Composition for dyeing keratinous fibres with a cationic direct dye and an anionic surfactant

Abstract

The invention relates to a composition for dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in an appropriate dyeing medium, at least one cationic direct dye of a given formula, and which is characterized in that it contains, in addition, at least one anionic surfactant chosen from the group consisting of acyl isethionates, acyl taurates, sulphosuccinates, acyl sarcosinates, acyl glutamates, polyoxyalkylenated ether carboxylic acids and their salts, fatty glucamide sulphates, alkyl galactoside uronates, anionic derivatives of alkyl polyglucosides and mixtures thereof.

Description

[0001] The invention relates to a composition for dyeing keratinous fibres, in particular human keratinous fibres such as hair, comprising, in an appropriate dyeing medium, at least one cationic direct dye of a given formula, and at least one particular anionic surfactant.

[0002] The subject of the invention is also the dyeing methods and devices using the said composition.

[0003] In the hair domain, it is possible to distinguish two types of dyeing.

[0004] The first is the semipermanent or temporary dyeing, or direct dyeing, which involves dyes capable of bringing the natural colour of the hair a more or less marked colour modification which is resistant, where appropriate, to several shampooings. These dyes are called direct dyes; they can be used with or without oxidizing agent. In the presence of oxidizing agent, the aim is to obtain a lightening dyeing. Lightening dyeing is performed by applying to the hair the fresh mixture of a direct dye and of an oxidizing agent and makes it possible in particular to obtain, by lightening of the melanin of the hair, an advantageous effect such as a uniform colour in the case of grey hair or to make the colour stand out in the case of naturally pigmented hair.

[0005] The second is permanent dyeing or oxidation dyeing. The latter is performed with so-called “oxidation” dyes comprising oxidation dye precursors and couplers. The oxidation dye precursors, commonly called “oxidation bases” are compounds which are initially colourless or faintly coloured which develop their dyeing power inside the hair in the presence of oxidizing agents added at the time of use, leading to the formation of coloured and dyeing compounds. The formation of these coloured and dyeing compounds results either-from an oxidative condensation of the “oxidation bases” with themselves, or an oxidative condensation of the “oxidation bases” with colour modifying compounds commonly called “couplers” and generally present in the dyeing compositions used in oxidation dyeing.

[0006] To vary the shades obtained with the said oxidation dyes, or to increase their shimmer, direct dyes are sometimes added to them.

[0007] Among the cationic direct dyes available in the field of dyeing of keratinous fibres, especially human keratinous fibres, compounds are already known whose. structure is developed in the text which follows; nevertheless, these dyes lead to colours which exhibit characteristics which are still inadequate from the point of view of the intensity and homogeneity of the colour distributed along the fibre; it is said, in this case, that the colour is too selective, and from the point of view of fastness, in terms of resistance to various attacks to which the hair may be subjected (light, adverse weather conditions, shampooings).

[0008] However, after major research studies carried out on this question, the applicant has just now discovered that it is possible to obtain novel compositions for dyeing keratinous fibres which are capable of giving intense and only slightly selective colours which are quite resistant nevertheless to the various attacks to which the hair may be subjected, by combining at least one particular anionic surfactant with at least one cationic direct dye known in the prior art and which have the respective formulae defined hereinafter.

[0009] This discovery forms the basis of the present invention.

[0010] The first subject of the present invention is therefore a composition for dyeing keratinous fibres and in particular human keratinous fibres such as hair, containing in an appropriate dyeing medium, (i) at least one cationic direct dye whose structure corresponds to the formulae (I) to (IV) defined hereinafter, characterized in that it contains in addition (ii) at least one particular anionic surfactant.

[0011] (i) The cationic direct dye which can be used according to the present invention is a compound chosen from those of the following formulae (I), (II), (III), (III′), (IV):

[0012] a) the compounds of the following formula (I): 1

[0013] in which:

[0014] D represents a nitrogen atom or the —CH group,

[0015] R1 and R2, which are identical or different, represent a hydrogen atom; a C1-C4 alkyl radical which may be substituted with a —CN, —OH or —NH2 radical or form with a carbon atom of the benzene ring an optionally oxygen-containing or nitrogen-containing heterocycle which may be substituted with one or more C1-C4 alkyl radicals; a 4′-aminophenyl radical,

[0016] R3 and R′3, which are identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano, C1-C4 alkyl, C1-C4 alkoxy or acetyloxy radical,

[0017] X− represents an anion which is preferably chosen from chloride, methylsulphate and acetate,

[0018] A represents a group chosen from the following structures A1 to A19: 2 3

[0019] in which R4 represents a C1-C4 alkyl radical which may be substituted with a hydroxyl radical and R5 represents a C1-C4 alkoxy radical, with the proviso that when D represents —CH, A represents A4 or A13 and R3 is different from an alkoxy radical, then R1 and R2 do not simultaneously denote a hydrogen atom;

[0020] b) the compounds of the following formula (II): 4

[0021] in which:

[0022] R6 represents a hydrogen atom or a C1-C4 alkyl radical,

[0023] R7 represents a hydrogen atom, an alkyl radical which may be substituted with a —CN radical or with an amino group, a 4′-aminophenyl radical or forms with R6 an optionally oxygen-containing and/or nitrogen-containing heterocycle which may be substituted with a C1-C4 alkyl radical,

[0024] R8 and R9, which are identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, a —CN radical,

[0025] X− represents an anion which is preferably chosen from chloride, methylsulphate and acetate,

[0026] B represents a group chosen from the following structures B1 to B6: 5

[0027] in which R10 represents a C1-C4 alkyl radical, R11 and R12, which are identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;

[0028] c) the compounds of the following formulae (III) and (III′): 6

[0029] in which:

[0030] R13 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical,

[0031] R14 represents a hydrogen atom, a C1-C4 alkyl radical or forms with a carbon atom of the benzene ring a heterocycle which is optionally oxygen-containing and/or substituted with one or more C1-C4 alkyl groups,

[0032] R15 represents a hydrogen or halogen atom such as bromine, chlorine, iodine of fluorine,

[0033] R16 and R17, which are identical or different, represent a hydrogen atom or a C1-C4 alkyl radical,

[0034] D1 and D2, which are identical or different, represent a nitrogen atom or the —CH group,

[0035] m=0 or 1, it being understood that when R13 represents an unsubstituted amino group, then D1 and D2 simultaneously represent a —CH group and m=0,

[0036] X− represents an anion which is preferably chosen from chloride, methylsulphate and acetate,

[0037] E represents a group chosen from the following structures E1 to E8: 7

[0038] in which R′ represents a C1-C4 alkyl radical;

[0039] when m=0 and D1 represents a nitrogen atom, then E may also denote a group having the following structure E9: 8

[0040] in which R′ represents a C1-C4 alkyl radical,

[0041] d) the compounds of the following formula (IV):

G—N══N—J  (IV)

[0042] in which:

[0043] the symbol G represents a group chosen from the following structures G1 to G3: 9

[0044] in which structures G1 to G3,

[0045] R18 denotes a C1-C4 alkyl radical, a phenyl radical which may be substituted with a C1-C4 alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine;

[0046] R19 denotes a C1-C4 alkyl radical or a phenyl radical;

[0047] R20 and R21, which are identical or different, represent a C1-C4 alkyl radical, a phenyl radical, or form together in G1 a benzene ring which is substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals, or form together in G2 a benzene ring which is optionally substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals;

[0048] R20 may denote, in addition, a hydrogen atom;

[0049] Z denotes an oxygen or sulphur atom or an —NR19 group;

[0050] M represents a group —CH, —CR (R denoting C1-C4 alkyl), or —NR22(X−)r;

[0051] K represents a group —CH, —CR (R denoting C1-C4 alkyl), or —NR22(X−)r;

[0052] P represents a group —CH, —CR (R denoting C1-C4 alkyl), or —NR22(X−)r; r denotes zero or 1;

[0053] R22 represents an O− atom, a C1-C4 alkoxy radical or a C1-C4 alkyl radical;

[0054] R23 and R24, which are identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, a C1-C4 alkoxy radical or an —NO2 radical;

[0055] X− represents an anion which is preferably chosen from chloride, iodide, methylsulphate, ethylsulphate, acetate and perchlorate;

[0056] with the proviso that

[0057] if R22 denotes O−, then r denotes zero;

[0058] if K or P or M denote —N—(C1-C4 alkyl)X−, then R23 or R24 is different from a hydrogen atom;

[0059] if K denotes —NR22(X−)r′, then M=P=—CH, —CR;

[0060] if M denotes —NR22(X−)r, then K=P=—CH, —CR;

[0061] if P denotes —NR22(X−)r, then K=M and denote —CH or —CR;

[0062] if Z denotes a sulphur atom with R21 denoting C1-C4 alkyl, then R20 is different from a hydrogen atom;

[0063] if Z denotes —NR22 with R19 denoting C1-C4 alkyl, then at least one of the R18, R20 or R21 radicals of the group having the structure G2 is different from a C1-C4 alkyl radical;

[0064] the symbol J represents:

[0065] (a) a group having the following structure J1: 10

[0066] in which structure J1,

[0067] R25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a radical —OH, —NO2, —NHR28, —NR29R30, —NHCO(C1-C4alkyl), or forms with R26 a 5- or 6-membered ring containing or otherwise one or more heteroatoms chosen from nitrogen, oxygen or sulphur;

[0068] R26 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, or forms with R27 or R28 a 5- or 6-membered ring containing or otherwise one or more heteroatoms chosen from nitrogen, oxygen or sulphur;

[0069] R27 represents a hydrogen atom, an —OH radical, an —NHR28 radical, an —NR29R30 radical;

[0070] R28 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a phenyl radical;

[0071] R29 and R30, which are identical or different, represent a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical;

[0072] (b) a 5- or 6- membered nitrogen-containing heterocycle group which is capable of containing other heteroatoms and/or carbonyl-containing groups and which may be substituted with one or more C1-C4 alkyl, amino or phenyl radicals,

[0073] and in particular a group having the following structure J2: 11

[0074] in which structure J2,

[0075] R31 and R32, which are identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, a phenyl radical;

[0076] Y denotes the —CO— radical or the radical 12

[0077] n=0 or 1, with, when n denotes 1, U denotes the —CO— radical.

[0078] In the structures (I) to (IV) defined above, the C1-C4 alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.

[0079] The cationic direct dyes of formulae (I), (II), (III) and (III′) which can be used in the dyeing compositions in accordance with the invention are known compounds which are described, for example, in patent applications WO 95/01772, WO 95/15144 and EP-A-0,714,954. Those of formula (IV) which can be used in the dyeing compositions in accordance with the invention are known compounds which are described, for example, in patent applications FR-2,189,006, FR-2,285,851 and FR-2,140,205 and its certificates of addition.

[0080] Among the cationic direct dyes of formula (I) which can be used in the dyeing compositions in accordance with the invention, there may be mentioned more particularly the compounds corresponding to the following structures (I1) to (I54): 13 14 15 16 17 18

[0081] Among the compounds having the structures (I1) to (I54) which are described above, the compounds corresponding to the structures (I1), (I2), (I14) and (I31) are most particularly preferred.

[0082] Among the cationic direct dyes of formula (II) which can be used in the dyeing compositions in accordance with the invention, there may be mentioned more particularly the compounds corresponding to the following structures (I1) to (I19): 19

[0083] Among the cationic direct dyes of formula (III) which can be used in the dyeing compositions in accordance with the invention, there may be mentioned more particularly the compounds corresponding to the following structures (III1) to (III18): 20 21

[0084] Among the particular compounds having the structures (III1) to (III18) which are described above, the compounds corresponding to the structures (III4), (III5) and (III13) are most particularly preferred.

[0085] Among the cationic direct dyes of formula (III′) which can be used in the dyeing compositions in accordance with the invention, there may be mentioned more particularly the compounds corresponding to the following structures (III′1) to (III′3): 22

[0086] Among the cationic direct dyes of formula. (IV) which can be used in the dyeing compositions in accordance with the invention, there may be mentioned more particularly the compounds having the following structures (IV)1 to (IV) 77: 23 24 25 26 27 28 29 30 31

[0087] The cationic direct dye(s) used according to the invention preferably represent from 0.001 to 10% by weight approximately of the total weight of the dyeing composition and still more preferably from 0.005 to 5% by weight approximately of this weight.

[0088] (ii) The anionic surfactant which can be used according to the present invention is chosen from the group consisting of:

[0089] (ii)1—acyl isethionates;

[0090] (ii)2—acyl taurates;

[0091] (ii)3—sulphosuccinates;

[0092] (ii)4—acyl sarcosinates;

[0093] (ii)5—acyl glutamates;

[0094] (ii)6—polyoxyethylenated ether carboxylic acids and their salts;

[0095] (ii)7—fatty glucamide sulphates;

[0096] (ii)8—alkyl galactoside uronates;

[0097] (ii)9—anionic derivatives of alkyl polyglucosides;

[0098] (ii)10—mixtures thereof.

[0099] The preferred acyl isethionates (ii)1 and acyl taurates (ii)2 in accordance with the invention correspond to the following general structure:

R1—CH2—CH2—SO3 −M+  (V)

[0100] where R1 denotes an R2COO group or an R2CONR3 group with R2 denoting a saturated or unsaturated, linear or branched C8-C30 aliphatic group and R3 denoting a hydrogen atom or a C1-C4 alkyl radical, and where M denotes H, ammonium, Na or K or an organic amine, in particular alkanolamine, residue.

[0101] The preferred sulphosuccinates (ii)3 which can be used according to the invention correspond to the following general structure: 32

[0102] where R2 and M have the same meanings indicated above for formula (V).

[0103] The preferred acyl sarcosinates (ii)4 and acyl glutamates (ii)5 which can be used according to the invention correspond to the following general structure: 33

[0104] where R2 and M have the same meanings indicated above for formula (V);

[0105] R4 denotes CH3 and R5 denotes hydrogen-, or alternatively,

[0106] R4 denotes hydrogen and R5 denotes —CH2CH2COO−M+.

[0107] The polyoxyalkylenated ether carboxylic acids and their salts (ii)6 in accordance with the invention are preferably those comprising from 2 to 50 ethylene oxide groups, and mixtures thereof. The anionic surfactants of the polyoxyalkylenated ether carboxylic acid or salt type are in particular those which correspond to the following formula (VIII):

R5545 OC2H4&Parenclosest;n—OCH2COOA  (VIII)

[0108] in which:

[0109] R6 denotes an alkyl or alkylaryl group, and n is an integer or a decimal number (mean value) which may vary from 2 to 24 and preferably from 3 to 10, the alkyl radical having between 6 and 20 carbon atoms approximately, and aryl preferably denoting phenyl, A denotes H, ammonium, Na, K, Li, Mg or a monoethanol-amine or triethanolamine residue. It is also possible to use mixtures of compounds of formula (VIII), in particular mixtures in which the R6 groups are different.

[0110] Compounds of formula (VIII) are sold for example by the company KAO under the names AKYPOS (NP40, NP70, OP40, OP80, RLM25, RLM38, RLMQ 38 NV, RLM 45, RLM 45 NV, RLM 100, RLM 100 NV, RO 20, RO 90, RCS 60, RS 60, RS 100, RO 50) or by the company SANDOZ under the names SANDOPAN (DTC Acid, DTC).

[0111] The fatty glucamide sulphates (ii)7 which can be used according to the invention are those described in patent application DE-4443645, the content of which forms an integral part of the description.

[0112] The alkyl galactoside uronates (ii)8 which can be used according to the invention are those described in patent EP-B-0,701,430, the content of which forms an integral part of the description.

[0113] The anionic derivatives of alkyl polyglucoside (ii)9 are preferably chosen from:

[0114] alkyl polyglucoside sulphates or sulphonates or mixtures thereof;

[0115] alkyl polyglucoside ether carboxylates;

[0116] alkyl polyglucoside sulphosuccinates;

[0117] alkyl polyglucoside isethionates;

[0118] alkyl polyglucoside phosphates.

[0119] These anionic derivatives of alkyl polyglucoside are in particular described in applications DE-3918135, DE-4021760, DE-4239390, DE-4336803, DE-4337035 and U.S. Pat. No. 5,001,004.

[0120] The anionic surfactants (ii) used according to the invention preferably represent from 0.05 to 30% by weight approximately of the total weight of the dyeing composition and still more preferably from 0.1 to 15% by weight approximately of this weight.

[0121] The appropriate dyeing medium (or carrier) generally consists of water or of a mixture of water and of at least one organic solvent for solubilizing the compounds which would not be sufficiently soluble in water. As organic solvent, there may be mentioned for example the C1-C4 lower alkanols such as ethanol and isopropanol, the aromatic alcohols such as benzyl alcohol as well as similar products and mixtures thereof.

[0122] The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dyeing composition, and still more preferably between 5 and 30% by weight approximately.

[0123] The pH of the dyeing composition in accordance with the invention is generally between 2 and 11 approximately, and preferably between 5 and 10 approximately. It may be adjusted to the desired value by means of acidifying or alkalinizing agents normally used in dyeing keratinous fibres.

[0124] Among the acidifying agents, there may be mentioned, by way of example, the inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

[0125] Among the alkalinizing agents, there may be mentioned, by way of example, aqueous ammonia, alkali metal carbonates, alkanolamines such as mono-, di- and triethanolamines as well as derivatives thereof, sodium or potassium hydroxides and the compounds having the following formula (VIII): 34

[0126] in which W is a propylene residue which is optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; R7, R8, R9 and R10, which are identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical.

[0127] The dyeing composition in accordance with the invention may, in addition to the cationic direct dye(s) (i) defined above, contain one or more additional direct dyes which may for example be chosen from the nitrobenzene dyes, the anthraquinone dyes, the naphthoquinone dyes, the triarylmethane dyes, the. xanthene dyes, the noncationic azo dyes.

[0128] When it is intended for oxidation dyeing, the dyeing composition in accordance with the invention contains, in addition to the cationic direct dye(s) (i), one or more oxidation bases chosen from the oxidation bases conventionally used for oxidation dyeing and among which there may be mentioned in particular the para-phenylenediamines, the bis-phenylalkylenediamines, the para-aminophenols, the ortho-aminophenols and the heterocyclic bases. When they are used, the oxidation base(s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dyeing composition, and still more preferably from 0.005 to 6% by weight approximately of this weight.

[0129] When it is intended for oxidation dyeing, the dyeing composition in accordance with the invention may also contain, in addition to the cationic direct dye (i) and the anionic surfactant (ii) as well as oxidation bases, one or more couplers so as to modify or increase the shimmer of the shades obtained using the cationic direct dye(s) (i) and the oxidation base(s).

[0130] The couplers which can be used in the dyeing composition in accordance with the invention may be chosen from the couplers conventionally used in oxidation dyeing and among which there may be mentioned in particular the meta-phenylenediamines, the meta-aminophenols, the meta-diphenols and the heterocyclic couplers. When they are present, the coupler(s) preferably represent from 0.0001 to 10% by weight approximately of the total weight of the dyeing composition and still more preferably from 0.005 to 5% by weight approximately of this weight.

[0131] The dyeing composition in accordance with the invention may also contain various adjuvants which are conventionally used in hair-dyeing compositions, such as antioxidants, penetrating agents, sequestrants, perfumes, buffers, dispersing agents, film-forming agents, ceramides, preservatives, screening agents and opacifying agents.

[0132] Of course, persons skilled in the art will be careful to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the dyeing composition in accordance with the invention are not, or not substantially, altered by the addition(s) envisaged.

[0133] The dyeing composition according to the invention may be provided in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other form appropriate for dyeing keratinous fibres, and in particular human hair. It may be obtained by freshly mixing a composition, which is optionally pulverulent, containing the cationic direct dye(s) with a composition containing the anionic surfactant.

[0134] When the combination of the cationic direct dye (i) and of the anionic surfactant (ii) according to the invention is used in a composition intended for oxidation dyeing (one or more oxidation bases are then used, optionally in the presence of one or more couplers) or when it is used in a composition intended for direct lightening dyeing, then the dyeing composition in accordance with the invention contains, in addition, at least one oxidizing agent chosen for example from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such the perborates and persulphates, and enzymes such as peroxidases, laccases and oxidoreductases containing two electrons. The use of hydrogen peroxide or of enzymes is particularly preferred.

[0135] Another subject of the invention is a method of dyeing keratinous fibres and in particular human keratinous fibres such as hair using the dyeing composition as defined above.

[0136] According to a first variant of this dyeing method in accordance with the invention, at least one dyeing composition as defined above is applied to the fibres for a sufficient time to develop the desired colour, after which they are rinsed, optionally washed with shampoo, rinsed again and dried.

[0137] The time necessary for the development of the colour on the keratinous fibres is generally between 3 and 60 minutes and still more preferably 5 and 40 minutes.

[0138] According to a second variant of this dyeing method in accordance with the invention, at least one dyeing composition as defined above is applied to the fibres for a sufficient time to develop the desired colour, with no final rinsing.

[0139] According to a particular embodiment of this dyeing method, and when the dyeing composition in accordance with the invention contains at least one oxidation base and at least one oxidizing agent, the dyeing method comprises a preliminary stage consisting of storing in a separate form, on the one hand, a composition (A1) comprising, in an appropriate dyeing medium, at least one cationic direct dye (i) as defined above and at least one oxidation base and, on the other hand, a composition (B1) containing, in an appropriate dyeing medium, at least one oxidizing agent, and then mixing them at the time of use before applying this mixture to the keratinous fibres, the composition (A1) or the composition (B1) containing the anionic surfactant (ii) as defined above.

[0140] According to another particular embodiment of this dyeing method, and when the dyeing composition in accordance with the invention contains at least one oxidizing agent, the dyeing method comprises a preliminary stage consisting of storing in a separate form, on the one hand, a composition (A2) comprising, in an appropriate dyeing medium, at least one cationic direct dye (i) as defined above and, on the other hand, a composition (B2) containing, in an appropriate dyeing medium, at least one oxidizing agent, and then mixing them at the time of use before applying this mixture to the keratinous fibres, the composition (A2) or the composition (B2) containing the anionic surfactant as defined above.

[0141] Another subject of the invention is a multicompartment deviceor dyeing “kit” or any other multicompartment packaging system in which a first compartment contains composition (A1) or (A2) as defined above and a second compartment contains composition (B1) or (B2) as defined above. These devices may be equipped with a means allowing the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the applicant's name.

[0142] The following examples are intended to illustrate the invention without, however, limiting the scope thereof.

EXAMPLES

Examples 1 to 5

[0143] The five direct dyeing compositions which are assembled in the following table were prepared: (all contents expressed in grams) 1 Example Example Example Example Example 1 2 3 4 5 Cationic direct dye of  0.2 formula (I1) Cationic direct dye of  0.2 formula (I14) Cationic direct dye of  0.15 formula (I31) Cationic direct dye of  0.12 formula (IV)10 Cationic direct dye of  0.10 formula (IV)27 Triethanolamine cocoyl  5.0 AS* glutamate sold under the name ACYLGLUTAMATE CT12 by the company AJINOMOTO Sodium lauroyl  5.0 AS* sarcosinate sold under the name ORAMIX L30 by the company SEPPIC Sodium cocoyl  5.0 AS* isethionate sold under the name JORDAPON CI POWDER by the company PPG Lauryl ether  5.0 AS* carboxylic acid containing 10 EO sold under the name AKYPO RLM 100 by the company KAO Sodium salt of  5.0 AS* tartaric ester of cocoyl polyglucoside sold under the name GUCAROL AGE ET by the company CESALPINA Ethanol 10 10 10 10 10 2-Amino-2-methyl-1- pH 9 pH 9 pH 9 pH 9 pH 9 propanol . . . qs Demineralized 100 100 100 100 100 water . . . qs AS* denotes Active Substance

[0144] The above compositions were each applied for 30 minutes to locks of natural grey hair which is 90% white. The hair locks were then rinsed, washed with a standard shampoo and then dried.

[0145] The locks were dyed in the following shades: 2 Examples Shades obtained 1 dark red 2 dark orange 3 dark violet 4 dark red 5 dark purple

Claims

1. Composition for dyeing keratinous fibres and in particular human keratinous fibres such as hair, containing in an appropriate dyeing medium, (i) at least compound chosen from those of the following formulae (I), (II), (III), (III′), (IV):

a) the compounds of the following formula (I):

35

in which:

D represents a nitrogen atom or the —CH group,

R1 and R2, which are identical or different, represent a hydrogen atom; a C1-C4 alkyl radical which may be substituted with a —CN, —OH or —NH2 radical or form with a carbon atom of the benzene ring an optionally oxygen-containing or nitrogen-containing heterocycle which may be substituted with one or more C1-C4 alkyl radicals; a 4′-aminophenyl radical,

R3 and R′3, which are identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano, C1-C4 alkyl, C1-C4 alkoxy or acetyloxy radical,

X− represents an anion which is preferably chosen from chloride, methylsulphate and acetate,

A represents a group chosen from the following structures A1 to A19:

36 37

in which R4 represents a C1-C4 alkyl radical which may be substituted with a hydroxyl radical and R5 represents a C1-C4 alkoxy radical, with the proviso that when D represents —CH, A represents A4 or A13 and R3 is different from an alkoxy radical, then R1 and R2 do not simultaneously denote a hydrogen atom;

b) the compounds of the following formula (II):

38

in which:

R6 represents a hydrogen atom or a C1-C4 alkyl radical,

R7 represents a hydrogen atom, an alkyl radical which may be substituted with a —CN radical or with an amino group, a 4′-aminophenyl radical or forms with R6 anoptionally oxygen-containing and/or nitrogen-containing heterocycle which may be substituted with a C1-C4 alkyl radical,

R8 and R9, which are identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, a —CN radical,

X− represents an anion which is preferably chosen from chloride, methylsulphate and acetate,

B represents a group chosen from the following structures B1 to B6:

39

in which R10 represents a C1-C4 alkyl radical, R11 and R12, which are identical or different, represent a hydrogen atom or a C1-C4 alkyl radical;

c) the compounds of the following formulae (III) and (III′):

40

in which:

R13 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine or an amino radical,

R14 represents a hydrogen atom, a C1-C4 alkyl radical or forms with a carbon atom of the benzene ring a heterocycle which is optionally oxygen-containing and/or substituted with one or more C1-C4 alkyl groups,

R15 represents a hydrogen or halogen atom such as bromine, chlorine, iodine of fluorine,

R16 and R17, which are identical or different, represent a hydrogen atom or a C1-C4 alkyl radical,

D1 and D2, which are identical or different, represent a nitrogen atom or the -CH group,

m=0 or 1,

it being understood that when R13 represents an unsubstituted amino group, then D1 and D2 simultaneously represent a —CH group and m=0,

X− represents an anion which is preferably chosen from chloride, methylsulphate and acetate,

E represents a group chosen from the following structures E1 to E8:

41

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

when m=0 and D1 represents a nitrogen atom, then E may also denote a group having the following structure E9:

42

in which R′ represents a C1-C4 alkyl radical,

d) the compounds of the following formula (IV):

G—N══N—J  (IV)

in which:

the symbol G represents a group chosen from the following structures G1 to G3:

43

in which structures G1 to G3,

R18 denotes a C1-C4 alkyl radical, a phenyl radical which may be substituted with a C1-C4 alkyl radical or a halogen atom chosen from chlorine, bromine, iodine and fluorine;

R19 denotes a C1-C4 alkyl radical or a phenyl radical;

R20 and R21, which are identical or different, represent a C1-C4 alkyl radical, a phenyl radical, or form together in G1 a benzene ring which is substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals, or form together in G2 a benzene ring which is optionally substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals;

R20 may denote, in addition, a hydrogen atom;

Z denotes an oxygen or sulphur atom or an —NR19 group;

M represents a group —CH, —CR (R denoting C1-C4 alkyl), or —NR22(X−)r;

K represents a group —CH, —CR (R denoting C1-C4 alkyl), or —NR22(X−)r;

P represents a group —CH, —CR (R denoting C1-C4 alkyl), or —NR22(X−)r; r denotes zero or 1;

R22 represents an O− atom, a C1-C4 alkoxy radical or a C1-C4 alkyl radical;

R23 and R24, which are identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, a C1-C4 alkoxy radical or an —NO2 radical;

X− represents an anion which is preferably chosen from chloride, iodide, methylsulphate, ethylsulphate, acetate and perchlorate;

with the proviso that

if R22 denotes O31, then r denotes zero;

if K or P or M denote —N—(C1-C4 alkyl)X−, then R23 or R24 is different from a hydrogen atom;

if K denotes —NR22(X−)r′, then M=P=—CH, —CR;

if M denotes —NR22(X−)r, then K=P=—CH, —CR;

if P denotes —NR22(X−)r, then K=M and denote —CH or —CR;

if Z denotes a sulphur atom with R21 denoting C1-C4 alkyl, then R20 is different from a hydrogen atom;

if Z denotes —NR22 with R19 denoting C1-C4 alkyl, then at least one of the R18, R20 or R21 radicals of G2 is different from a C1-C4 alkyl radical;

the symbol J represents:

(a) a group having the following structure J1:

44

in which structure J1,

R25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a radical —OH, —NO2, —NHR28, —NR29R30, —NHCO(C1-C4alkyl), or forms with

R26 a 5- or 6-membered ring containing or otherwise one or more heteroatoms chosen from nitrogen, oxygen or sulphur;

R26 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl or C1-C4 alkoxy radical, or forms with R27 or R28 a 5- or 6-membered ring containing or otherwise one or more heteroatoms chosen from nitrogen, oxygen or sulphur;

R27 represents a hydrogen atom, an —OH radical, an —NHR28 radical, an —NR29R30 radical;

R28 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a phenyl radical;

R29 and R30, which are identical or different, represent a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical;

(b) a 5- or 6- membered nitrogen-containing heterocycle group which is capable of containing other heteroatoms and/or carbonyl-containing groups and which may be substituted with one or more C1-C4 alkyl, amino or phenyl radicals,

and in particular a group having the following structure J2:

45

in which structure J2,

R31 and R32, which are identical or different, represent a hydrogen atom, a C1-C4 alkyl radical, a phenyl radical;

Y denotes the —CO—radical or the radical

46

n=0 or 1, with, when n denotes 1, U denotes the —CO—radical.

the said composition being characterized in that it contains, in addition,

(ii) at least one anionic surfactant chosen from the group comprising:

(ii)1—acyl isethionates;

(ii)2—acyl taurates;

(ii)3—sulphosuccinates;

(ii)4—acyl sarcosinates;

(ii)5—acyl glutamates;

(ii)6—polyoxyethylenated ether carboxylic acids and their salts;

(ii)7—fatty glucamide sulphates;

(ii)8—alkyl galactoside uronates;

(ii)9—anionic derivatives of alkyl polyglucosides;

(ii)10—mixtures thereof.

2. Composition according to claim 1, characterized in that the cationic direct dyes of formula (I) are chosen from the compounds corresponding to the following structures (I1) to (I54):

47 48 49 50 51 52 53

3. Composition according to claim 2, characterized in that the cationic direct dyes correspond to the structures (I1), (I2), (I14), and (I31).

4. Composition according to claim 1, characterized in that the cationic direct dyes of formula (II) are chosen from the compounds corresponding to the following structures (II1) to (II9):

54 55

5. Composition according to claim 1, characterized in that the cationic direct dyes of formula (III) are chosen from the compounds corresponding to the following structures (III1) to (III18):

56 57

6. Composition according to claim 5, characterized in that the cationic direct dyes of formula (III) are chosen from the compounds corresponding to the structures (III4), (III5) and (III13).

7. Composition according to claim 1, characterized in that the cationic direct dyes of formula (III′) are chosen from the compounds corresponding to the following structures (III′1) to (III′3):

58

8. Composition according to claim 1, characterized in that the cationic direct dyes of formula (IV) are chosen from the compounds corresponding to the following structures (IV)1 to (IV)77:

59 60 61 62 63 64 65 66 67 68 69

9. Composition according to any one of the preceding claims, characterized in that the cationic direct dye(s) of formulae (I), (II), (III), (III′) or (IV) represent from 0.001 to 10% by weight of the total weight of the composition.

10. Composition according to claim 9, characterized in that the cationic direct dye(s) of formulae (I), (II), (III), (III′) or (IV) represent from 0.005 to 5% by weight of the total weight of the composition.

11. Composition according to any one of the preceding claims, characterized in that the anionic surfactant (ii) of the acyl isethionate (ii)1 and acyl taurate (ii)2 type corresponds to the general formula:

R1—CH2—CH2—SO3−M+  (V)

in which:

R1 denotes an R2COO group or an R2CONR3 group with R2 denoting a saturated or unsaturated, linear or branched C8-C30 aliphatic group and R3 denoting a hydrogen atom or a C1-C4 alkyl radical, and

where M denotes H, ammonium, Na or K or an organic amine residue.

12. Composition according to any one of claims 1 to 10, characterized in that the anionic surfactant (ii) of the sulphosuccinate (ii)3 type corresponds to the general formula:

70

in which R2 and M have the same meanings as those indicated in claim 11.

13. Composition according to any one of claims 1 to 10, characterized in that the anionic surfactant (ii) of the acyl sarcosinate (ii)4 and acyl glutamate (ii)5 type corresponds to the general formula:

71

in which, R2 and M have the same meanings as those indicated in claim 11; R4 denotes CH3 and R5 denotes hydrogen, or alternatively R4 denotes hydrogen and R5 denotes —CH2CH2—COO−M+.

14. Composition according to any one of claims 1 to 10, characterized in that the anionic surfactant (ii) of the polyoxyalkylenated ether carboxylic acid or salt (ii)6 type comprises 2 to 50 ethylene oxide groups.

15. Composition according to claim 14, characterized in that the polyoxyalkylenated ether carboxylic acid or salt corresponds to the following formula (VIII):

R6&Parenopenst;OC2H4&Parenclosest;n—OCH2COOA  (VII)

in which:

R6 denotes a C6-C20 alkyl or (C6-C20)alkylaryl group, and n is an integer or a decimal number (mean value) which may vary from 2 to 24 and preferably from 3 to 10, A denotes H, ammonium, Na, K, Li, Mg or a monoethanol-amine or triethanolamine residue.

16. Composition according to claim 15, characterized in that the aryl radical denotes phenyl.

17. Composition according to any one of claims 1 to 10, characterized in that the anionic surfactant (ii) of the anionic derivative of alkyl polyglucoside (ii)9 type is chosen from the group consisting of:

alkyl polyglucoside sulphates or sulphonates or mixtures thereof;

alkyl polyglucoside ether carboxylates;

alkyl polyglucoside sulphosuccinates;

alkyl polyglucoside isethionates;

alkyl polyglucoside phosphates.

18. Composition according to any one of the preceding claims, characterized in that the anionic surfactant(s) represent from 0.05 to 30% by weight of the total weight of the composition.

19. Composition according to claim 18, characterized in that the anionic surfactant(s) represent from 0.1 to 15% by weight of the total weight of the composition.

20. Composition according to any one of the preceding claims, characterized in that the appropriate dyeing medium (or carrier) consists of water or of a mixture of water and of at least one organic solvent.

21. Composition according to any one of the preceding claims, characterized in that it has a pH of between 2 and 11, and preferably between 5 and 10.

22. Composition according to any one of the preceding claims, characterized in that it is intended for oxidation dyeing and in that it contains one or more oxidation bases chosen from the para-phenylenediamines, the bis-phenylalkylenediamines, the para-aminophenols, the ortho-aminophenols and the heterocyclic bases.

23. Composition according to claim 22, characterized in that the oxidation base(s) represent 0.0005 to 12% by weight of the total weight of the dyeing composition.

24. Composition according to claim 23, characterized in that the oxidation base(s) represent 0.005 to 6% by weight of the total weight of the dyeing composition.

25. Composition according to any one of claims 22 to 24, characterized in that it contains one or more couplers chosen from the the meta-phenylenediamines, the meta-aminophenols, the meta-diphenols and the heterocyclic couplers.

26. Composition according to claim 25, characterized in that the coupler(s) represent from 0.0001 to 10% by weight of the total weight of the dyeing composition.

27. Composition according to claim 26, characterized in that the coupler(s) represent from 0.005 to 5% by weight of the total weight of the dyeing composition.

28. Composition according to any one of the preceding claims, characterized in that it is intended for direct lightening dyeing or oxidation dyeing and in that it then contains at least one oxidizing agent.

29. Method of dyeing keratinous fibres and in particular human keratinous fibres such as hair, characterized in that at least one dyeing composition as defined in any one of claims 1 to 28 is applied to the fibres for a sufficient time to develop the desired colour, after which they are rinsed, optionally washed with shampoo, rinsed again and dried.

30. Method of dyeing keratinous fibres and in particular human keratinous fibres such as hair, characterized in that at least one dyeing composition as defined in any one of claims 1 to 28 is applied to the fibres for a sufficient time to develop the desired colour, with no final rinsing.

31. Method of dyeing keratinous fibres and in particular human keratinous fibres such as hair, characterized in that it comprises a preliminary stage consisting of storing in a separate form, on the one hand, a composition (A1) comprising, in an appropriate dyeing medium, at least one cationic direct dye (i) as defined in the preceding claims and at least one oxidation base and, on the other hand, a composition (B1) containing, in an appropriate dyeing medium, at least one oxidizing agent, and then mixing them at the time of use before applying this mixture to the keratinous fibres, the composition (A1) or the composition (B1) containing the anionic surfactant (ii) as defined in the preceding claims.

32. Method of dyeing keratinous fibres and in particular human keratinous fibres such as hair, characterized in that it comprises a preliminary stage consisting of storing in a separate form, on the one hand, a composition (A2) comprising, in an appropriate dyeing medium, at least one cationic direct dye (i) as defined in the preceding claims and, on the other hand, a composition (B2) containing, in an appropriate dyeing medium, at least one oxidizing agent, and then mixing them at the time of use before applying this mixture to the keratinous fibres, the composition (A2) or the composition (B2) containing the anionic surfactant (ii) as defined in the preceding claims.

33. Multicompartment device or multicompartment dyeing “kit”, characterized in that a first compartment contains composition (A1) or (A2) as defined in claim 31 or 32 and a second compartment contains composition (B1) or (B2) as defined in claim 31 or 32.