EP2076238A1

EP2076238A1 - Composition for the direct dyeing of keratinous fibres comprising at least one ammonium salt of 18mea and at least one direct dye, colouring method starting from the composition

Info

Publication number: EP2076238A1
Application number: EP07821438A
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: WO2008049768A1

Abstract

The present invention relates to a composition for the direct dyeing of keratinous fibres, in particular human keratinous fibres, such as the hair, comprising, in a medium appropriate for dyeing, i) at least one anionic or cationic direct dye and ii) at least one specific ammonium salt derived from 18MEA. The invention also relates to the dyeing method employing the said composition. The dyeing compositions of the invention have improved cosmetic properties; in particular, they leave an excellent feel on the hair after colouring the keratinous fibres.

Description

COMPOSITION FOR THE DIRECT DYEING OF KERATINOUS FIBRES

COMPRISING AT LEAST ONE AMMONIUM SALT OF 18MEA AND AT

LEAST ONE DIRECT DYE, COLOURING METHOD STARTING FROM

THE COMPOSITION

The present invention relates to a composition for the direct dyeing of keratinous fibres, in particular human keratinous fibres, such as the hair, comprising, in a medium appropriate for dyeing, at least one cationic or anionic direct dye and at least one specific ammonium salt .

It is known to dye keratinous fibres and in particular human hair with dyeing compositions comprising direct dyes. These dyes can be anionic, cationic or neutral. The conventional dyes which are used are in particular dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, cationic azo, xanthene, acridine, azine or triarylmethane type or natural dyes.

These dyes, which are coloured and colouring molecules having an affinity for the fibres, are applied to the keratinous fibres for a time necessary for the desired colouring to be obtained and then rinsed out.

The colourings which result therefrom are particularly chromatic colourings which, however, are temporary or semipermanent as the nature of the interactions which bind direct dyes to the keratinous fibre and their desorption from the surface and/or from the core of the fibre are responsible for their weak dyeing power and for their poor resistance to washing operations or to perspiration. In addition, these direct dyes are generally sensitive to light due to the weak resistance of the chromophore with regard to photochemical attacks and result over time in dulling of the colour of the hair .

The cationic direct dyes available in the field of the dyeing of keratinous fibres, in particular human keratinous fibres, are known to include dyes, generally known as Arianor dyes, comprising an exocyclic quaternary trialkylammonium group, which result in colourings exhibiting characteristics which are still inadequate .

Moreover, in order to improve the colouring power and the treatment or shaping effect on the hair, it is known to add a quaternary ammonium salt to the dyes of Arianor type (JP 2004/099475) .

However, whether as regards the power and the chromaticity of the shades obtained, as regards the homogeneity of the colour distributed along the fibre, and as regards the toughness, in terms of resistance to the various attacks to which the hair may be subjected, or as regards the aesthetic and cosmetic appearance of the fibres, the colouring obtained is unsatisfactory.

The aim of the present invention is to develop direct dyeing compositions possessing improved cosmetic properties which also make it possible to obtain powerful and chromatic shades which are luminous, with low selectivities and good persistence with regard to chemical agents, such as shampoos or perms, or natural agents, such as light, perspiration or sebum.

This aim is achieved by the present invention, a subject-matter of which is a composition for the direct dyeing of keratinous fibres, in particular human keratinous fibres, such as the hair, comprising, in a medium appropriate for dyeing: i) at least one direct dye chosen from anionic direct dyes and direct dyes possessing an endocyclic cationic charge; and ii) at least one ammonium salt of formula (I) : in which formula (I) :

R represents a CH₃CH₂-CH (R₃) -CH₂- (CH₂) _m- group, with R₃ representing a saturated or unsaturated and linear or branched alkyl group and m representing an integer of between 0 and 30 inclusive;

■ Ri and R2, which are identical or different, represent a group chosen from i) alkyl; ii) alkenyl; iii) alkoxy and iv) alkenyloxy and v) aryl; it being possible for the alkyl or alkenyl group of the groups from i) to iv) to be interrupted by one or more identical or different heteroatoms chosen from oxygen, sulphur or 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 of between 1 and 6 inclusive, preferably 3;

■ Y represents an alkyl or alkoxy group; it being possible for the alkyl group of the alkyl or alkoxy groups to be interrupted by one or more identical or different heteroatoms chosen from oxygen, sulphur or N(Ra) with Ra as defined above;

■ Q^" represents the anionic counterion associated with the quaternary ammonium.

The invention is also targeted at a method for colouring keratinous fibres and in particular human keratinous fibres, such as the hair, which consists in applying, to the fibres, the composition of the invention .

In addition, a subject-matter of the present invention is the use, as direct dye in direct dyeing compositions for keratinous fibres, of a combination comprising i) at least one direct dye chosen from anionic direct dyes and direct dyes possessing an endocyclic cationic charge; and ii) at least one ammonium salt of formula (I) as defined above.

The composition of the present invention makes it possible to obtain a colouring of keratinous fibres of very good quality in terms of power, of homogeneity and of toughness which additionally exhibits, after colouring, a particularly pleasant feel on the fibres, in particular on the dry fibres. The colouring is persistent with regard in particular to shampoos. Moreover, the disentangling of the fibres is facilitated and the particularly shiny appearance of the keratinous fibres is highly attractive.

Within the meaning of the present invention, and unless otherwise indicated: an "alkyl radical" is a linear or branched Ci- Ci6, preferably Ci-Cβ, hydrocarbon radical; an "alkenyl radical" is a linear or branched C₂-

C16 hydrocarbon radical comprising from 1 to 5 conjugated or nonconjugated π double bonds, preferably a Ci-Cβ hydrocarbon radical comprising 1 or 2 double bonds; an "alkoxy radical" is an alkyl-oxy (alkyl-O-) radical for which the alkyl radical is a radical as defined above; an "alkenyloxy radical" is an alkenyl-oxy radical for which the alkenyl radical is a radical as defined above; a "polyhaloalkyl radical" is an alkyl radical comprising from 1 to 6 identical or different halogens, such as trifluoromethyl; - an "aryl" radical represents a mono- or fused or nonfused polycyclic group comprising from 6 to 19 carbon atoms, at least one ring of which is aromatic; preferably, the aryl radical is a phenyl, biphenyl, naphthyl, xylyl, anthracyl, phenanthryl, indenyl or tetrahydronaphthyl; the term "optionally substituted aryl" or "optionally substituted benzo" implies that the aryl radical can be substituted by one or more substituents chosen from i) a halogen; ii) alkyl; iii) alkoxy; iv) hydroxyl : OH; v) nitro: NO2; vi) nitroso: NO; vii) cyano : CN; viii) RO-C(O)-, R₅-C(O)O- or R₂N-C(O)-NR₆- with R₅ representing a hydrogen atom, a Ci-C₄ alkyl group or a hydroxyl group and R and R₆, which are identical or different, representing a hydrogen atom or an alkyl group, preferably a Ci-C₄ alkyl group; ix) sulphamoyl; x) trihaloalkyl, preferably CF₃; xi) aminoalkoxy, preferably Ci-C₄ aminoalkoxy; xii) (di) (alkyl) amino; xiii) (di) (alkyl) aminocarbonyl; xiv) R¹C(O)-N(R)- with R and R', which are identical or different, representing a hydrogen atom or an alkyl group, preferably a Ci-C₄ alkyl group; xv) carboxylate C(O)OM with M representing an alkali metal cation, such as sodium or potassium; xvi) sulphonate S(O)₂OM with M as defined above; xvii) sulphonic S(O)₂OH; a "heterocyclic radical" is a nonaromatic monocyclic radical comprising from 5 to 6 ring members which comprises from 1 to 3 heteroatoms chosen from nitrogen, oxygen and sulphur atoms; preferably, the heterocycles are chosen from the pyridyl, piperazyl, morpholinyl, thiomorpholinyl, piperidyl and pyrrolidinyl groups; - an "anionic counterion" is an anion or an anionic group associated with the cationic charge of the ammonium; more particularly, the anionic counterion is chosen from i) halides, such as: chloride or bromide; ii) nitrates; iii) sulphonates, including Ci-C₆ alkylsulphonates : AIk-S(O)₂O-, such as methylsulphonate and ethylsulphonate; iv) arylsulphonates : Ar-S(O)₂O-, such as benzenesulphonate and toluenesulphonate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulphates: AIk-O-S (O) O^~, such as methyl sulphate and ethyl sulphate; x) aryl sulphates: Ar-O-S (0)0^~, such as phenyl sulphate and tolyl sulphate; xi) alkoxy sulphates: AIk-O-S (0) 2θ^~, such as methoxy sulphate and ethoxy sulphate; xii) aryloxy sulphates: Ar-O-S (0) 2θ^~; xiii) phosphate; xiv) acetate; xv) triflate; and xvi) borates, such as tetrafluoroborate; a "cationic counterion" is a cation or a cationic group associated with the anionic charge of the acid dye; more particularly, it is chosen from the cations of atoms of alkali metals, such as sodium or potassium, and of alkaline earth metals, such as calcium.

The anionic direct dyes of the invention are dyes commonly referred to as "acid" direct dyes for their affinity with alkaline substances. The term "anionic direct dyes" is understood to mean any direct dye comprising, in its structure, at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation originating from a metal or from an amine or an ammonium ion. The anionic dyes can be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthra- quinone dyes, indigoids and acid natural dyes.

Mention may be made, as acid dyes according to the invention, of the dyes of following formulae (II) , (II¹), (HI), (HI¹), (IV), (IV), (V), (V), (VI), (VII) , (VIII) and (IX) :

a) diaryl anionic azo dyes of formula (II) or (II¹) :

ich formulae (II) and (II¹) :

^■ R₇, R₈, Rg, Rio, R'₇, R' 8, R' 9 and R'io, which are identical or different, represent a hydrogen atom or a group chosen from: - alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X) -X"-, with

R° representing a hydrogen atom or an alkyl or aryl group and X, X' and X", which are identical or different, representing an oxygen or 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 counterion;

(O)CO^"- M⁺, with M⁺ as defined above; R"-S(0)2~/ with R" representing a hydrogen atom, an alkyl group or 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 optionally substituted aryl or alkyl group and X' as defined above; (di) (alkyl) amino; aryl (alkyl) amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)₂S(O^")- M⁺ and iv) alkoxy with M⁺ as defined above; optionally substituted heteroaryl; preferably a benzothiazolyl group; cycloalkyl; in particular cyclohexyl, Ar-N=N-, with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O)₂S(O^")- M⁺ or phenylamino groups; or then two adjacent groups R₇ with R₈ or R₈ with R₉ or R₉ with Ri₀ together form a fused benzo group A'; and R'₇ with R'₈ or R'₈ with R'₉ or R'₉ with R'io together form a fused benzo group B'; with A' and B' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)₂S(O^")- M⁺; iv) hydroxyl; 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) optionally substituted aryl (alkyl) amino; with M⁺, R°, X, X', X" and Ar as defined above; " W represents a sigma σ bond, an oxygen or sulphur atom or a divalent radical i) -NR-, with R as defined above, or ii) methylene -C (R_a) (Rb)-, with R_a and R]₃, which are identical or different, representing a hydrogen atom or an aryl group, or then R_a and R]₃ form, together with the carbon atom which carries them, a spiro cycloalkyl; preferably, W represents a sulphur atom or R_a and R_b together form a cyclohexyl; it being understood that the formulae (II) and (II¹) comprise at least one sulphonate radical (O)₂S(O-)- M⁺ or one carboxylate radical (O)CO^"- M⁺ on one of the A, A', B, B' or C rings; preferably sodium sulphonate.

Mention may be made, as example of dyes of formula (II) , of: 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 mention may be made, as example of dyes of formula

(II¹), of: Acid Red 111, Acid Red 134, Acid Yellow 38.

b) pyrazolone anionic azo dyes of formulae (III) and (HI¹) :

in which formulae (III) and (III¹):

^■ Rn, Ri2 and R13, which are identical or different, represent a hydrogen or halogen atom or an alkyl or -(O)₂S(O^") M⁺ group, with M⁺ as defined above; ■ Ri₄ represents a hydrogen atom, an alkyl group or a -C(O)O^" M⁺ group, with M⁺ as defined above;

^■ Ri₅ represents a hydrogen atom;

^■ Ri6 represents an oxo group, in which case R'i6 is absent, or then R₁₅ with R_i6 together form a double bond;

^■ Ri₇ and R_i8, which are identical or different, represent a hydrogen atom or a group chosen from:

(O)₂S(O^")- M⁺, with M⁺ as defined above; Ar-O-S(O)₂-, with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups; ^■ Rig and R20 together form either a double bond or an optionally substituted benzo group D ' ;

^■ R'i6, R'i9 and R'20, which are identical or different, represent a hydrogen atom or an alkyl or hydroxyl group;

^■ R21 represents a hydrogen atom or an alkyl or alkoxy group;

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

^■ Y represents either a hydroxyl group or an oxo group;

^■ represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxyl group;

it being understood that the formulae (III) and (III¹) comprise at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺ on either of the D or E rings; preferably sodium sulphonate.

Mention may be made, as example of dyes of formula (III), of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and mention may be made, as example of dyes of formula (III¹), of: Acid Yellow 17.

c) anthraquinone dyes of formulae (IV) and (IV) :

in which formulae (IV) and (IV) :

^■ R₂₂, R23, R24, R25, R26 and R₂₇, which are identical or different, represent a hydrogen or halogen atom or a group chosen from: - alkyl; hydroxyl, mercapto; alkoxy, alkylthio; optionally substituted aryloxy or arylthio, preferably substituted by one or more groups chosen from alkyl and (O)₂S(O^")- M⁺, with M⁺ as defined above; aryl (alkyl) amino optionally substituted by one or more groups chosen 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 an NR₂₈R₂₉ group with R₂₈ and R₂₉, which are identical or different, representing a hydrogen atom or a group chosen from: alkyl; polyhydroxyalkyl, such as hydroxyethyl; aryl optionally substituted by one or more groups, particularly i) alkyl, such as methyl, n-dodecyl or n-butyl; ii) (O)₂S(O^")- M⁺, with M⁺ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)- or R°-X'-C (X) -X"-, with R°, X, X' and X" as defined above; preferably, R° represents an alkyl group; cycloalkyl; in particular cyclohexyl;

^■ Z represents a group chosen from hydroxyl and NR'₂₈R'₂₉ with R'₂₈ and R'₂₉, which are identical or different, representing the same atoms or groups as R₂₈ and R₂₉ as defined above;

it being understood that the formulae (IV) and (IV) comprise at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺; preferably sodium sulphonate

Mention may be made, as example of dyes of formula (IV), of: 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 mention may be made, as example of dyes of formula (IV), of: Acid Black 48.

d) nitro dyes of formulae (V), (V) and (V"):

in which formulae (V) and (V) :

^■ R₃₀, R31 and R32, which are identical or different, represent a hydrogen or halogen atom or a group chosen from: alkyl; - alkoxy optionally substituted by one or more hydroxyl groups, alkylthio optionally substituted by one or more hydroxyl groups; hydroxyl, mercapto; nitro, nitroso; - polyhaloalkyl;

- R°-C(X)-X'-, R°-X'-C(X)- or 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; particularly, R30, R31 and R32 represent a hydrogen atom;

^■ R_c and Rd, which are identical or different, represent a hydrogen atom or an alkyl group;

^■ W is as defined above; W particularly represents an -NH- group;

^■ ALK represents a divalent, linear or branched, Ci-Cβ alkylene group; particularly, ALK represents a -CH2-CH2- group;

^■ n has the value 1 or 2; ■ P represents an integer of between 1 and 5 inclusive;

^■ q represents an integer of between 1 and 4 inclusive;

^■ u has the value 0 or 1; ■ when n has a value 1, J represents a nitro or nitroso group, particularly a nitro group;

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

^■ M' represents a hydrogen atom or a cationic counterion;

^■ 'L"_% ^"YN , which is present or absent, represents a benzo group optionally substituted by one or more R30 groups as defined above;

it being understood that the formulae (V) and (V) comprise at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺; preferably sodium sulphonate .

Mention may be made, as example of dyes of formula (V) , of: Acid Brown 13; Acid Orange 3; mention may be made, as example of dyes of formula (V), of: Acid Yellow 1, sodium salt of 2, 4-dinitro-l-naphthol-7-sulphonic acid, 2-piperidino-5-nitrobenzenesulphonic acid, 2- (4' -N, N- (2 "-hydroxyethyl) amino-2 ' -nitro) anilineethanesulphonic acid or 4- (β-hydroxyethylamino) -3-nitrobenzenesulphonic acid.

e) triarylmethane dyes of formula (VI) :

in which formula (VI) :

^■ R₃₃, R₃₄, R₃₅ and R₃₆, which are identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl group and benzyl group optionally substituted by an (O) _mS (CT)- M⁺ group, with M⁺ and m as defined above;

^■ R3₇, R38 r R39/ R40/ R41/ R-42/ R43 and R44, which are identical or different, represent a hydrogen atom or a group chosen from: alkyl; alkoxy, alkylthio; (di) (alkyl) amino; hydroxyl, mercapto; - nitro, nitroso;

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

(O)CO^"- M⁺, with M⁺ as defined above; or then two adjacent groups R41 with R₄₂ or R₄₂ with R₄₃ or R₄₃ with R₄₄ together form a fused benzo group: I'; with I' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)₂S(O^")- M⁺; iv) hydroxyl; 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' and X" as defined above; particularly, R₃₇ to R₄o represent a hydrogen atom and R₄1 to R₄₄, which are identical or different, represent a hydroxyl or (O)₂S(O^")- M +^" group; and, when R₄₃ with R₄₄ together form a benzo group, it is preferably substituted by a (O)₂S (0^") - group;

it being understood that at least one of the G, H, I or I' rings comprises at least one sulphonate radical (O)₂S(O^")- or one carboxylate radical -C(O)O^"; preferably sulphonate .

Mention may be made, as example of dyes of formula (VI) , of: Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 50.

f) dyes derived from xanthene of formula (VII) :

in which formula (VII) : ^■ R.45, R-46, R47 and R48, which are identical or different, represent a hydrogen atom or a halogen atom;

^■ R49, R50, R51 and R52, which are identical or different, represent a hydrogen or halogen atom or a group chosen from: - alkyl; alkoxy, alkylthio; hydroxyl, mercapto; - nitro, nitroso;

(O)CO^"- M⁺, with M⁺ as defined above; particularly, R₅₃ R₅₄, R₅₅ and R₄s represent a hydrogen or halogen atom;

^■ G represents an oxygen or sulphur atom or an NR_e group with R_e as defined above; particularly, G represents an oxygen atom;

^■ L represents an alkoxide 0^~ M⁺; a thioalcoholate S^~ M⁺ or an NR_f group, with R_f representing a hydrogen atom or an alkyl group, and M⁺ as defined above; M⁺ is particularly sodium or potassium;

^■ L' represents an oxygen or sulphur atom or an ammonium group: N⁺R_fR_g, with R_f and R_g, which are identical or different, representing a hydrogen atom or an optionally substituted aryl or alkyl group; L' particularly represents an oxygen atom or a phenylamino group optionally substituted by one or more alkyl or (0)_mS(0^")- M⁺ groups, with m and M⁺ as defined above;

^■ Q and Q' , which are identical or different, represent an oxygen or sulphur atom; particularly, Q and Q' represent an oxygen atom; ■ M⁺ is as defined above.

Mention may be made, as example of dyes of formula (VII), of: Acid Yellow 73, Acid Red 51, Acid Red 87, Acid Red 92, Acid Red 95, Acid Violet 9. g) dyes derived from indole of formula (VIII) :

in which formula (VIII) :

^■ R-53 / R-54 / R-55 / R-56 / R-57 r R-58 r R-59 and R.60 r whi ch are identical or different, represent a hydrogen atom or a group chosen from:

- alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso;

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

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

^■ R₁ and Rh, which are identical or different, represent a hydrogen atom or an alkyl group; it being understood that the formula (VIII) comprises at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺; preferably sodium sulphonate .

Mention may be made, as example of dyes of formula (VIII), of: Acid Blue 74.

h) dyes derived from quinoline of formula (IX) : in which formula (IX) :

^■ R.61 represents a hydrogen or halogen atom or an alkyl group;

^■ R₆2, R63 and R.64, which are identical or different, represent a hydrogen atom or an (O)₂S(O^")- M⁺ group, with M⁺ representing a hydrogen atom or a cationic counterion;

^■ or then R₆i with R₆2 or R₆i with R₆₄ together 0 form a benzo group optionally substituted by one or more (O)₂S(O^")- M⁺ groups, with M⁺ representing a hydrogen atom or a cationic counterion; it being understood that the formula (IX) comprises at least one sulphonate radical (O)₂S(O^")- M⁺, 5 preferably sodium sulphonate.

Mention may be made, as example of dyes of formula (IX) , of: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5. 0 More particularly, the dyes of formulae (II) to (VII) of use in the invention are chosen from:

(CI. 45380) Acid Red 87 (VII)

(CI. 10316) Sodium salt of 2, 4-dinitro-l-naphthol-7-sulphonic acid (V)

(CI. 10383) Acid Orange 3 (V)

(CI. 13015) Acid Yellow 9 / Food Yellow 2 (II)

(CI. 14780) / Direct Rec 1 45 / Food Red 13 (II)

(CI. 13711) Acid Black 52 (II)

(CI. 13065) Acid Yellow 36 (II)

(CI. 14700) Sodium salt of l-hydroxy-2- (5 ' -sulphonato-2', 4'- xylylazo) -naphthalene-4-sulphonic acid / Food Red 1 (II)

(CI. 14720) Acid Red 14 / Food Red 3 / Mordant Blue 79 (II)

(CI. 14805) Sodium salt of 4-hydroxy-3- [ (2-methoxy-5- nitrophenyl) diaza] -6- (phenylamino) naphthalene-2- sulphonic acid / Acid Brown 4 (II)

(CI. 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (II)

(CI. 15985) Food Yellow 3 / Pigment Yellow 104 (II)

(CI. 16185) Acid Red 27 / Food Red 9 (II)

(CI. 16230) Acid Orange 10 / Food Orange 4 (II)

(CI. 16250) Acid Red 44 (II)

(CI. 17200) Acid Red 33 / Food Red 12 (II)

(CI. 15685) Acid Red 184 (II)

(CI. 19125) Acid Violet 3 (II)

(CI. 18055) Sodium salt of l-hydroxy-2- (4'- (acetamido) phenylazo) -8-acetamidonaphthalene-3, 6- disulphonic acid / Acid Violet 7 / Food Red 11 (II)

(CI. 18130) Acid Red 135 (II)

(CI. 19130) Acid Yellow 27 (III)

(CI. 19140) Acid Yellow 23 / Food Yellow 4 (III)

(CI. 20170) 4 ' - (sulphonato-2 ' ' , 4 ' ' -dimethyl) bis (2, 6- phenylazo) -1 , 3-dihydroxybenzene / Acid Orange 24 (II)

(CI. 20470) Sodium salt of l-amino-2- (4 ' -nitrophenylazo) -7- phenylazo-8-hydroxynaphthalene-3, 6-disulphonic acid / Acid Black 1 (II)

(CI. 23266) (4- ( (4-Methylphenyl) sulphonyloxy) phenylazo) -2,2'- dimethyl-4- ( (2-hydroxy-5, 8- disulphonato) naphthylazo) biphenyl / Acid Red 111

(ii¹)

(CI. 27755) Food Black 2 (II)

(CI. 25440) 1- (4 ' -sulphonatophenylazo) -4- ( (2"-hydroxy-3"- acetylamino-6", 8"-disulphonato) naphthylazo) -6- sulphonatonaphthalene (tetrasodium salt) / Food Black 1 (II)

(CI. 42090) Acid Blue 9 (VI)

(CI. 60730) Acid Violet 43 (IV)

(CI. 61570) Acid Green 25 (IV)

(CI. 62045) Sodium salt of l-amino-4-cyclohexylamino-9, 10- anthraquinone-2-sulphonic acid / Acid Blue 62 (IV)

(CI. 62105) Acid Blue 78 (IV)

The majority of these dyes 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, BDl 2JB, England.

The anionic dyes which are more particularly preferred are the dyes denoted in the Colour Index under the code C.I. 58005 (monosodium salt of 1, 2-dihydroxy-9, 10- 0 anthraquinone-3-sulphonic acid), C.I. 60730 (monosodium salt of 2- [ (9, 10-dihydro-4-hydroxy-9, 10-dioxo-l- anthracenyl) amino] -5-methylbenzenesulphonic acid), C.I. 15510 (monosodium salt of 4- [ (2-hydroxy-l- naphthyl) azo] benzenesulphonic acid), C.I. 15985 5 (disodium salt of 6-hydroxy-5- [ (4-sulphophenyl) azo] -2- naphthalenesulphonic acid), C.I. 17200 (disodium salt of 5-amino-4-hydroxy-3- (phenylazo) -2, 7- naphthalenedisulphonic acid), C.I. 20470 (disodium salt of l-amino-2- (4 ' -nitrophenylazo) -7-phenylazo-δ-hydroxy- 0 3, 6-naphthalenedisulphonic acid), C.I. 42090 (disodium salt of N-ethyl-N- [4- [ [4- [ethyl [ (3- sulphophenyl) methyl] amino] phenyl] (2-sulphophenyl) - methylene] -2, 5-cyclohexadien-l-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 ] benzenesulphonic acid) .

Use may also be made of compounds corresponding to the mesomeric or tautomeric forms of the structures (II) to (IX) .

The anionic direct dye or dyes particularly represent from 0.001 to 20% by weight approximately of the total weight of the composition and preferably from 0.005 to 10% by weight approximately. More particularly, the anionic dye or dyes represent from 0.01 to 5% by weight.

Within the meaning of the present invention, the term "cationic azo, methine or azomethine direct dye" is understood to mean a dye capable of colouring keratinous fibres in the absence of any oxidizing agent comprising, in its structure, at least one -Ti=T₂- group, Ti and T₂ denoting, independently of one another, a nitrogen atom or a CH group.

Within the meaning of the present invention, the term "cationic direct dye possessing an endocyclic cationic charge" is understood to mean any direct dye comprising, in its structure, at least one quaternized nitrogen atom included in a ring. The term "dye with permanent cationic charge" is used, in contrast to dyes comprising functional groups with primary, secondary or tertiary amines. It being understood that the quaternized atom included in the ring cannot represent a nitroso group (NO) .

Particularly, the term "cationic direct dye possessing an endocyclic quaternary ammonium group" is understood to mean a dye capable of colouring keratinous fibres in the absence of any oxidizing agent comprising, in its structure, at least one saturated or unsaturated heterocycle comprising, in its sequence of ring members, at least one nitrogen atom carrying a positive permanent charge, the said heterocycle comprising from 4 to 8 ring members and being optionally fused with one or more other aromatic nuclei or heterocycles and optionally comprising one or more other heteroatoms chosen from nitrogen, sulphur and oxygen. Each of these rings can optionally be substituted.

The nitrogen atom carrying a permanent positive charge is preferably substituted by an optionally substituted C1-C30 alkyl radical or by an optionally substituted phenyl radical.

The optional substituents of the alkyl groups are preferably chosen from halogen atoms or hydroxyl, amino, mono- or di (C1-C4) alkylamino, mono- or dihydroxy (Ci-C₄) alkylamino, C6-C30 aryl or cyano groups.

The optional substituents of the aryl groups are preferably chosen from halogen atoms or C1-C30 alkyl, hydroxyl, amino, mono- or di (Ci-C₄) alkylamino, mono- or dihydroxy (Ci-C₄) alkylamino, cyano, nitro or C2-C10 acyl groups.

Preferably, this substituent on the nitrogen atom carrying a permanent charge is a Ci-C₄ alkyl group.

More preferably still, this substituent is a methyl group .

Mention may more particularly be made, as azo, methine or azomethine direct dyes possessing a quaternary ammonium group included in a ring in the context of the present invention, of: i) the following direct dyes described in Patent Application EP 1 025 834: of formula (X) G-N=N-J (X) in which : the symbol G represents a group chosen from the following structures Gi to G3 :

in which:

> R₂₄ denotes a Ci-C₄ alkyl radical or a phenyl radical which can be substituted by a Ci-C₄ alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine;

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

> R₂₆ and R₂₇, which are identical or different, represent a Ci-C₄ alkyl radical or a phenyl radical or together form, in Gi, a benzene ring substituted by one or more Ci-C₄ alkyl, Ci-C₄ alkoxy or NO₂ radicals or together form, in G₂, a benzene ring optionally substituted by one or more Ci-C₄ alkyl, Ci-C₄ alkoxy or NO₂ radicals;

> R₂₆ can additionally denote a hydrogen atom;

> Z denotes an oxygen or sulphur atom or an -NR₂₅ group;

> M represents a -CH, -CR (R denoting Ci-Cz alkyl) or -NR₂₈ (X^") _r group;

> K represents a -CH, -CR (R denoting Ci-Cz alkyl) or -NR₂₈ (X^") _r group; > P represents a -CH, -CR (R denoting Ci-C₄ alkyl) or -NR₂₈ (X^") _r group;

> r denotes zero or 1 ;

> R28 represents an 0^~ atom, a Ci-C₄ alkoxy radical or a Ci-C₄ alkyl radical;

^ R29 and R30, which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci- C₄ alkyl radical, a Ci-C₄ alkoxy radical or an -NO2 radical;

> X^~ represents an anionic counterion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate; he symbol J represents: a) a group of following structure Ji:

in which:

> R₃₁ represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-C₄ alkyl radical, a Ci-C₄ alkoxy radical or an -OH, -NO₂, -NHR₃₄, -NR₃₅R₃₆ or -NHCO (Ci-C₄) alkyl radical or forms, with R₃₂, a 5- or 6-membered ring comprising or not comprising one or more heteroatoms chosen from nitrogen, oxygen or sulphur;

> R₃₂ represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-C₄ alkyl radical or a Ci-C₄ alkoxy radical;

> or forms, with R₃₃ or R₃₄, a 5- or 6-membered ring comprising or not comprising one or more heteroatoms chosen from nitrogen, oxygen or sulphur; > R₃₃ represents a hydrogen atom, an -OH radical, an -NHR₃₄ radical or an -NR₃₅R₃₆ radical; > R34 represents a hydrogen atom, a Ci-C₄ alkyl radical, a Ci-C₄ monohydroxyalkyl radical, a C2~C₄- polyhydroxyalkyl radical or a phenyl radical; ^ R35 and R36, which are identical or different, represent a Ci-C₄ alkyl radical, a Ci-C₄ monohydroxyalkyl radical or a C₂~C₄ polyhydroxyalkyl radical;

b) a 5- or 6-membered nitrogenous heterocyclic group capable of including other heteroatoms and/or carbonyl groups and which can be substituted by one or more Ci-C₄ alkyl, amino or phenyl radicals, and in particular a group of following structure

J₂:

in which

> R₃₇ and R₃₈, which are identical or different, represent a hydrogen atom, a Ci₃-Ci₀ alkyl radical or a phenyl radical;

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

^ n represents 0 or 1 with, when n denotes 1, U denoting the -CO- radical;

ii) of following formula (XI) :

in which:

> R12 represents a hydrogen atom or a Ci-C₄ alkyl radical, > Ri3 represents a hydrogen atom, an alkyl radical which can be substituted by a -CN radical or by an amino group, or a 4'- aminophenyl radical or forms, with R12, an optionally oxygen-comprising and/or nitrogen- comprising heterocycle which can be substituted by a C1-C4 alkyl radical,

^ Ri₄ and Ri5, which are identical or different, represent a hydrogen atom, a halogen atom, such as bromine, chlorine, iodine or fluorine, a Ci- C₄ alkyl or Ci-C₄ alkoxy radical or a -CN radical,

> X^~ represents an anion preferably chosen from chloride, methyl sulphate and acetate,

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

B1 B2 B3

B4 B5 B6

in which Ri₆ represents a Ci-C₄ alkyl radical, and Ri7 and R18/ which are identical or different, represent a hydrogen atom or a Ci-C₄ alkyl radical;

iii) the compounds of following formulae (XII) and (XIII) : in which:

> Rig represents a hydrogen atom, a Ci-C₄ alkoxy radical, a halogen atom, such as bromine, chlorine, iodine or fluorine, or an amino radical,

> R20 represents a hydrogen atom or a Ci-C₄ alkyl radical or forms, with a carbon atom of the benzene ring, a heterocycle which optionally comprises oxygen and/or is substituted by one or more Ci-C₄ alkyl groups,

> R21 represents a hydrogen atom or a halogen atom, such as bromine, chlorine, iodine or fluorine,

> R22 and R23, which are identical or different, represent a hydrogen atom or a Ci-C₄ alkyl radical,

^ Di and D2, which are identical or different, represent a nitrogen atom or the -CH group,

> m represents 0 or 1, it being understood that, when Ri₉ represents an unsubstituted amino group, then Di and D₂ simultaneously represent a -CH group and m = 0,

^ X^~ represents an anionic counterion preferably chosen from chloride, methyl sulphate and acetate,

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

E1

E6 E7 E8

i n wh i ch R ' represents a Ci-C₄ al kyl radical ;

when m represents 0 and when D₁ represents a nitrogen atom, then E can also denote a group of following structure E₉:

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

iv) the compounds of following formula (XIV)

in which: ^ Z and D, which are identical or different, represent a nitrogen atom or the -CH group, ^ R₇ and Rs, which are identical or different, represent a hydrogen atom; a Ci-C₄ alkyl radical which can be substituted by a -CN, -OH or -NH₂ radical or forms, with a carbon atom of the benzene ring, an optionally oxygen-comprising or nitrogen-comprising heterocycle which can be substituted by one or more Ci-C₄ alkyl radicals; or a 4 ' -aminophenyl radical,

^ Rg and R' 9, which are identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a Ci-C₄ alkyl radical, a Ci-C₄ alkoxy radical or an acetyloxy radical,

> X^~ represents an anionic counterion, preferably chosen from chloride, methyl sulphate and acetate,

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

*13 *14 A 15

l10

'16 *17

*18

*19

R 10

in which R₁₀, which are identical or different, represent a Ci-C₄ alkyl radical which can be substituted by a hydroxyl radical and Rn represents a Ci-C₄ alkoxy radical,

v) the dyes described in Patent Application EP 714 954, of formula (XV), (XVI) or (XVII):

A-N-Z₉-N- "AA₁₁ R₁ R₂

(XVII) in which:

> A and Ai are, independently of one another, the residues of formula:

> Z represents an aliphatic or aromatic diamine residue,

> Ri and R2 represent, independently of one another, a hydrogen atom or a Ci-C₄ alkyl group or can form, together with two nitrogen atoms to which they are attached and with Z or Z₂, a 5-, 6- or 7-membered ring,

^ X represents the residue of a link forming a bridge,

> n represents an integer 2, 3 or 4,

> Zi represents an aromatic diamine residue,

> Z₂ represents an aliphatic diamine residue,

> KK represents a coupler compound residue, ^ R3 and R₄ represent, independently of one another, a hydrogen atom or a Ci-C₄ alkyl group,

> R₅ and Re represent, independently of one another, a hydrogen atom, a Ci-C₄ alkyl group or a Ci-C₄ alkoxy group, > An^" represents an anionic counterion which is preferably colourless.

and the cationic dyes described in Patent Applications

WO 95/01772, WO 95/15144, EP 714 954, EP 1 170 000, EP 1 166 753, EP 1 166 754 and EP 1 170 001, other than the above dyes. The passage in these applications devoted to cationic dyes is incorporated in the present patent application.

Preferably, use will be made of the dyes Basic Red 51 of formula (XVIII) :

Basic Yellow 87 of formula (XIX)

and Basic Orange 31 of formula (XX) :

Mention may be made, as examples of dyes possessing an endocyclic cationic charge according to the invention, of the following dyes:

- cationic dyes possessing xanthene rings, such as Basic Red 1, Basic Red 3, Basic Red 4, Basic Violet 10 and Basic Violet 11; - cationic dyes possessing acridine rings, such as Basic Orange 15, Basic Orange 16 and Basic Orange 17;

- cationic dyes possessing benzothiazole rings, such as Basic Blue 41 and Basic Blue 67; - cationic dyes possessing phenothiazine rings, such as Basic Blue 9;

- cationic dyes possessing triazole rings, such as Basic Red 22 and Basic Red 46;

- cationic dyes possessing thiazole rings, such as Bas ic Red 2 9 ;

- cationic dyes possessing phenazine rings, such as Basic Red 2 ;

- cationic dyes possessing indolenine rings, such as Basic Red 14, Basic Yellow 13, Basic Yellow 28 and

Basic Yellow 29;

- cationic dyes possessing phenoxazine rings, such as Basic Blue 6.

The azo, methine or azomethine direct dye or dyes possessing an endocyclic cationic charge according to the invention preferably represent from 0.0001 to 20% by weight approximately of the total weight of the dyeing composition and more particularly still from 0.001 to 10% by weight approximately of this weight. Very advantageously, the direct dye or dyes possessing an endocyclic cationic charge represent from 0.01 to 5% by weight approximately of the total weight of the dyeing composition.

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

According to a specific embodiment of the invention, the ammonium salt of formula (I) comprises an R group representing an alkyl group comprising between 8 and 40 carbon atoms and m is an integer of between 3 and 25 inclusive, advantageously between 10 and 20. More advantageously, the ammonium salt of formula (I) does not have an R radical resulting from anteiso-lanoleic acid.

The ammonium salt of formula (I) particularly comprises an R₃ group which represents an alkyl group comprising less than 12 carbon atoms, particularly from 1 to 6 carbon atoms; by way of example, R₃ represents a methyl group; and Ri and R2 particularly represent an alkyl or alkoxy group comprising from 1 to 8 carbon atoms, such as ethoxy, polyethoxy, propoxy, polypropoxy or methyl.

Another alternative form relates to the ammonium salt of formula (I) comprising a group Y representing an alkoxy group, such as ethoxy, polyethoxy, propoxy or polypropoxy, or an alkyl group comprising from 1 to 6 carbon atoms. According to a specific embodiment, Y represents an ethyl group.

Q^~ represents the anionic counterion of the ammonium salt of formula (I) which can be chosen from halides, alkyl sulphates, such as methyl sulphate and ethyl sulphate, alkoxy sulphates, such as methoxy sulphate and ethoxy sulphate, phosphates, lactate, citrate and acetate.

According to a specific embodiment, the ammonium salt of formula (I) is 18MEA in quaternized form which comprises an R group originating from 18- methyleicosanoic acid, i.e. R₃ is a methyl and m has the value 15.

The term "18MEA in quaternized form" implies a quaternary ammonium salt derived from methyleicosanoic fatty acid (MethylEicosanoic Acid - 18MEA) .

Such a compound 18MEA in quaternized form is sold by Croda (Incroquat Behenyl 18MEA) . More particularly, 18MEA in quaternized form corresponds to the quaternized derivatives of methyleicosanoic acid of Cio~ C40 isoalkylamidopropylethyldimonium methosulphate R- C(O)-NH-(CH₂)S-N⁺(Me)₂Et CH₃CH₂-OSO₃ ^" with R representing the following alkyl group: CH₃CH₂-CH (CH₃) -CH₂- (CH₂) ₁₅- .

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

The ammonium salt of formula (I) above occurs in the composition of the invention in an amount of between 0.001 and 2% by weight, with respect to the total weight of the composition, particularly between 0.01 and 1%. Advantageously, the ammonium salt occurs in the composition in an amount of between 0.02 and 0.4%.

The dyeing composition can additionally comprise direct dyes other than anionic acid direct dyes or cationic direct dyes possessing an endocyclic cationic charge. These other direct dyes of use according to the invention are chosen, for example, from neutral or cationic nitro direct dyes, neutral or cationic azo direct dyes, neutral or cationic azomethine dyes, neutral or cationic quinone and in particular anthraquinone direct dyes, neutral or cationic azine direct dyes, cationic triarylmethane direct dyes, neutral or cationic indoamine direct dyes and natural or anionic direct dyes and cationic direct dyes possessing an exocyclic cationic charge.

Mention may be made, among benzene direct dyes, without implied limitation, of the following compounds: 1, 4-diamino-2-nitrobenzene, l-amino-2-nitro-4- (β- hydroxyethylamino) benzene, l-amino-2-nitro-4- (bis (β- hydroxyethyl) amino) benzene, 1, 4-bis (β-hydroxyethyl- amino) -2-nitrobenzene, 1- (β-hydroxyethylamino) -2-nitro- 4- (bis (β-hydroxyethyl) amino) benzene, 1- (β-hydroxyethylamino) -2-nitro-4-aminobenzene, 1- (β-hydroxyethylamino) - 2-nitro-4- (ethyl (β-hydroxyethyl) amino) benzene, 1-amino- 3-methyl-4- (β-hydroxyethylamino) -6-nitrobenzene, 1- amino-2-nitro-4- (β-hydroxyethylamino) -5-chlorobenzene, 1, 2-diamino-4-nitrobenzene, l-amino-2- (β-hydroxyethylamino) -5-nitrobenzene, 1, 2-bis (β-hydroxyethylamino) -4-nitrobenzene, l-amino-2-tris (hydroxylmethyl) - methylamino-5-nitrobenzene, l-hydroxy-2-amino-5-nitro- benzene, l-hydroxy-2-amino-4-nitrobenzene, l-hydroxy-3- nitro-4-aminobenzene, l-hydroxy-2-amino-4, 6-dinitro- benzene, 1- (β-hydroxyethyloxy) -2- (β-hydroxyethylamino) - 5-nitrobenzene, l-methoxy-2- (β-hydroxyethylamino) -5- nitrobenzene, 1- (β-hydroxyethyloxy) -3-methylamino-4- nitrobenzene, 1- (β,γ-dihydroxypropyloxy) -3-methylamino-

4-nitrobenzene, 1- (β-hydroxyethylamino) -4- (β,γ- dihydroxypropyloxy) -2-nitrobenzene, 1- (β,γ-dihydroxy- propylamine) -4-trifluoromethyl-2-nitrobenzene, 1- (β- hydroxyethylamino) -4-trifluoromethyl-2-nitrobenzene, 1-

(β-hydroxyethylamino) -3-methyl-2-nitrobenzene, 1- (β- aminoethylamino) -5-methoxy-2-nitrobenzene, l-hydroxy-2- chloro-6-ethylamino-4-nitrobenzene, 1-hydroxy-2-chloro- 6-amino-4-nitrobenzene, l-hydroxy-6- (bis (β-hydroxy- ethyl) amino) -3-nitrobenzene, 1- (β-hydroxyethylamino) -2- nitrobenzene and l-hydroxy-4- (β-hydroxyethylamino) -3- nitrobenzene .

Mention may also be made, among azo direct dyes, of the following dyes, described in the Colour Index International, 3^rd edition:

Acid Yellow 9, Acid Black 1, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Acid Yellow 23 and Acid Orange 24.

Mention may also be made of 1- (4 ' -aminodiphenylazo) -2- methyl-4- (bis (β-hydroxyethyl) amino) benzene and 4- hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulphonic acid.

Mention may thus be made, among additional azo, methine or azomethine direct dyes, of the following dyes, described in the Colour Index International, 3^rd edition:

Disperse Red 17, Disperse Orange 3, Disperse Black 9, Basic Red 76, Basic Yellow 57, Basic Brown 16, Basic Brown 17, Basic Red 51, Basic Orange 31 and Basic Yellow 87.

Mention may be made, among quinone direct dyes, of the following dyes:

Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7, Basic Blue 22 and Disperse Violet 15; and of the following compounds: l-aminopropylamino-4- (methylamino) anthraquinone,

1- (aminopropylamino) anthraquinone, 5- (β-hydroxyethyl) - 1, 4-diaminoanthraquinone, 2- (aminoethylamino) anthraquinone and 1 , 4-bis (β, γ-dihydroxypropylamino) anthraquinone .

Mention may be made, among quinone direct dyes, of the following dyes:

Basic Blue 22, Disperse Violet 4, Disperse Blue 1, Disperse Violet 1, Disperse Blue 3, Disperse Blue 7 and Basic Blue 99.

Mention may be made, among additional azine dyes, of the compounds Basic Blue 17 and Basic Red 2.

Mention may be made, among additional triarylmethane dyes, of the following compounds:

Basic Green 1, Basic Violet 3, Basic Violet 14, Basic Blue 7 and Basic Blue 26.

Mention may be made, among additional indoamine dyes, of the following compounds:

2- (β-hydroxyethylamino) -5-{4 ' - [bis (β- hydroxyethyl) amino] anilino } -1 , 4-benzoquinone; 2- (β-hydroxyethylamino) -5- (2 ' -methoxy-4 ' - aminoanilino) -1, 4-benzoquinone;

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

3- (N- (3'-chloro-4'- (methylamino) phenyl) ureido) -6- methyl-1 , 4-benzoquinone imine; - 3- [4 ' -N- (ethyl, carbamylmethyl) -amino] -phenyl- ureido-6-methyl-l , 4-benzoquinone imine .

Mention may be made, among additional natural direct dyes which can be used according to the invention, of lawsone, juglone, alizarin, purpurin, purpurogallin, protocatechualdehyde, indigo, isatin, curcumin, spinulosin or apigenidin. Use may also be made of the extracts or decoctions comprising these natural dyes and in particular cataplasms or henna-based extracts.

The additional direct dye or dyes particularly represent from 0.001 to 20% by weight approximately of the total weight of the composition and preferably from 0.005 to 10% by weight approximately. More particularly, the additional direct dye or dyes represent from 0.01 to 5% by weight.

The composition of the present invention can furthermore comprise oxidation bases and couplers conventionally used for colouring by oxidation.

Mention may be made, by way of example, of para- phenylenediamines, bisphenylalkylenediamines, para- aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

The couplers are, for example, meta-phenylenediamine couplers, meta-aminophenol couplers, meta-diphenol couplers, naphthalene couplers, heterocyclic couplers, and their addition salts.

The oxidizing agent of use in the oxidation colouring is preferably chosen from hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates or ferrocyanides, or persalts, such as perborates and persulphates . The use of hydrogen peroxide is particularly preferred. Use may also be made, as oxidizing agent, of one or more oxidation/reduction enzymes, such as laccases, peroxidases and 2-electron oxidoreductases, such as uricase, if appropriate in the presence of their respective donor or cofactor.

When they are present, the bases and couplers are each generally present in an amount of between 0.001 and 10% by weight approximately of the total weight of the dyeing composition, preferably between 0.005 and 6%.

The composition according to the invention can additionally comprise at least one compound of ceramide type.

Ceramides or their analogues are known to protect and/or repair the skin and/or hair fibres from the attacks of the various agents and treatments mentioned above. In particular, they have a barrier effect which limits the escape of proteins and they also strengthen cuticular cohesion. A description has been given, for example, in Patent Applicatoin WO 00/44345 of a means for improving cosmetic properties, such as disentangling of the hair, by the application of a composition comprising a compound of ceramide type, such as N-oleoyldihydrosphingosine, in combination with a hydrogenated sunflower wax and behenyl- trimethylammonium chloride in water.

According to the present invention, the term "compound of ceramide type" is understood to mean ceramides and/or glycoceramides and/or pseudoceramides and/or neoceramides, which may be natural or synthetic, of formula (XXI) below.

Compounds of ceramide type are described, for example, in Patent Applications DE4424530, DE4424533, DE4402929, DE4420736, WO 95/23807, EP-A-O 646 572, WO 95/16665, FR-2 673 179, EP-A-O 227 994, WO 94/07844, WO 94/24097 and WO 94/10131, the teachings of which are included here by way of reference.

The compounds of ceramide type which can be used according to the present invention correspond to the following general formula (XXI) : ich formula (XXI) :

^■ Ri₄ denotes: i) a saturated or unsaturated and linear or branched Ci-C₅₀, preferably C₅-C₅₀, hydrocarbon radical, it being possible for this radical to be substituted by one or more hydroxyl groups optionally esterified by an acid Ri₉COOH, with Ri₉ being a saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated Ci- C₃₅ hydrocarbon radical, it being possible for the hydroxyl group or groups of the R_i9 radical to be esterified by a saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated Ci-C₃₅ fatty acid; ii) an R' '- (NR-CO) _q-R' radical, with R denoting a hydrogen atom or a mono- or polyhydroxylated, preferably monohydroxylated, Ci-C₂₀ hydrocarbon radical; R' and R" are hydrocarbon radicals, the sum of the carbon atoms of which is between 9 and 30, R' being a divalent radical; q denotes 0 or 1; or iii) an R₂₀-O-CO-(CH₂) radical; R₂₀ denotes a Ci-C₂₀ hydrocarbon radical and p is an integer of from 1 to 12 inclusive;

^■ Ri₅ is chosen from a hydrogen atom, a radical of saccharide type, in particular a (glycosyl) _n, (galactosyl) or sulphogalactosyl radical, a sulphate or phosphate residue, a phosphorylethylamine radical and a phosphorylethylammonium radical, in which n is an integer of between 1 and 4 inclusive and m is an integer of between 1 and 8 inclusive;

^■ Ri6 denotes a saturated or unsaturated and hydroxylated or nonhydroxylated Ci-C₃₃ hydrocarbon radical, it being possible for the hydroxyl group or groups to be esterified by an inorganic acid or an acid R19COOH, R19 having the same meanings as above, and it being possible for the hydroxyl group or groups to be etherified by a (glycosyl) , (galactosyl) , sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium radical, it also being possible for Ri₆ to be substituted by one or more Ci-Ci₄ alkyl radicals; preferably, Ri₆ denotes a C15-C26 α-hydroxyalkyl radical, the hydroxyl group optionally being esterified by a C16-C30 α-hydroxy acid; ■ Ri₇ denotes a hydrogen atom, a saturated or unsaturated, linear or branched, optionally hydroxylated, C3-C50 nonalkoxylated hydrocarbon radical, such as a methyl or ethyl radical, or an R₂I-O-CO-(CH₂) radical, R₂1 denotes a Ci-C₂₀ hydrocarbon radical and p is an integer varying from 1 to 12; in particular, Ri₇ represents a Cio~ C₂o alkyl group_; ■ Riβ denotes a hydrogen atom or a saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated, C1-C30 hydrocarbon radical, it being possible for the hydroxyl group or groups to be etherified by a (glycosyl) , (galactosyl) , sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium radical; particularly, Rig represents a hydrogen atom.

Preference is given, among the compounds of formula (XXI) , to the ceramides and/or glycoceramides with the structure described by Downing in Journal of Lipid

Research Vol. 35, 2060-2068, 1994, or those described in French Patent Application FR-2 673 179, the teachings of which are included here by way of reference.

The compounds of ceramide type more particularly preferred according to the invention are the compounds of formula (XXI) for which Ri₄ denotes an optionally hydroxylated alkyl or alkenyl derived from C14-C22 fatty acids; particularly, Ri₄ represents a C12-C20 alkenyl chain comprising one or two π double bonds, preferably one; Ri₅ denotes a hydrogen atom; and R16 denotes an optionally hydroxylated linear Cn-Ci₇ radical and preferably C13-C15 radical; more particularly, Ri₆ represents an alkyl group, such as methyl or ethyl, hydroxylated by one or more hydroxyl groups, preferably by one hydroxyl group.

Such compounds are, for example:

- 2-N-linoleoylaminooctadecane-l , 3-diol,

- 2-N-oleoylaminooctadecane-l, 3-diol,

- 2-N-palmitoylaminooctadecane-l , 3-diol, - 2-N-stearoylaminooctadecane-l, 3-diol,

- 2-N-behenoylaminooctadecane-l, 3-diol,

- 2-N- [2-hydroxypalmitoyl] aminooctadecane-1, 3- diol,

- 2-N-stearoylaminooctadecane-l, 3, 4-triol and in particular N-stearoylphytosphingosine,

- 2-N-palmitoylaminohexadecane-l, 3-diol, or the mixtures of these compounds.

Use may also be made of specific mixtures, such as, for example, the mixtures of ceramide(s) 2 and of ceramide(s) 5 according to the Downing classification.

Use may also be made of the compounds of formula (XXI) for which R_i4 denotes a saturated or unsaturated alkyl radical derived from C12-C22 fatty acids; Ri₅ denotes a galactosyl or sulphogalactosyl radical; and Ri₆ denotes a saturated or unsaturated C12-C22 hydrocarbon radical and preferably a CH (OH) -CH=CH- (CH₂) 12-CH3 group.

Mention may be made, by way of example, of the product composed of a mixture of glycoceramides sold under the trade name Glycocer by Waitaki International Biosciences . Use may also be made of the compounds of formula (XXI) described in Patent Applications EP-A-O 227 994 and WO 94/07844.

Such compounds are, for example, Questamide H (bis (N- hydroxyethyl-N-cetyl) malonamide) , sold by Quest.

Use may also be made of N-docosanoyl-N-methyl-D- glucamine, described in Patent Application WO 94/24097.

The concentration of compounds of ceramide type can vary between 0.0001% and 20% by weight approximately, with respect to the total weight of the composition, and from between 0.001 and 10% by weight approximately and more preferably still between 0.01 and 3% by weight .

The medium appropriate for dyeing, also known as dyeing vehicle, is generally composed of water or of a mixture of water and of at least one organic solvent in order to dissolve the compounds which would not be sufficiently soluble in water. Mention may be made, as organic solvent, for example, of lower Ci-C₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers, such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol monomethyl ether; and aromatic alcohols, such as benzyl alcohol or phenoxyethanol; and their mixtures.

The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately, with respect to the total weight of the dyeing composition, and more preferably still between 5 and 30% by weight approximately.

The dyeing composition in accordance with the invention can also include various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surface- active agents or their mixtures, other than the cationic surface-active agents of formula (I), anionic, cationic, nonionic, amphoteric or zwitterionic polymers or their blends, inorganic or organic thickening agents and in particular anionic, cationic, non-ionic and amphoteric polymeric associative thickeners, antioxidizing agents, penetration agents, sequestering agents, fragrances, buffers, dispersing agents, conditioning agents, such as, for example, volatile or non-volatile and modified or unmodified silicones, film-forming agents, ceramides, preserving agents or opacifying agents.

The composition according to the invention can also comprise one or more fatty alcohols: R""-OH, with R"" representing an alkyl or alkenyl group having from 8 to

30 carbon atoms, these fatty alcohols being introduced in the pure form or in the form of a mixture. Mention may more particularly be made, among them, of lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol and their mixtures.

The above adjuvants are generally present in an amount of, for each of them, between 0.01 and 20% by weight, with respect to the weight of the composition.

The pH of the dyeing composition in accordance with the invention is generally between 2 and 11.5 approximately and preferably between 6 and 11.5 approximately. It can be adjusted to the desired value by means of acidifying or basifying agents commonly used in dyeing keratinous fibres or alternatively using conventional buffering systems .

Mention may be made, among basifying agents, by way of example, of aqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines and their derivatives, hydroxyalkylamines, such as 2-amino-2-methylpropanol, and ethylenediamines which are oxyethylenated and/or oxypropylenated, sodium hydroxide, potassium hydroxide and the compounds of following formula (XXII) :

^R\

N—T N ₍XXIi₎

R^c R^d in which formula (XXII) :

T is a propylene residue optionally substituted by a hydroxyl group or a Ci-C₄ alkyl radical;

R^a, R^b, R^c and R^d, which are identical or different, represent a hydrogen atom or a Ci-C₄ alkyl or a Ci-C₄ hydroxyalkyl radical.

The acidifying agents are conventionally, by way of example, inorganic or organic acids, such as hydrochloric acid, orthophosphoric acid, carboxylic acids, such as tartaric acid, citric acid or lactic acid, or sulphonic acids.

The dyeing composition according to the invention can be provided in various formulation forms, such as in the liquid, lotion, cream or gel form or in any other form appropriate for carrying out dyeing of keratinous fibres .

It can also be packaged under pressure in an aerosol container in the presence of a propellant and form a mousse .

Another subject-matter of the present invention is a dyeing method starting from the composition described above.

According to a specific embodiment, this dyeing method according to the invention consists in applying the composition of the invention, in leaving it to act for a leave-in time preferably varying from 1 to 60 minutes approximately and more preferably from 10 to 45 minutes approximately, then rinsing the fibres, and then optionally washing them with a shampoo, then rinsing them again and then drying them.

A concrete example illustrating the invention is shown below without, however, exhibiting a limiting nature.

EXAMPLES

The following composition was prepared:

Colouring composition 1: (expressed as percentage by weight as is)

Colouring composition 2: (expressed as percentage by weight as is)

Mode of application

The dyeing shampoos (compositions 1 and 2) prepared in the proportions mentioned above are applied to permed grey hair comprising 90% of white hairs.

After a leave-in time of 30 minutes, the hair is rinsed and dried.

The hair coloured with these compositions exhibits good dyeing properties and a very good feel, in particular with regard to dry hair.

Claims

1. Composition for the dyeing of keratinous fibres, in particular human keratinous fibres, such as the hair, comprising, in a medium appropriate for dyeing: i) at least one direct dye chosen from anionic direct dyes and cationic direct dyes possessing an endocyclic cationic charge; and ii) at least one ammonium salt of formula (I) :

in which formula (I) :

■ 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 of between 1 and 6 inclusive;

2. Composition according to the preceding claim, in which the anionic direct dye is comprised within one of the following formulae (II), (H'), (III), (III¹), (IV), (IV), (V), (V), (VI), (VII), (VIII) and (IX) and their mesomeric or tautomeric forms:

in which formulae (II) and (II¹):

^■ R₇, R₈, R₉, Ri₀, R'₇, R's, R' 9 and R'io, which are identical or different, represent a hydrogen atom or a group chosen from:

- alkyl; - alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso;

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

(O)CO^"- M⁺, with M⁺ as defined above; R"-S(0)2~/ with R" representing a hydrogen atom, an alkyl group or 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 optionally substituted aryl or alkyl group and X' as defined above; (di) (alkyl) amino; - aryl (alkyl) amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)₂S(O^")- M⁺ and iv) alkoxy with M⁺ as defined above; optionally substituted heteroaryl; - cycloalkyl;

Ar-N=N-, with Ar representing an optionally substituted aryl group; or then two adjacent groups R₇ with R₈ or R₈ with R₉ or R₉ with Ri₀ together form a fused benzo group A'; and R'₇ with R'₈ or R'₈ with R'₉ or R'₉ with R'io together form a fused benzo group B'; with A' and B' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)₂S(O^")- M⁺; iv) hydroxyl; 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) optionally substituted aryl (alkyl) amino; with M⁺, R°, X, X', X" and Ar as defined above; " W represents a sigma σ bond, an oxygen or sulphur atom or a divalent radical i) -NR-, with R as defined above, or ii) methylene -C (R_a) (Rb)-, with R_a and R]₃, which are identical or different, representing a hydrogen atom or an aryl group, or then R_a and R_b form, together with the carbon atom which carries them, a spiro cycloalkyl; it being understood that the formulae (II) and (II¹) comprise at least one sulphonate radical (O)₂S(O-)- M⁺ or one carboxylate radical (O)CO^"- M⁺ on one of the A, A', B, B' or C rings; preferably sodium sulphonate;

in which formulae (III) and (III¹): ■ Rn, Ri₂ and R_i3, which are identical or different, represent a hydrogen or halogen atom or an alkyl or -(O)₂S(O^") M⁺ group, with M⁺ as defined above;

^■ Ri₄ represents a hydrogen atom, an alkyl group or a -C(O)O^" M⁺ group, with M⁺ as defined above;

^■ Ri₅ represents a hydrogen atom;

^■ Ri₆ represents an oxo group, in which case R'i6 is absent, or then R₁₅ with R_i6 together form a double bond; ■ Ri₇ and R_i8, which are identical or different, represent a hydrogen atom or a group chosen from: (O)₂S(O^")- M⁺, with M⁺ as defined above; Ar-O-S(O)₂-, with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups;

^■ Ri₉ and R₂₀ together form either a double bond or an optionally substituted benzo group D ' ;

^■ R'i6, R'i9 and R'20, which are identical or different, represent a hydrogen atom or an alkyl or hydroxyl group; ^■ R.21 represents a hydrogen atom or an alkyl or alkoxy group;

^■ R_a and Rb, which are identical or different, are as defined above;

^■ Y represents either a hydroxyl group or an oxo group;

it being understood that the formulae (III) and (III¹) comprise at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺ on either of the D or E rings;

in which formulae (IV) and (IV) :

^■ R₂₂, R23, R24, R25, R26 and R₂₇, which are identical or different, represent a hydrogen or halogen atom or a group chosen from: alkyl; hydroxyl, mercapto; alkoxy, alkylthio; - optionally substituted aryloxy or arylthio; aryl (alkyl) amino optionally substituted by one or more groups chosen 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 an NR₂₈R₂₉ group with R28 and R29, which are identical or different, representing a hydrogen atom or a group chosen from: alkyl; polyhydroxyalkyl, such as hydroxyethyl; aryl optionally substituted by one or more groups, particularly i) alkyl, such as methyl, n-dodecyl or n-butyl; ii) (O)₂S(O^")- M⁺, with M⁺ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)- or R°-X'-C (X) -X"-, with R°, X, X' and X" as defined above;

^■ Z represents a group chosen from hydroxyl and NR'₂₈R'₂9 with R'₂₈ and R'29, which are identical or different, representing the same atoms or groups as R₂₈ and R₂g as defined above;

it being understood that the formulae (IV) and (IV) comprise at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺; preferably sodium sulphonate;

in which formulae (V) and (V): ^■ R₃O, R-31 and R32, which are identical or different, represent a hydrogen or halogen atom or a group chosen from:

- alkyl; - alkoxy optionally substituted by one or more hydroxyl groups, alkylthio optionally substituted by one or more hydroxyl groups; hydroxyl, mercapto; nitro, nitroso; - polyhaloalkyl;

- R°-C(X)-X'-, R°-X'-C(X)- or 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 ;

^■ R_c and Rd, which are identical or different, represent a hydrogen atom or an alkyl group; ■ W is as defined above;

^■ ALK represents a divalent, linear or branched, Ci-Cβ alkylene group;

^■ n has the value 1 or 2;

^■ p represents an integer of between 1 and 5 inclusive;

^■ q represents an integer of between 1 and 4 inclusive;

^■ u has the value 0 or 1;

^■ when n has a value 1, J represents a nitro or nitroso group;

^■ when n has a value 2, J represents an oxygen or sulphur atom or a divalent radical -S(0)_m-, with m representing an integer 1 or 2;

^■ M' represents a hydrogen atom or a cationic counterion;

^■ , which is present or absent, represents a benzo group optionally substituted by one or more R30 groups as defined above; it being understood that the formulae (V) and (V) comprise at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺

in which formula (VI) :

^■ R₃₃, R₃₄, R₃₅ and R₃₆, which are identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl;

^■ R3₇/ R38 r R39/ R40/ R41/ R-42/ R43 and R44, which are identical or different, represent a hydrogen atom or a group chosen from: - alkyl; alkoxy, alkylthio; (di) (alkyl) amino; hydroxyl, mercapto; nitro, nitroso; - R°-C(X)-X'-, R°-X'-C(X)- or R° -X ' -C (X) -X"-, with R° representing a hydrogen atom or an alkyl or aryl group and X, X' and X", which are identical or different, representing an oxygen or sulphur atom or NR, with R representing a hydrogen atom or an alkyl group;

(O)CO^"- M⁺, with M⁺ as defined above; or then two adjacent groups R_4i with R₄₂ or R₄₂ with R₄₃ or R₄₃ with R₄₄ together form a fused benzo group: I'; with I' optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O)₂S(O^")- M⁺; iv) hydroxyl; 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' and X" as defined above; particularly, R₃₇ to R₄o represent a hydrogen atom and R41 to R44, which are identical or different, represent a hydroxyl or (O)₂S(O-)- M group; and, when R₄₃ with R₄₄ together form a benzo group, it is preferably substituted by an (O)₂S (0^") - group;

it being understood that at least one of the G, H, I or I ' rings comprises at least one sulphonate radical

(O)₂S(O )- or one carboxylate radical -C(O)O ;

in which formula (VII) :

^■ R45, R46, R₄₇ and R48, which are identical or different, represent a hydrogen atom or a halogen atom; ■ R49, R50, R51 and R52, which are identical or different, represent a hydrogen or halogen atom or a group chosen from: - alkyl; alkoxy, alkylthio; - hydroxyl, mercapto; nitro, nitroso;

(O)CO^"- M⁺, with M⁺ as defined above; particularly, R₅₃ R₅₄, R₅₅ and R₄₈ represent a hydrogen or halogen atom; ■ G represents an oxygen or sulphur atom or an NR_e group with R_e as defined above;

^■ L represents an alkoxide 0^~ M⁺; a thioalcoholate S^~ M⁺ or an NR_f group, with R_f representing a hydrogen atom or an alkyl group, and M⁺ as defined above;

■ L' represents an oxygen or sulphur atom or an ammonium group: N⁺R_fR_g, with R_f and R_g, which are identical or different, representing a hydrogen atom or an optionally substituted aryl or alkyl group;

^■ Q and Q¹ , which are identical or different, represent an oxygen or sulphur atom;

^■ M⁺ is as defined above;

ich formula (VIII) :

^■ R₅₃, R₅₄, R₅₅, R₅₆, R₅₇, R₅S, R59 and R₆₀, which are identical or different, represent a hydrogen atom or a group chosen from: alkyl; alkoxy, alkylthio; hydroxyl, mercapto; nitro, nitroso;

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

■ G represents an oxygen or sulphur atom or an NR_e group with R_e as defined above; ^■ R₁ and Rh, which are identical or different, represent a hydrogen atom or an alkyl group; it being understood that the formula (VIII) comprises at least one sulphonate radical (O)₂S(O^")- M⁺ or one carboxylate radical -C(O)O^" M⁺

in which formula (IX) :

^■ Rεi represents a hydrogen or halogen atom or an alkyl group;

^■ R₆2, Rδ3 and R₆₄, which are identical or different, represent a hydrogen atom or an

(O)₂S(O^")- M⁺ group, with M⁺ representing a hydrogen atom or a cationic counterion;

^■ or then Rεi with R₆2 or R₆i with R₆₄ together form a benzo group optionally substituted by one or more (O)₂S(O^")- M⁺ groups, with M⁺ representing a hydrogen atom or a cationic counterion; it being understood that the formula (IX) comprises at least one sulphonate radical (O)₂S(O^")- M⁺.

3. Composition according to Claim 1, in which the cationic direct dye possessing an endocyclic cationic charge is chosen from the formulae (X) to (XX) and their mesomeric or tautomeric forms:

i) the dyes of formula (X)

G-N=N-J (X) in which: - the symbol G represents a group chosen from the following structures Gi to G3 :

ich:

> R₂₅ denotes a Ci-C₄ alkyl radical or a phenyl radical; ^ R₂₆ and R₂₇, which are identical or different, represent a Ci-C₄ alkyl radical or a phenyl radical or together form, in Gi, a benzene ring substituted by one or more Ci-C₄ alkyl, Ci-C₄ alkoxy or NO₂ radicals or together form, in G₂, a benzene ring optionally substituted by one or more Ci-C₄ alkyl, Ci-C₄ alkoxy or NO₂ radicals;

> R₂₆ can additionally denote a hydrogen atom;

^ Z denotes an oxygen or sulphur atom or an -NR₂₅ group; > M represents a -CH, -CR (R denoting Ci-Cz alkyl) or -NR₂₈ (X^") _r group;

> K represents a -CH, -CR (R denoting Ci-Cz alkyl) or -NR₂₈ (X^") _r group;

> P represents a -CH, -CR (R denoting Ci-Cz alkyl) or -NR₂₈ (X^") _r group;

> r denotes zero or 1;

> R₂₈ represents an O^" atom, a Ci-C₄ alkoxy radical or a Ci-C₄ alkyl radical; > R₂9 and R30, which are identical or different, represent a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci- C4 alkyl radical, a C1-C4 alkoxy radical or an -NO2 radical;

^ X represents an anion preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate, acetate and perchlorate; he symbol J represents: a) a group of following structure Ji:

in which:

> R₃₁ represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a Ci-C₄ alkyl radical, a Ci-C₄ alkoxy radical or an -OH, -NO₂, -NHR₃₄, -NR₃₅R₃₆ or - NHCO (Ci-C₄) alkyl radical or forms, with R₃₂, a 5- or 6-membered ring comprising or not comprising one or more heteroatoms chosen from nitrogen, oxygen or sulphur;

^ or forms, with R₃₃ or R₃₄, a 5- or 6-membered ring comprising or not comprising one or more heteroatoms chosen from nitrogen, oxygen or sulphur; > R₃₃ represents a hydrogen atom, an -OH radical, an -NHR₃₄ radical or an -NR₃₅R₃₆ radical;

> R₃₄ represents a hydrogen atom, a Ci-C₄ alkyl radical, a Ci-C₄ monohydroxyalkyl radical, a C₂-C₄- polyhydroxyalkyl radical or a phenyl radical; > R₃₅ and R₃₆, which are identical or different, represent a Ci-C₄ alkyl radical, a Ci-C₄ monohydroxyalkyl radical or C₂-C₄ polyhydroxyalkyl radical;

J₂:

in which:

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

^ n represents 0 or 1 with, when n denotes 1, U denoting the -CO- radical;

ii) of following formula (XI) :

in which:

> R12 represents a hydrogen atom or a Ci-C₄ alkyl radical,

> Ri₃ represents a hydrogen atom, an alkyl radical which can be substituted by a -CN radical or by an amino group, or a 4'- aminophenyl radical or forms, with Ri₂, an optionally oxygen-comprising and/or nitrogen- comprising heterocycle which can be substituted by a Ci-C₄ alkyl radical,

> Ri₄ and Ri₅, which are identical or different, represent a hydrogen atom, a halogen atom, such as bromine, chlorine, iodine or fluorine, a Ci-

C₄ alkyl or Ci-C₄ alkoxy radical or a -CN radical,

^ X^~ represents an anion preferably chosen from chloride, methyl sulphate and acetate,

^ B represents a group chosen from the following structures Bi to B₆:

B1 B2 B3

B4 B5 B6

in which Ri₆ represents a Ci-C₄ alkyl radical, and Ri₇ and Ri₈, which are identical or different, represent a hydrogen atom or a Ci-C₄ alkyl radical;

iii) the compounds of following formulae (XII) and (XIII) :

(XIII) in which :

^ R22 and R23, which are identical or different, represent a hydrogen atom or a Ci-C₄ alkyl radical,

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

> X^~ represents an anion preferably chosen from chloride, methyl sulphate and acetate, > E represents a group chosen from the following structures Ei to E₈:

E6 E7 E8

i n wh i ch R ' represents a Ci-C₄ al kyl radical ;

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

iv) the compounds of following formula (XIV) :

in which:

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

> R₇ and Rs, which are identical or different, represent a hydrogen atom; a Ci-C₄ alkyl radical which can be substituted by a -CN, -OH or -NH₂ radical or forms, with a carbon atom of the benzene ring, an optionally oxygen-comprising or nitrogen-comprising heterocycle which can be substituted by one or more Ci-C₄ alkyl radicals; or a 4 ' -aminophenyl radical,

> R₉ and R' 9, which are identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical, a Ci-C₄ alkyl radical, a Ci-C₄ alkoxy radical or an acetyloxy radical,

^ X^~ represents an anion, preferably chosen from chloride, methyl sulphate and acetate,

^ A represents a group chosen from the following structures Ai to Ai₉:

*13 *14 A 15

l10

^16 *17

*18

*19

R 10

the dyes of formula (XV) , (XVI) or (XVII) :

A-N-Z₉-N-A₁ R₁ R₂

(XVII) in which:

> A and Ai are, independently of one another, the residues of formula:

> Z represents an aliphatic or aromatic diamine residue,

^ X represents the residue of a link forming a bridge,

> n represents an integer 2, 3 or 4,

> Zi represents an aromatic diamine residue,

> Z₂ represents an aliphatic diamine residue,

> R₅ and Re represent, independently of one another, a hydrogen atom, a Ci-C₄ alkyl group or a Ci-C₄ alkoxy group, > An^" represents a colourless anion.

4. Composition according to any one of the preceding claims, in which the cationic direct dye possessing an endocyclic cationic charge is chosen from the formulae (XVIII), (XIX) and (XX):

5. Composition according to any one of the preceding claims, in which the anionic direct dye or dyes or the cationic direct dye or dyes possessing an endocyclic cationic charge are present in an amount of from 0.001 to 20% by weight approximately of the total weight of the composition to be confirmed.

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

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

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

9. Composition according to any one of the preceding claims, in which the ammonium salt of formula (I) comprises an R group in which R₃ represents a methyl and m has the value 15.

10. Composition according to any one of the preceding claims, in which the ammonium salt of formula (I) is a quaternized derivative of methyleicosanoic acid of Ci₀- C40 isoalkylamidopropylethyldimonium methosulphate .

11. Composition according to any one of the preceding claims, in which the ammonium salt of formula (I) occurs in the composition of the invention in an amount of between 0.001 and 2% by weight, with respect to the total weight of the composition.

12. Composition according to any one of the preceding claims, which additionally comprises at least one compound of ceramide type.

13. Composition according to the preceding claim, in which the compound of ceramide type is of formula

(XXI) :

in which formula (XXI ) :

^■ Ri₄ denotes : i) a saturated or unsaturated and linear or branched Ci-C₅₀, preferably C₅-C₅₀, hydrocarbon radical, it being possible for this radical to be substituted by one or more hydroxyl groups optionally esterified by an acid Ri₉COOH, with R₁₉ being a saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated C₁- C₃₅ hydrocarbon radical, it being possible for the hydroxyl group or groups of the R₁₉ radical to be esterified by a saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated C1-C35 fatty acid; ii) an R' '- (NR-CO) _q-R' radical, with R denoting a hydrogen atom or a mono- or polyhydroxylated, preferably monohydroxylated, C1-C20 hydrocarbon radical; R' and R" are hydrocarbon radicals, the sum of the carbon atoms of which is between 9 and

30, R'' being a divalent radical; q denotes 0 or 1; or iii) an R₂O-O-CO-(CH₂) radical; R₂o denotes a Ci-C₂O hydrocarbon radical and p is an integer of from 1 to 12 inclusive;

^■ Ri₅ is chosen from a hydrogen atom, a radical of saccharide type, in particular a (glycosyl) _n,

(galactosyl) or sulphogalactosyl radical, a sulphate or phosphate residue, a phosphorylethylamine radical and a phosphorylethylammonium radical, in which n is an integer of between 1 and 4 inclusive and m is an integer of between 1 and 8 inclusive;

^■ Ri6 denotes a saturated or unsaturated and hydroxylated or nonhydroxylated C1-C33 hydrocarbon radical, it being possible for the hydroxyl group or groups to be esterified by an inorganic acid or an acid R19COOH, R19 having the same meanings as above, and it being possible for the hydroxyl group or groups to be etherified by a (glycosyl) , (galactosyl) , sulphogalactosyl, phosphorylethyl- amine or phosphorylethylammonium radical, it also being possible for Ri₆ to be substituted by one or more Ci-Ci₄ alkyl radicals; preferably, Ri₆ denotes a Ci₅-C₂₆ α-hydroxyalkyl radical, the hydroxyl group optionally being esterified by a Ci₆-C3o α-hydroxy acid;

^■ Ri₇ denotes a hydrogen atom, a saturated or unsaturated, linear or branched, optionally hydroxylated, C3-C50 nonalkoxylated hydrocarbon radical, such as a methyl or ethyl radical, or an R₂I-O-CO-(CH₂) radical, R₂1 denotes a Ci-C₂₀ hydrocarbon radical and p is an integer varying from 1 to 12;

^■ Riβ denotes a hydrogen atom or a saturated or unsaturated, linear or branched, optionally mono- or polyhydroxylated, C1-C30 hydrocarbon radical, it being possible for the hydroxyl group or groups to be etherified by a (glycosyl) , (galactosyl) , sulphogalactosyl, phosphorylethylamine or phosphorylethylammonium radical.

14. Composition according to the preceding claim, in which the compound of ceramide type is of formula (XXI) in which Ri₄ denotes a Ci₂-C₂O alkenyl chain comprising one or two π double bonds; Ri₅ denotes a hydrogen atom; R16 denotes an optionally hydroxylated linear Cn-Ci₇ radical; Ri₇ represents a Cio-C₂o alkyl group and Rig represents a hydrogen atom.

15. Composition according to any one of Claims 12 to

14, in which the compound of ceramide type is chosen from:

- 2-N-linoleoylaminooctadecane-l, 3-diol,

- 2-N-oleoylaminooctadecane-l, 3-diol, - 2-N-palmitoylaminooctadecane-l, 3-diol,

- 2-N-stearoylaminooctadecane-l, 3-diol,

- 2-N-behenoylaminooctadecane-l, 3-diol,

- 2-N- [2-hydroxypalmitoyl ] aminooctadecane-1, 3- diol, - 2-N-stearoylaminooctadecane-l, 3, 4-triol and in particular N-stearoylphytosphingosine,

- 2-N-palmitoylaminohexadecane-l , 3-diol, or the mixtures of these compounds.

16. Composition according to any one of Claims 12 to

15, in which the concentration of compounds of ceramide type can vary between 0.0001% and 20% by weight approximately, with respect to the total weight of the composition .

17. Method for dyeing keratinous fibres and in particular human keratinous fibres, such as the hair, which consists in applying, to the fibres, a composition as defined in any one of the preceding claims .

18. Use of a combination comprising i) at least one direct dye chosen from anionic direct dyes as defined in Claim 1 or Claim 2 and cationic direct dyes as defined in Claim 3 or Claim 4; and ii) at least one ammonium salt of formula (I) as defined in any one of Claims 1 and 6 to 10; for the colouring of keratinous fibres and in particular of human keratinous fibres, such as the hair.