulphates, tartrates, lactates and acetates.

The composition of the invention also contains at least one ammonium salt with formula (I) as defined above.

In a particular embodiment of the invention, the ammonium salt with formula (I) includes a group R representing an alkyl group containing 8 to 40 carbon atoms, m being an integer between 3 and 25 inclusive, advantageously between 10 and 20.

In particular, the ammonium salt with formula (I) contains a group R₃ which represents an alkyl group comprising less than 12 carbon atoms, particularly 1 to 6 carbon atoms; as an example, R₃ represents a methyl group and Ri and R₂ particularly represent an alkyl or alkoxy group containing 1 to 8 carbon atoms, such as: ethoxy, polyethoxy, propoxy, polypropoxy or methyl.

Another variation concerns the ammonium salt with formula (I) containing a group Y representing an alkoxy group such as: ethoxy, polyethoxy, propoxy, polypropoxy, or alkyl containing 1 to 6 carbon atoms. In a particular embodiment, Y represents an ethyl group.

Q^" represents the anionic counter-ion of the ammonium salt with formula (I), which may be selected from halides, alkyl sulphates such as methyl sulphate and ethyl sulphate; alkoxysulphates such as methoxysulphate and ethoxysulphate; phosphates; lactate; citrate; acetate and tartrate.

In an embodiment, the ammonium salt of formula (I) is not derived from linolic acid especially anteiso linolinic acid.

In a particular embodiment, the ammonium salt with formula (I) is 18MEA in the quaternized form, which comprises a group R deriving from 18- methyl eicosanoic acid, i.e. R₃ is a methyl and m is 16.

The term "18MEA in the quaternized form" means a quaternary ammonium salt derived from the fatty acid methyl eicosanoic acid (Methyl Eicosanoic Acid - 18MEA). Such a 18MEA compound in the quaternized form is sold by CRODA

(Incroquat Behenyl 18 MEA). More specifically, "18MEA in the quaternized form" corresponds to quaternized eicosanoic acid derivatives of Ci₀-C₄₀ lsoalkylamidopropylethyldimonium methosulphate: R-C(O)-NH-(CH₂)₃-N⁺(Me)₂Et, CH₃CH₂-OSO₃ ^" , with R representing the following alkyl group: CH₃CH₂-CH(CH₃)- CH₂-(CH₂)I₆-.

The ammonium salt with formula (I) above is present in the composition of the invention in a quantity in the range 0.001 % to 2% by weight with respect to the composition weight, in particular in the range 0.01 % to 1 %. Advantageously, the ammonium salt is present in the composition in a quantity in the range 0.02% to 0.4%.

The composition of the invention also contains a) either a compound of the ceramide type or b) a quaternary polyammonium polymer with formula (II): a) Either the composition of the invention also contains at least one ceramide type compound.

Ceramides or their analogues are known to protect and/or repair skin and/or hair fibres from attack by the various agents and treatments cited above. In particular, they have a barrier effect which limits protein loss, and they also reinforce cuticular cohesion. As an example, international patent application WO 00/44345 describes a means for improving cosmetic properties such as untangling the hair by applying a composition comprising a ceramide type compound such as N- oleoyldihydrosphingosine in association with a hydrogenated sunflower wax and behenyl trimethyl ammonium chloride in water. In accordance with the present invention, the term "ceramide type compound" means natural or synthetic ceramides and/or glycoceramides and/or pseudoceramides and/or neoceramides, with formula (I) below.

Ceramide type compounds have, for example, been described in patent applications DE4424530, DE4424533, DE4402929, DE4420736,

WO95/23807, EP-A-0646572, WO95/16665, FR-2 673 179,

EP-A-0227994 and WO 94/07844, WO94/24097, WO94/10131 the teachings of which are hereby included by reference.

Ceramide type compounds which may be used in the present invention have the following general formula (XX):

in which formula (XX): R-J4 designates: i) a linear or branched, saturated or unsaturated hydrocarbon radical C1-C50, preferably C₅-C₅O, said radical possibly being substituted with one or more hydroxy groups which may be esterified by an acid R₁₉COOH, with Rig being a linear or branched, saturated or unsaturated Ci-C3₅hydrocarbon radical, which may be mono- or polyhydroxylated, the hydroxy group or groups of radical R19 possibly being esterified by a linear or branched, saturated or unsaturated Ci-C₃₅fatty acid, which may be mono- or polyhydroxylated; ii) a R"-(NR-CO)_q-R' radical, with R designating a hydrogen atom or a mono- or polyhydroxylated, preferably mono-hydroxylated C_rC₂o hydrocarbon radical, R' and R" are hydrocarbon radicals wherein the sum of the carbon atoms is in the range 9 to 30, R' being a divalent radical; q designates 0 or 1 ; or iii) a R₂o-O-CO-(CH₂)_p radical, R₂o designating a C_rC₂o hydrocarbon radical, p being an integer in the range 1 to 12 inclusive;

^■ R-₁₅ is selected from a hydrogen atom, a saccharide type radical, in particular a (glycosyl)_n, (galactosyl)_m or sulphogalactosyl radical, a sulphate or phosphate residue, a phosphorylethylamine radical and a phosphorylethylammonium radical, in which n is an integer in the range 1 to 4 inclusive, and m is an integer in the range 1 to 8 inclusive;

^■ R-16 designates a saturated or unsaturated, hydroxylated or non- hydroxylated CrC₃₃ hydrocarbon radical, the hydroxy group or groups possibly being esterified by a mineral acid or an acid Ri₉COOH, Ri₉ having the meanings given above, the hydroxyl group or groups possibly being etherified by a (glycosyl)_n, (galactosyl)_mj sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium radical, Riβ possibly being substituted with one or more Ci-Ci₄ alkyl radicals; preferably, Ri₆ designates a Ci₅-C₂₆ α-hydroxyalkyl radical, the hydroxyl group optionally being esterified by a Ci₆-C₃₀ α- hydroxyacid;

^■ R-J7 designates a hydrogen atom, a saturated or unsaturated, linear or branched non-alkoxylated C₃-Cs₀ hydrocarbon radical, optionally hydroxylated such as a methyl, ethyl or a R₂I-O-CO-(CH₂) radical, Rs designates a CrC₂O hydrocarbon radical, p is an integer from 1 to 12; in particular, Ri₇ represents a Ci₀-C₂₀ alkyl group;

^■ R-J8 designates a hydrogen atom or a saturated or unsaturated, linear or branched CrC₃₀ hydrocarbon radical, which may be mono- or polyhydroxylated, the hydroxy group or groups possibly being etherified by (glycosyl)_n, (galactosyl)_mj sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium, radical; in particular, R^s represents a hydrogen atom. Preferred compounds with formula (XX) include ceramides and/or glycoceramides the structures of which have been described by DOWNING in the Journal of Lipid Research Vol. 35, 2060-2068, 1994, or those described in French patent FR-2 673 179, the teachings of which are included herewith by reference.

More particular ceramide type compounds in accordance with the invention are compounds with formula (XX) wherein Ri₄ designates an alkyl or alkenyl derivative of Ci₄-C₂₂ fatty acids which may be hydroxylated; in particular, Ri₄ represents a Ci₂-C_2O alkenyl chain comprising one or more π double bonds, preferably one; Ri₅ designates a hydrogen atom; and Ri₆ designates a linear Cn- Ci7 radical which may be hydroxylated and preferably Ci₃-Ci₅; more particularly, Ri6 represents an alkyl group such as methyl or ethyl hydroxylated by one or more hydroxy groups, preferably one hydroxy group.

Examples of such compounds are: - 2-N-linoleoylamino-octadecane-1 ,3-diol;

- 2-N-oleoylamino-octadecane-1 ,3-diol;

- 2-N-palmitoylamino-octadecane-1 ,3-diol;

- 2-N-stearoylamino-octadecane-1 ,3-diol;

- 2-N-behenoylamino-octadecane-1 ,3-diol; - 2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1 ,3-diol;

- 2-N-stearoyl amino-octadecane-1 ,3,4 triol and in particular N- stearoyl phytosphingosine;

- 2-N-palmitoylamino-hexadecane-1 ,3-diol; or mixtures of said compounds. It is also possible to use specific mixtures, for example, such as mixtures of ceramide 2 and ceramide 5 using DOWNING's classification.

It is also possible to use compounds with formula (XX) wherein Ri₄ designates a saturated or unsaturated alkyl radical derived from Ci₂-C₂₂ fatty acids; Ri₅ designates a galactosyl or sulphogalactosyl radical; and Ri₆ designates a saturated or unsaturated Ci₂-C₂₂ hydrocarbon radical and preferably a CH(OH)-CH=CH-(CH₂)i₂.CH₃ group. An example which may be cited is the product constituted by a mixture of glycoceramides, sold under the trade name GLYCOCER by WAITAKI INTERNATIONAL BIOSCIENCES.

It is also possible to use compounds with formula (XX) described in patent applications EP-A-0227994 and WO 94/07844.

Examples of such compounds are QUESTAMIDE H (bis-(N- hydroxyethyl N-cetyl) malonamide) sold by QUEST.

It is also possible to use N-docosanoyl N-methyl-D-glucamine described in patent application WO94/24097. The concentration of ceramide type compounds may be in the range about 0.0001 % to 20% by weight with respect to the total composition weight, preferably in the range about 0.001 % to 10% and more preferably in the range 0.01 % to 3% by weight; r the composition of the invention also contains at least one quaternary polyammonium with formula (II) as defined above, preferably those comprising groups R₄, R₅, Re and R₇ independently representing a methyl or ethyl radical and Q ^" representing the anionic counter-ion of the polyammonium which may be selected from the halide, sulphate, sulphite, sulphides, nitrate, acetate, borate, citrate, tartrate, bisulphate, bisulphite, sulphate, phosphate, more preferably the halide ion such as the chloride, bromide or iodide.

Particularly preferred polymers with formula (II) are those in which R₄, R₅, Re and R₇, represent a methyl radical and n = 3, p = 6 and Q'^" = Cl^", and especially those for which the molecular mass, determined by gel permeation chromatography, is in the range 9500 to 9900.

Other particularly preferred polymers with formula (II) are those in which R₄ and R5 represent a methyl radical, Re and R₇ represent an ethyl radical and n = p = 3 and Q = Br, and especially those for which the molecular mass, determined by gel permeation chromatography, is about

1200.

Said quaternary polyammonium compounds with formula (II) are prepared and described in French patent FR-A-2 270 846. A particular embodiment of the invention concerns ionene quaternary polyammonium compounds such as Hexadimethrine Chloride corresponding to a polymer of N, N, N', N'- tetramethylhexamethylenediamine and 1 ,3-dichloropropylene. The composition of the invention may also contain dialkyldiallylammonium cyclohomopolymers comprising, as the principal constituent of the chain, motifs with the following structure (III):

in which formula (III): ■ k and t are equal to 0 or 1 , the sum k + t being equal to 1 ;

^■ Ri, independently of each other, designates a hydrogen atom or a methyl radical;

^■ R₂ and R₃, 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 amidoalkyl group (Ci-C₄), or R₂ and R₃ may, jointly with the nitrogen atom to which they are attached, designate heterocyclic groups such as piperidinyl or morpholinyl; R₂ and R₃ independently of each other preferably designate an alkyl group containing 1 to 4 carbon atoms; ■ Q"^" represents an anionic counter ion associated with the quaternary ammonium, and may be selected from halides such as the bromide or chloride; acetate; alkyl sulphates such as methyl sulphate and ethyl sulphate; alkoxysulphates such as methoxysulphate and ethoxysulphate; citrate; tartrate and phosphates. These polymers have in particular been described in French patent

FR-A- 2 080 759 and in its patent of addition, FR-A- 2 190 406.

Preferred polymers as defined above are those with formula (III) wherein R₁ designates hydrogen, and R₂ and R₃ designate a methyl radical. A particular compound of this latter genre which may be cited is the dimethyldiallylammonium chloride homopolymer sold under the trade name "Merquat 100" by Calgon (and its low mass average molecular mass homologues). In the composition of the invention, the quantity by weight of the dialkyldiallylammonium cyclohomopolymer with formula (III) is preferably in the range about 0.05% to 5%, more preferably in the range 0.1 % to 3%.

The quantity by weight of quaternary polyammonium compounds with motifs with formula (II) is preferably in the range from about 0.05% to 10%, more preferably in the range 0.2% to 5% with respect to the total composition weight.

The composition of the invention may also contain one or more direct dyes. Said direct dyes may in particular be selected from neutral, cationic or anionic dyes.

The term "neutral direct dye" means any direct dye which does not have in its molecular structure a quaternized nitrogen atom or COOR or SO3R substituents, where R designates a hydrogen atom, or a cation deriving from a metal or an amine, or an ammonium ion. Neutral direct dyes which may be cited are benzene direct dyes such as:

1 ,4-diamino-2-nitrobenzene, 1 -amino-2 nitro-4-β-hydroxyethylaminobenzene,1 - amino-2 nitro-4-bis(β-hydroxyethyl)-aminobenzene, 1 ,4-bis(β-hydroxyethylamino)- 2-nitrobenzene, 1 -β-hydroxyethylamino-2-nitro-4-bis-(β-hydroxyethylamino)- benzene, 1-β-hydroxyethylamino-2-nitro-4-aminobenzene, 1 -β-hydroxyethylamino- 2-nitro-4-(ethyl)(β-hydroxyethyl)-aminobenzene, 1 -amino-3-methyl-4-β-hydroxy- ethylamino-6-nitrobenzene, 1 -amino-2-nitro-4-β-hydroxyethylamino-5-chloro- benzene, 1 ,2-diamino-4-nitrobenzene, 1-amino-2-β-hydroxyethylamino-5- nitrobenzene, 1 ,2-bis-(β-hydroxyethylamino)-4-nitrobenzene, 1-amino-2-tris- (hydroxymethyl)methylamino-5-nitrobenzene, 1 -hydroxy-2-amino-5-nitrobenzene, 1 -hydroxy-2-amino-4-nitrobenzene, 1 -hydroxy-3-nitro-4-aminobenzene, 1 -hydroxy- 2-amino-4,6-dinitrobenzene, 1 -β-hydroxyethyloxy-2-β-hydroxyethylamino-5- nitrobenzene, 1 -methoxy-2-β-hydroxyethylamino-5-nitrobenzene, 1 -β-hydroxy- ethyloxy-3-methylamino-4-nitrobenzene, 1 -β,γ-dihydroxypropyloxy-3-methylamino- 4-nitrobenzene, 1 -β-hydroxyethylamino-4-β,γ-dihydroxypropyloxy-2-nitrobenzene, 1 -β,γ-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, 1 -β-hydroxyethyl- amino-4-trifluoromethyl-2-nitrobenzene, 1 -β-hydroxyethylamino-3-methyl-2-nitro- benzene, 1 -β-aminoethylamino-5-methoxy-2-nitrobenzene, 1 -hydroxy-2-chloro-6- ethylamino-4-nitrobenzene, 1 -hydroxy^-chloro-θ-amino^-nitrobenzene, 1 - hydroxy-6-bis-(β-hydroxyethyl)-amino-3-nitrobenzene, 1 -β-hydroxyethylamino-2- nitrobenzene, 1 -hydroxy-4-β-hydroxyethylamino-3-nitrobenzene.

Neutral azo dyes which may be cited are Disperse Orange 3, Disperse Red 17, Disperse Black 9 and HC Yellow 7.

Neutral quinone dyes which may be cited are Disperse Violet 4, Disperse Blue 1 , Disperse Violet 1 , Disperse Blue 3, Disperse Blue 7, Natural Orange 6 and HC Blue 14.

Cationic direct dyes which may be used in the invention have at least one quaternized atom in their structure constituting at least one permanent cationic charge. This charge may be endocyclic or exocyclic. The term "endocyclic charge" means that the charge is present on a heteroatom included in a cycle. Thus, preferred direct dyes of the invention which may be mentioned are cationic direct dyes which have an endocyclic charge. Cationic direct dyes with an exocyclic charge which may be cited are the dyes Basic Red 76, Basic Yellow 57, Basic Brown 16, Basic Brown 17, Basic Blue 99 and Basic Blue 22.

Endocyclic cationic direct dyes which may be cited are azo, methine or azomethine direct dyes with a quantitative ammonium group included in a cycle: i) the following colourants described in patent application EP 1 025 834 with formula (IV):

G-N=N-J (IV)

in which:

- the symbol G represents a group selected from the following structures d to G3:

hich:

> R2₄ designates a Ci-C₄ alkyl radical, a phenyl radical which may be substituted with a Ci-C₄ alkyl radical or a halogen atom selected from chlorine, bromine, iodine and fluorine;

> R25 designates a Ci-C₄ alkyl radical or a phenyl radical;

> R26 and R27, which may be identical or different, represent a Ci-C₄ alkyl radical, a phenyl radical or together in Gi form a benzene ring substituted with one or more CrC₄ alkyl radicals, C_rC₄ alkoxy radicals or NO₂ radicals, or together in G₂ form a benzene ring which may be substituted with one or more CrC₄ alkyl, Ci-C₄ alkoxy or NO₂ radicals;

> R₂₆ may also designate a hydrogen atom;

> Z designates an oxygen or sulphur atom or an -NR₂₅ group; > M represents a -CH, -CR (R designating d-C₄ alkyl), or -NR₂₈(X^")r group;

> K represents a -CH, -CR (R designating Ci-C₄ alkyl),or -NR₂₈(X^")r group;

> P represents a -CH, -CR (R designating Ci-C₄ alkyl), or -NR₂₈(X^")r group;

> r designates zero or 1 ; > R₂₈ represents an O^~ atom, a CrC₄ alkoxy radical or a CrC₄ alkyl radical;

> R₂9 and R30, which may be identical or different, represent a hydrogen or halogen atom selected from chlorine, bromine, iodine and fluorine, a CrC₄ alkyl radical, a CrC₄ alkoxy radical or a -NO₂ radical; > X^~ represents an anion, preferably selected from chlorine, iodine, methyl sulphate, ethyl sulphate, acetate and perchlorate;

- the symbol J represents: a) a group with the following structure J-i:

in which,

> R₃₁ represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a CrC₄ alkyl radical, a CrC₄ alkoxy, a -OH, - NO₂, -NHR₃₄, -NR35R36, CrC₄ -NHCOalkyl radical, or with R₃₂ forms a cycle with 5 or 6 links which may or may not contain several heteroatoms selected from nitrogen, oxygen and sulphur;

> R₃₂ represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a CrC₄ alkyl radical, a CrC₄ alkoxy radical, > or with R₃₃ or R₃₄ forms a cycle with 5 or 6 links which may or may not contain one or more heteroatoms selected from nitrogen, oxygen and sulphur;

> R₃₃ represents a hydrogen atom, a -OH radical, a -NHR₃₄ radical, or an - NR₃₅R36 radical; > R₃₄ represents a hydrogen atom, a C_rC₄ alkyl radical, a C_rC₄ monohydroxyalkyl radical, C₂-C₄ poly hydroxyalkyl or a phenyl radical;

> R₃5 and R₃6, which may be identical or different, represent a CrC₄ alkyl radical, a CrC₄ monohydroxyalkyl radical or a C₂-C₄ polyhydroxyalkyl radical;

b) a heterocyclic nitrogen-containing group with 5 or 6 links which is capable of including other heteroatoms and/or carbonyl groups and which may be substituted with one or more CrC₄ alkyl, amino or phenyl radicals; and in particular a group with the following structure J₂: in wh ich ,

> R37 and R38, which may be identical or different, represent a hydrogen atom, a C₁₃-C₁₀ alkyl radical, a phenyl radical;

> Y designates the radical -CO- or the radical -C(CH₃)=;

> n represents 0 or 1 , with, when n designates 1 , U designating the radical -CO-;

ii) with the following formula (V):

in which:

> R₁₂ represents a hydrogen atom or a CrC₄ alkyl radical,

> Ri3 represents a hydrogen atom, an alkyl radical which may be substituted with a radical -CN or with an amino group, a 4'-aminophenyl radical or with Ri₂ forms a heterocycle which may contain oxygen and/or nitrogen which may be substituted with a C_rC₄ alkyl radical;

> Ri₄ and R₁₅, which may be identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a CrC₄ alkyl radical or CrC₄ alkoxy radical or a -CN radical;

> X^" represents an anion, preferably selected from the chloride, methyl sulphate and acetate;

> B represents a group selected from the following structures Bi to B₆:

in which R₁₆ represents a CrC₄ alkyl radical;

Ri7 and Ris, which may be identical or different, represent a hydrogen atom or a CrC₄ alkyl radical;

iii) compounds with the following formulae (Vl) and (VII):

in which:

> Rig represents a hydrogen atom, a CrC₄ alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical,

> R_2O represents a hydrogen atom, a CrC₄ alkyl radical or with a carbon atom of the benzene ring forms a heterocycle which may optionally contain oxygen and/or be substituted with one or more CrC₄ alkyl groups; > R21 represents a hydrogen atom or a halogen atom such as bromine, chlorine, iodine or fluorine;

> R22 and R23, which may be identical or different, represent a hydrogen atom or a C_rC₄ alkyl radical;

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

> m represents 0 or 1 ; it being understood that when R^ g represents a non substituted amino group, then Di and D₂ simultaneously represent a -CH group and m = 0;

> E represents a group selected from the following structures Ei to E₈:

in which R' represents a CrC₄ alkyl radical;

when m represents O and D₁ represents a nitrogen atom, then E may also designate a group with the following structure E₉: in which R' represents a CrC₄ alkyl radical,

iv) compounds with the following formula (VIII):

in which:

> Z and D, which may be identical or different, represent a nitrogen atom or the -CH group;

> R₇ and Rs, which may be identical or different, represent a hydrogen atom; a Ci-C₄ alkyl radical which may be substituted with a -CN, -OH or

-NH₂ radical or together with a carbon atom of the benzene cycle form a heterocycle which may contain oxygen or nitrogen, which may be substituted with one or more Ci-C₄ alkyl radicals; or a 4'-aminophenyl radical; > Rg and R'g, which may be identical or different, represent a hydrogen atom or halogen atom selected from chlorine, bromine, iodine and fluorine, a cyano radical, a CrC₄ alkyl radical, a CrC₄ alkoxy radical, or an acetyloxy radical;

> X^" represents an anion, preferably selected from the chloride, methyl sulphate and acetate,

> A represents a group selected from the following structures Ai to Ai₉:

in which R₁₀, which may be identical or different, represent a CrC₄ alkyl radical which may be substituted with a hydroxyl radical and Rn represents a CrC₄ alkoxy radical;

v) the dyes described in patent application EP-714 954 with formulae (IX), (X), or (Xl):

in which

> A and A₁, independently of each other, are residues with formula:

> Z represents an aliphatic or aromatic diamine residue;

> Ri and R₂, independently of each other represent a hydrogen atom, a CrC₄ alkyl group or may together with the 2 nitrogen atoms to which they are attached or with Z and Z₂ form a cycle with 5, 6 or 7 links; > X represents the residue of a link forming a bridge;

> n represents the integer 2, 3 or 4;

> Zi represents an aromatic diamine residue;

> Z₂ represents an aliphatic diamine residue;

> KK represents a coupling agent residue; > R₃ and R₄ independently represent a hydrogen atom or a CrC₄ alkyl group;

> R₅ and R₆, independently represent a hydrogen atom, a C_rC₄ alkyl group or a CrC₄ alkoxy group;

> An^" represents an anionic counter ion, particularly colourless; as well as the cationic dyes described in patent applications WO 95/01 772, WO 95/15 144, EP 714 954, EP 1 170 000 EP 1 166 753, EP 1 166 754 and EP 1 170 001 , which differ from the above dyes. The passage of these applications devoted to cationic dyes is hereby incorporated into the present application.

Preferably, dyes with the following formulae are used: Basic Red 51 with the following formula:

Basic Yellow 87 with the following formula:

as well as Basic Orange 31 with the following formula:

Examples of dyes with an endocyclic cationic charge in accordance with the invention which may be cited are as follows:

- cationic dyes with xanthene cycles, such as Basic Red 1 , Basic Red 3, Basic Red 4, Basic Violet 10 or Basic Violet 11 ;

- cationic dyes with acridine cycles, such as Basic Orange 15, Basic Orange 16 or Basic Orange 17;

- cationic dyes with benzothiazole cycles, such as Basic Blue 41 or Basic Blue 67;

- cationic dyes with phenothiazine cycles, such as Basic Blue 9; - cationic dyes with triazole cycles, such as Basic Red 22 or Basic Red 46;

- cationic dyes with thiazole cycles, such as Basic Red 29;

- cationic dyes with phenazine cycles, such as Basic Red 2;

- cationic dyes with indolenine cycles, such as Basic Red 14, Basic Yellow 13 , Basic Yellow 28 or Basic Yellow 29; - cationic dyes with phenoxazine cycles, such as Basic Blue 6.

Anionic or acid direct dyes which may be used in the invention have in their structure at least one CO2R or SO3R group, in which R designates a hydrogen atom or a cation deriving from a metal or an amine, or an ammonium ion. The anionic dyes may be selected from acid direct nitro dyes, acid azo dyes, acid azine dyes, acid triaryl methane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and natural acid dyes.

Acid dyes in accordance with the invention which may be cited are colourants with the following formulae (XII), (XII'), (XIII), (XIII'), (XIV), (XIV), (XV),

(XV), (XVI), (XVII), (XVIII) and (XIX):

a) anionic diaryl azo dyes with formulae (XII) or (XM'): hich formulae (XII) and (XII'):

^■ R₇, Re, R9, R10, R'7, R'β, R'9 and R'i₀, which may be identical or different, represent a hydrogen atom or a group selected from:

- alkyl;

- alkoxy, alkylthio;

- hydroxy, mercapto;

- nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- in which R⁰ represents a hydrogen atom, an alkyl or aryl group; X, X' and X", which may be identical or different, represent an oxygen atom, a sulphur atom or NR with R representing a hydrogen atom or an alkyl group;

- (O)₂S(O^~)-, M⁺ with M⁺ representing a hydrogen atom or a cationic counter-ion;

- (O)CO^"-, M⁺ with M⁺ as defined above;

- R"-S(O)₂-, with R" representing a hydrogen atom, an alkyl group, an aryl, (di)(alkyl)amino or aryl(alkyl)amino group; preferably a phenylamino or phenyl group; - R"'-S(O)2-X'- with R'" representing an alkyl group, an aryl group which may optionally be substituted, and X' is as defined above;

- (di)(alkyl)amino;

- aryl(alkyl)amino optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O)2S(O^~)-, M⁺ and iv) alkoxy with M⁺ as defined above; - heteroaryl optionally substituted; preferably a benzothiazolyl group;

- cycloalkyl; especially cyclohexyl;

- Ar-N=N- with Ar representing an aryl group, optionally substituted; preferably a phenyl group optionally substituted with one or more alkyl groups, (O)2S(O^~)-, M⁺ or phenylamino;

- or two contiguous groups R₇ with R₈ or R₈ with R₉ or R₉ with Ri₀ together form a fused benzo A' group; and R'₇ with R'₈ or R'₈ with R'₉ or R'₉ with R'io together form a fused benzo B' group; with A' and B' optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O)₂S(O^")-, M⁺; iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'-C(X)-; ix) R°-X'-C(X)-X"-; x) Ar-N=N- and xi) aryl(alkyl)amino, optionally substituted; with M⁺, R°, X, X', X" and Ar as defined above;

^■ W represents a sigma bond σ, an oxygen atom, a sulphur atom or a divalent radical i) -NR- with R as defined above, or ii) methylene -

C(R₃)(Rb)- with R₃ and R_b, which may be identical or different, representing a hydrogen atom or an aryl group, or R₃ and R_b together with the carbon atom carrying them form a spiro cycloalkyl; preferably, W represents a sulphur atom or R₃ and Rb together form a cyclohexyl group; it being understood that formulae (XII) and (XM') include at least one sulphonate (O)₂S(O^")-, M⁺ radical or a carboxylate (O)CO^"-, M⁺ radical on one of cycles A, A', B, B' or C; preferably sodium sulphonate;

Examples of dyes with formula (XII) which may be cited are: Acid Red 1 , Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red

33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41 , Acid Red 42, Acid Red

44, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food

Red 1 , Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange

19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117,

Acid Black 1 , Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food

Black 1 , Food Black 2; and examples of dyes with formula (XM') which may be cited are: Acid Red 111 , Acid Red 134, Acid Yellow 38; b) pyrrazolone anionic azo dyes with formulae (XIII) and (XIM'):

in which formulae (XIII) and (XIII'):

^■ R-M, R-I2 and Ri₃, which may be identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or -(O)₂S(O^~), M⁺ with M⁺ as defined above;

^■ Ru represents a hydrogen atom, an alkyl group or a -C(O)O^", M⁺ group with M⁺ as defined above;

^■ R-15 represents a hydrogen atom;

^■ R-₁₆ represents an oxo, group in which case R'i₆ is absent, or R₁₅ with R₁₆ together form a double bond

^■ R₁₇ and R₁₈, which may be identical or different, represent a hydrogen atom or a group selected from:

- (O)₂S(O^")-, M⁺ with M⁺ as defined above;

- Ar-O-S(O)₂- with Ar representing an aryl group which may be substituted; preferably a phenyl group which may be substituted with one or more alkyl groups; ■ R₁₉ and R₂o, together form either a double bond or a benzo D' group, which may be substituted;

^■ R'₁₆, R'-i9 and R'₂o, which may be identical or different, represent a hydrogen atom or an alkyl group or a hydroxy group; ^■ R₂i represents a hydrogen atom, an alkyl group, or an alkoxy group;

^■ Ra and R_a, which may be identical or different, are as defined above; preferably, R₃ represents a hydrogen atom and R_b represents an aryl group;

^■ Y represents either a hydroxy group or an oxo group; ■ Represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;

It being understood that formulae (XIII) and (XIM') comprise at least one sulphonate (O)₂S(O^")-, M⁺ radical or a carboxylate -C(O)O^", M⁺ radical on one of cycles D or E; preferably sodium sulphonate;

Examples of dyes with formula (XIII) which may be cited are: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and an example of a dye with formula (XIM') which may be cited is: Acid Yellow 17;

c) anthraquinone dyes with formulae (XIV) and (XIV):

in which formulae (XIV) and (XIV):

^■ R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen atom, a halogen atom or a group selected from:

- alkyl;

- hydroxy, mercapto;

- alkoxy, alkylthio; - aryloxy or arylthio, optionally substituted, preferably substituted with one or more groups selected from alkyl and (O)2S(O^~)-, M⁺ with M⁺ as defined above;

- aryl(alkyl)amino, optionally substituted, preferably substituted with one or more groups selected from alkyl and (O)2S(O^~)-, M⁺ with M⁺ as defined above;

- (di)(alkyl)amino;

- (di)(hydroxyalkyl)amino;

- (O)₂S(O^")-, M⁺ with M⁺ as defined above; ■ Z' represents a hydrogen atom or a NR28R29 group with R₂e and R29, which may be identical or different, representing a hydrogen atom or a group selected from:

- alkyl;

- polyhydroxyalkyl such as hydroxyethyl; - aryl, optionally substituted with one or more groups, particularly i) alkyl such as methyl, n-dodecyl, n-butyl; ii) (O)₂S(O^")-, M⁺ with M⁺ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°, X, X' and X" as defined above; preferably, R° represents an alkyl group;

- cycloakyl; particularly cyclohexyl; ■ Z, represents a group selected from hydroxy and NR'28R'29 with R'₂₈ and

R'29, which may be identical or different, representing the same atoms or groups as R28 and R29 as defined above; it being understood that formulae (XIV) and (XIV) include at least one sulphonate (O)₂S(O^")-, M⁺ radical or a carboxylate -C(O)O^", M⁺ radical; preferably sodium sulphonate;

Examples of colourants with formula (XIV) which may be cited are: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251 , Acid Green 25, Acid Green 41 , Acid Violet 42, Acid Violet 43, Mordant Red 3; and an example of a colourant with formula (XIV) which may be cited is: Acid Black 48; d) nitro colourants with formulae (XV) and (XV):

in which formulae (XV) and (XV):

^■ R₃₀, R₃₁ and R₃₂, which may be identical or different, represent a hydrogen atom, a halogen atom or a group selected from

- alkyl;

- alkoxy optionally substituted with one or more hydroxy groups, alkylthio optionally substituted with one or more hydroxy groups;

- hydroxy, mercapto;

- nitro, nitroso;

- polyhalogenoalkyl;

- FT-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R°; X, X' and X" as defined above;

- (O)₂S(O^")-, M⁺ with M⁺ as defined above;

- (O)CO^"-, M⁺ with M⁺ as defined above;

(di)(alkyl)amino;

- (di)(hydroxyalkyl)amino; - heterocycloalkyl such as piperidino, piperazino or morpholino; in particular, R₃₀, R31 and R32 represent a hydrogen atom;

^■ Rc and Rd, which may be identical or different, represent a hydrogen atom or an alkyl group;

^■ W is as defined above; in particular, W represents a -NH- group; ^■ ALK represents a linear or branched divalent C_I-C_Θ alkylene group; in particular, ALK represents a -CH₂-CH₂- group;

^■ n is 1 or 2;

^■ p represents an integer in the range 1 to 5 inclusive; ■ q and t represent an integer in the range 1 to 4 inclusive;

^■ u is 0 or 1 ;

^■ when n is 1 , J represents a nitro or nitroso group, in particular nitro;

^■ when n is 2, J represents an oxygen atom, a sulphur atom or a divalent -S(O)_m- radical with m representing the integer 1 or 2; preferably, J represents a -SO₂- radical;

^■ esents a hydrogen atom or a cation ic counter-ion;

^■ , present or absent, represents a benzo group which may be substituted with one or more groups R30 as defined above;

it being understood that formulae (XV) and (XV) include at least one sulphonate (O)₂S(O^")-, M⁺ radical or a carboxylate -C(O)O^", M⁺ radical; preferably sodium sulphonate;

Examples of dyes with formula (XV) which may be cited are: Acid Brown 13; Acid Orange 3; examples of dyes with formula (XV) which may be cited are: Acid Yellow 1 , the sodium salt of 2,4-dinitro-1 -naphthol-7-sulphonic acid, 2-piperidino 5-nitro benzene sulphonic acid, 2(4'-N,N(2"-hydroxyethyl)amino-2'-nitro)aniline ethane sulphonic acid, 4-β-hydroxyethylamino-3-nitrobenzene sulphonic acid;

d) triarylmethane dyes with formula (XVI):

in which formula (XVI): ^■ R33, R34, R35 and R₃6, which may be identical or different, represent a hydrogen atom or a group selected from alkyl, aryl, which may be substituted and arylalkyl which may be substituted; in particular, an alkyl and benzyl group optionally substituted with a (O)_mS(O>, M⁺ group with M⁺ and m as defined above;

^■ R37, R38, R39, R40, R41, R42, R43 and R44, which may be identical or different, represent a hydrogen atom or a group selected from:

- alkyl;

- alkoxy, alkylthio; - (di)(alkyl)amino;

- hydroxy, mercapto;

- nitro, nitroso;

- FT-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X"- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen atom, a sulphur atom or

NR with R representing a hydrogen atom or an alkyl group;

- (O)CO^"-, M⁺ with M⁺ as defined above; - or two contiguous groups R₄i with R₄₂ or R₄₂ with R₄₃ or R₄₃ with R₄₄ together form a fused benzo group: I'; with I' optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (O)2S(O^~)-, M⁺' iv) hydroxy; v) mercapto; vi) (di)(alkyl)amino; vii) R°-C(X)-X'-; viii) R°-X'- C(X)-; ix) R°-X'-C(X)-X"-; with M⁺, R°, X, X', X" as defined above; in particular R₃₇ to R₄₀ represent a hydrogen atom, and R₄i to R₄₄, which may be identical or different, represent a hydroxyl group or (O)₂S(O^")-, M⁺' and when R₄₃ with R₄₄ together form a benzo group, it is preferably substituted with a (O)₂S(O^")- group;

it being understood that at least one of cycles G, H, I or I' includes at least one sulphonate (O)₂S(O^")- radical or a carboxylate -C(O)O^" radical; preferably sulphonate; Examples of dyes with formula (XVI) which may be cited are: Acid Blue 1 ; Acid Blue 3; Acid Blue 7, Acid Blue 9; Acid Violet 49; Acid Green 50;

e) dyes derived from xanthene with formula (XVII):

in which formula (XVII):

^■ R45, R46, R47 and R₄8, which may be identical or different, represent a hydrogen atom or a halogen atom;

^■ R49, R50, R51 and R₅₂, which may be identical or different, represent a hydrogen atom, a halogen atom or a group selected from:

- alkyl;

- alkoxy, alkylthio;

- hydroxy, mercapto;

- nitro, nitroso; - (O)₂S(O^~)-, M⁺ with M⁺ representing a hydrogen atom or a cationic counter-ion;

- (O)CO^"-, M⁺ with M⁺ as defined above; in particular, R₅₃ R₅₄, R₅₅ and R₄s represent a hydrogen atom or a halogen atom; " G represents an oxygen atom, a sulphur atom or a NR_e group with R_e as defined above; in particular, G represents an oxygen atom;

^■ L represent an alcoholate O^", M⁺; a thioalcoholate S^", M⁺ or a NR_f group with R_f representing a hydrogen atom or an alkyl group and M⁺ as defined above; in particular, M⁺ is sodium or potassium; ■ L' represents an oxygen atom, a sulphur atom or an ammonium group:

N⁺R_fR₉, with R_f and R_9, which may be identical or different, representing a hydrogen atom, an alkyl group, an optionally substituted aryl group; in particular, L' represents an oxygen atom or a phenylamino group optionally substituted with one or more alkyl groups or (O)_mS(O^~)-, M⁺ with m and M⁺ as defined above;

Q and Q', which may be identical or different, represent an oxygen atom or a sulphur atom; in particular, Q and Q' represent an oxygen atom;

M⁺ is as defined above;

Examples of colourants with formula (XVII) which may be cited are: Acid Yellow 73; Acid Red 51 ; Acid Red 87; Acid Red 92; Acid Red 95 and Acid Violet 9; f) dyes derived from indole with formula (XVIII):

R53, R54, R55, R56, R57, Rsβ, R59 and R₆O, which may be identical or different, represent a hydrogen atom or a group selected from:

- alkyl;

- alkoxy, alkylthio;

- hydroxy, mercapto;

- nitro, nitroso;

- R°-C(X)-X'-, R°-X'-C(X)-, R°-X' -C(X)-X"- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X", which may be identical or different, representing an oxygen atom, a sulphur atom or NR with R representing a hydrogen atom or an alkyl group;

- (O)CO^"-, M⁺ with M⁺ as defined above;

G represents an oxygen atom, a sulphur atom or a NR_e group with R_e as defined above; in particular, G represents an oxygen atom; Ri and Rh, which may be identical or different, represent a hydrogen atom or an alkyl group; it being understood that formula (XVIII) includes at least one sulphonate (O)₂S(O^")-, M⁺ radical or a carboxylate -C(O)O^", M⁺ radical, preferably sodium sulphonate;

An example of a colourant with formula (XVIII) which may be cited is: Acid Blue 74.

g) colourants derived from quinoline with formula (XIX):

^■ R₆i represents a hydrogen atom, a halogen atom or an alkyl group; ■ R₆2, Rβ3, and R₆4, which may be identical or different, represent a hydrogen atom or an (O)₂S(O^")-, M⁺ group with M⁺ representing a hydrogen atom or a cationic counter-ion;

^■ or R₆i with R₆2 or R₆i with R₆4, together form a benzo group optionally substituted with one or more (O)₂S(O^")-, M⁺ groups with M⁺ representing a hydrogen atom or a cationic counter-ion; it being understood that formula (XIX) includes at least one sulphonate (O)₂S(O^")-, M⁺ radical, preferably sodium sulphonate.

Examples of colourants with formula (XIX) which may be cited are: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

More particularly, the dyes with formula (XII) to (XVII) which may be employed in the invention are selected from:

The majority of these colourants are described in particular in the Colour Index published by The Society of Dyers and Colourists, P.O. Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England.

More particularly preferred anionic dyes are the dyes designated in the Colour Index with the code C.I. 58005 (monosodium salt of 1 ,2-dihydroxy-9,10- anthraquinone-3-sulphonic acid), C.I. 60730 (monosodium salt of 2-[(9,1 O- dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl)-amino]-5-methyl-benzene sulphonic acid), C.I. 15510 (monosodium salt of 4-[(2-hydroxy-1 -naphthalenyl)-azo]- benzene sulphonic acid), C.I. 15985 (disodium salt of 6-hydroxy-5-[(4- sulphophenyl)-azo]-2-naphthalene sulphonic acid), C.I. 17200 (disodium salt of 5- amino-4-hydroxy-3-(phenylazo)-2,7-naphthalene disulphonic acid), C.I. 20470 (disodium salt of 1-amino-2-(4'-nitrophenylazo)-7-phenylazo-8-hydroxy-3,6- naphthalene disulphonic acid), C.I. 42090 (disodium salt of N-ethyl-N-[4-[[4- [ethyl[3-sulphophenyl)-methyl]-amino]-phenyl](2-sulphophenyl)-methylene]-2,5- cyclohexadien-1 -ylidene]-3-sulphobenzenemethanaminium hydroxide, internal salt) and C.I. 61570 (disodium salt of 2,2'-[(9,10-dihydro-9,10-dioxo-1 ,4- anthracenediyl)-diimino]-bis-[5-methyl]-benzene sulphonic acid).

It is also possible to use compounds corresponding to the mesomeric or tautomeric forms of structures (XII) to (XIX).

Natural direct dyes which may be used in the invention which may be cited are lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin and apigenidin. It is also possible to use extracts or decoctions containing these natural dyes and in particular cataplasms or extracts based on henna.

The direct dyes of the invention, when they are included in the composition, are present in a proportion by weight of 0.001 % to 20%, preferably 0.01 % to 10% of the total composition weight.

The medium appropriate for dyeing, also termed the dye support, is generally constituted by water or a mixture of water and at least one organic solvent to dissolve compounds which are not sufficiently soluble in water.

Examples of organic solvents which may be cited are CrC₄ lower alkanols such as ethanol or isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propyleneglycol, propylene glycol monomethylether, diethylene glycol monoethylether and monomethylether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

Preferably, the solvents are present in proportions which are preferably in the range about 1 % to 40% by weight with respect to the total weight of the dye composition, more preferably in the range about 5% to 30% by weight. The dye composition of the invention may also comprise a variety of adjuvants which are conventionally used in hair dye compositions, such as anionic surfactants, cationic surfactants other than those with formula (I), non-ionic, amphoteric or zwittehonic surfactants or mixtures thereof, mineral or organic thickening agents, in particular associative thickeners, anionic, cationic, non ionic and amphoteric polymers, antioxidants, penetrating agents, sequestrating agents, fragrances, buffers, dispersing agents, packaging agents such as volatile or nonvolatile silicones, which may be modified or unmodified, film-forming agents, preservatives or opacifying agents.

The composition of the invention may also contain one or more fatty alcohols: R""-OH, with R"" representing an alkyl or alkenyl group containing 8 to

30 carbon atoms, said fatty alcohols being introduced in the pure form or as a mixture. More particular examples which may be cited are lauric, cetyl, stearyl or oleic alcohols and mixtures thereof.

The above adjuvants are generally each present in a quantity in the range 0.01 % to 20% by weight with respect to the total composition weight.

The composition of the invention may also contain reducing agents or antioxidants. These may in particular be selected from sodium sulphite, thioglycolic acid, thiolactic acid, sodium bisulphite, dehydroascorbic acid, hydroquinone, 2-methyl-hydroquinone, ter-butyl-hydroquinone and homogentisic acid, and they are generally present in quantities of about 0.05% to 1.5% by weight with respect to the total composition weight.

Clearly, the skilled person will be careful to choose any complementary compounds so that the advantageous properties intrinsically attached to the oxidation dye composition of the invention is not altered or is not substantially altered by the envisaged adjuncts.

The pH of the dye composition of the invention is generally in the range about 3 to 12, and preferably in the range about 6 to 11.5. It may be adjusted to the desired value using the acidifying agents or alkalinizing agents normally used in dyeing keratinous fibres, or by means of conventional buffer systems.

Examples of alkalinizing agents which may be cited are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and thethanolamines as well as derivatives thereof, hydroxyalkylamines and ethylenediamines which may be oxyethylenated and/or oxypropylenated, sodium or potassium hydroxides and compounds with the following formula (XXI): in which formula (XXI):

W is a propylene residue, optionally substituted with a hydroxyl group or a CrC₄ alkyl radical; R_a, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a Ci-C₄ alkyl radical or a CrC₄ hydroxyalkyl radical.

The acidifying agents are conventionally, for example, mineral or organic acids such as hydrochloric acid, orthophosphohc acid, carboxylic acids such as tartaric acid, citric acid, lactic acid or sulphonic acids.

The dye composition of the invention may be presented in a variety of galenical forms, such as in the form of a liquid, lotion, cream, gel, or any other form which is appropriate for dyeing keratinous fibres.

It may also be packaged under pressure in an aerosol flask in the presence of a propellant and may form a foam.

The present invention also pertains to a method for dyeing using the composition described above.

In a particular implementation, the dyeing method of the invention consists of applying to keratinous fibres, in particular human keratinous fibres such as the hair, the composition which comprises i) at least one oxidation base, at least one coupling agent; ii) at least one ammonium salt with formula (I), and iii) at least one ceramide; in the presence of an oxidizing agent.

In this method the mixture may be produced extemporaneously, i.e. just when it is to be used, on dry or wet keratinous fibres, and then allowed to act for a time which is generally about 1 to 60 minutes, preferably about 10 to 45 minutes, then the fibres are rinsed, then optionally shampooed, then rinsed again and dried.

The oxidizing agent is preferably selected from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides and persalts such as perborates or persulphates. The use of hydrogen peroxide is particularly preferred. This oxidizing agent is advantageously constituted by a solution of hydrogen peroxide the titer of which may vary, more particularly from about 1 to 40 volumes, more preferably 5 to 40.

It is also possible to use as the oxidizing agent one or more oxido- reduction enzymes such as laccases, peroxidases and 2-electron oxidoreductases such as uricase, if appropriate in the presence of their respective donor or co- factor.

Illustrative non-limiting examples of the invention are given below.

EXAMPLES

The following compositions were prepared:

Dye compositions: (expressed as the percentage by weight as is)

Mode of application

The colourant compositions were diluted extemporaneously with the oxidizing agent in an amount of 1 part of dye composition per 1.5 parts of oxidizing composition. The oxidizing compositions were constituted by 20 volume hydrogen peroxide (pH close to 2-3).

The mixtures produced were applied to permed 90% white grey hair.

After leaving for 20 minutes, the hair was rinsed, washed with a standard shampoo and dried.

Hair coloured with Chestnut (composition 1 and 1 '), Dark copper auburn blond (composition 2 and 2'), Black (composition 3 and 3') or Intense red (composition 4 and 4') using these compositions had good dye properties and a very good feel, in particular with dry hair.

Claims

1. Composition for oxidation dyeing keratinous fibres comprising, in a medium appropriate for dyeing: i) at least one oxidation base; ii) at least one coupling agent; iii) at least one ammonium salt with formula (I) :

in which formula (I):

^■ R represents a CH₃CH₂-CH(RS)-CH₂-(CH₂)IT₁- group, with R₃ representing a linear or branched, saturated or unsaturated alkyl group, and m representing an integer in the range 0 to 30 inclusive;

^■ R₁ and R₂, which may be identical or different, represent a group selected from i) alkyl; ii) alkenyl; iii) alkoxy; iv) alkenyloxy; and v) aryl; the alkyl or alkenyl group of groups i) to iv) possibly being interrupted by one or more heteroatoms, which may be identical or different, selected from oxygen, sulphur and N(Ra) with Ra representing a hydrogen atom or an alkyl group; " X represents the following aminoalkylene group: -N(R₄)-(CH₂)_P-, with R₄ representing a hydrogen atom or a linear or branched alkyl group, and p representing an integer in the range 1 to 6 inclusive;

^■ Y represents an alkyl or alkoxy group; the alkyl group of the alkyl or alkoxy groups possibly being interrupted by one or more heteroatoms, which may be identical or different, selected from oxygen, sulphur and N(Ra) with Ra as defined above;

iv) at least one ceramide type compound or at least one quaternary polyammonium compound with formula (II) : in which formula (II):

^■ R₄, R₅, R₆ and R_7j which may be identical or different, designate an alkyl or hydroxyalkyl radical containing about 1 to 4 carbon atoms; " Ii and p are whole numbers from about 2 to 20; and

2. Composition according to the preceding claim, in which the oxidation base is selected from paraphenylenediamines with formula (A) below and their addition salts with an acid or an alkali:

in which formula (A): Ri represents a hydrogen atom, a CrC₄ alkyl radical, CrC₄ monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, alkoxy(Ci-C₄)alkyl(CrC₄), CrC₄ alkyl substituted with a nitrogen, phenyl or 4'-aminophenyl group;

R₂ represents a hydrogen atom, a CrC₄ alkyl radical, CrC₄ monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl, alkoxy(CrC₄)alkyl(C_rC₄) or C_rC₄ alkyl substituted with a nitrogen group;

R₃ represents a hydrogen atom, a halogen atom such as a chlorine atom, a CrC₄ alkyl radical, sulpho, carboxy, CrC₄ monohydroxyalkyl or CrC₄ hydroxyalkoxy, Ci-C₄ acetylaminoalkoxy, CrC₄ mesylaminoalkoxy or CrC₄ carbamoylaminoalkoxy, R₄ represents a hydrogen atom, a halogen atom or a CrC₄ alkyl radical.

3. Composition according to the preceding claim, in which the oxidation base is present in a concentration of 0.0001 % to 20% by weight of the total composition weight.

4. Composition according to any one of the preceding claims, in which the coupling agent is selected from meta-aminophenols, meta- phenylenediamines, metadiphenols, naphthols and heterocyclic coupling agents such as indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolothazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1 ,3- benzodioxoles, quinolines and their addition salts with an acid.

5. Composition according to the preceding claim, in which the coupling agent is present in a concentration of 0.0001 % to 20% by weight of the total composition weight.

6. Composition according to any one of the preceding claims, in which the ammonium salt with formula (I) comprises a group R representing an alkyl group which contains 8 to 40 carbon atoms, and m is an integer in the range 3 to 25 inclusive.

7. Composition according to any one of the preceding claims, in which the ammonium salt with formula (I) comprises an alkyl group R₃ containing less than 12 carbon atoms, and Ri and R₂ represent an aryl, alkyl or alkoxy group containing 1 to 8 carbon atoms.

8. Composition according to any one of the preceding claims, in which the ammonium salt with formula (I) comprises an alkoxy or alkyl group Y containing 1 to 6 carbon atoms.

9. Composition according to any one of the preceding claims, in which the ammonium salt with formula (I) comprises a group R in which R₃ represents a methyl and m is 16.

10. Composition according to any one of the preceding claims, in which the ammonium salt with formula (l)is a quaternized eicosanoic acid derivative Of Ci₀-C₄₀ lsoalkylamidopropylethyldimonium methosulphate.

11. Composition according to any one of the preceding claims, in which the ammonium salt with formula (I) is present in the composition of the invention in a quantity in the range 0.002% to 2% by weight with respect to the composition.

12. Composition according to any one of the preceding claims, in which the ceramide type compound has formula (XX):

in which formula (XX):

^■ R-|4 designates : i) a linear or branched, saturated or unsaturated hydrocarbon radical

C1-C50, preferably C₅-C₅O, said radical possibly being substituted with one or more hydroxy groups which may be esterified by an acid Ri₉COOH, with R₁₉ being a linear or branched, saturated or unsaturated Ci-C3₅hydrocarbon radical, which may be mono- or polyhydroxylated, the hydroxy group or groups of radical R19 possibly being esterified by a linear or branched, saturated or unsaturated Ci-C₃₅fatty acid, which may be mono- or polyhydroxylated; ii) a R"-(NR-CO)_q-R' radical, with R designating a hydrogen atom or a mono- or polyhydroxylated, preferably mono-hydroxylated C1-C20 hydrocarbon radical, R' and R" are hydrocarbon radicals wherein the sum of the carbon atoms is in the range 9 to 30, R' being a divalent radical; q designates 0 or 1 ; or iii) a R₂o-O-CO-(CH₂)_p radical, R₂o designating a CrC₂O hydrocarbon radical, p being an integer in the range 1 to 12 inclusive; R-|5 is selected from a hydrogen atom, a saccharide type radical, in particular a (glycosyl)_n, (galactosyl)_m or sulphogalactosyl radical, a sulphate or phosphate residue, a phosphorylethylamine radical and a phosphorylethylammonium radical, in which n is an integer in the range 1 to 4 inclusive, and m is an integer in the range 1 to 8 inclusive; R-|6 designates a saturated or unsaturated, hydroxylated or non- hydroxylated C₁-C₃₃ hydrocarbon radical, the hydroxy group or groups possibly being esterified by a mineral acid or an acid R19COOH, Rig having the meanings given above, the hydroxyl group or groups possibly being etherified by a (glycosyl)_n,

(galactosyl)_mj sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium radical, R16 possibly being substituted with one or more Ci-Ci₄ alkyl radicals; preferably, R16 designates a Cis-C₂6 α-hydroxyalkyl radical, the hydroxyl group optionally being esterified by a Ci₆-C₃₀ α- hydroxyacid;

^■ R-|7 designates a hydrogen atom, a saturated or unsaturated, linear or branched non-alkoxylated C3-C50 hydrocarbon radical, optionally hydroxylated such as a methyl, ethyl or a R_2I-O-CO-(CH₂) radical, R₈ designates a CrC₂₀ hydrocarbon radical, p is an integer from 1 to

12;

^■ R-|8 designates a hydrogen atom or a saturated or unsaturated, linear or branched CrCs₀ hydrocarbon radical, which may be mono- or polyhydroxylated, the hydroxy group or groups possibly being etherified by (glycosyl)_n, (galactosyl )_mj sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium radical.

13. Composition according to the preceding claim, in which the ceramide type compound has formula (XX) in which Ri₄ designates a C12-C20 alkenyl chain comprising one or two π double bonds; R15 designates a hydrogen atom; Ri₆ designates a linear Cn-Ci₇ radical which may be hydroxylated; Ri₇ represents a Ci₀-C₂O alkyl group and Ri₈ represents a hydrogen atom.

14. Composition according to any one of the preceding claims, in which the ceramide type compound is selected from:

- 2-N-linoleoylamino-octadecane-1 ,3-diol; - 2-N-oleoylamino-octadecane-1 ,3-diol;

- 2-N-palmitoylamino-octadecane-i ,3-diol;

- 2-N-stearoylamino-octadecane-1 ,3-diol;

- 2-N-behenoylamino-octadecane-1 ,3-diol;

- 2-N-[2-hydroxy-palmitoyl]-amino-octadecane-1 ,3-diol; - 2-N-stearoyl amino-octadecane-1 ,3,4 triol and in particular N- stearoyl phytosphingosine;

- 2-N-palmitoylamino-hexadecane-i ,3-diol; or mixtures of said compounds.

15. Composition according to any one of claims 1 to 11 , in which the quaternary polyammonium with formula (II) comprises the groups R₄, R5, R₆ and R₇ which independently represent a methyl or ethyl radical and Q'^" represents a halide counter ion.

16. Composition according to any one of claims 1 to 12, in which the quaternary polyammonium compound with formula (II) corresponds to the polymer of Λ/,Λ/,Λ/',Λ/-tetramethylhexamethylenediamine and 1 ,3- dichloropropylene.

17. Composition according to any one of the preceding claims, which further comprises the oxidizing agent.

18. Method for direct dyeing of keratinous fibres, consisting of applying a composition as defined in one of claims 1 , 6 to 17.

19. Method for oxidation dyeing of keratinous fibres, in particular human keratinous fibres such as hair, consisting of applying to the fibres a composition as defined in any one of the preceding claims in the presence of at least one oxidizing agent, which is mixed just at the moment the composition is to be used.

20. Use of an association comprising i) at least one oxidation base as defined in any one of Claims 1 to 3; ii) at least one coupling agent as defined in any one of Claims 1 and 4, 5; iii) at least one ammonium salt with formula (I) as defined in any one of Claims 1 and 6 to 11 ; iv) at least one ceramide type compound as defined in any one of Claims 1 , 12 to 14, or at least one polyammonium compound with formula (II) as defined in any one of Claims

1 , 15 and 16; to dye keratinous fibres and in particular human keratinous fibres such as hair.

21. Device comprising a first compartment comprising the composition according to any one of Claims 1 to 16 and a second compartment containing at least one oxidizing agent.