# Patent

## Title
Method of coloring porous material

## Abstract

Process of coloring porous material, which comprises

    a) applying to the material being colored at least one capped diazonium compound, and
    b) then causing the capped diazonium compound present on the material to react with the material.

## Background
The present invention relates to a method of colouring porous material, for example metal, wood or keratin-containing fibres, especially human hair, using capped diazonium compounds.
For colouring hair oxidation dyes are used in most cases; however, they too are not capable of satisfying all requirements. The fastness to washing properties are often inadequate and, in addition, the colouring conditions required often cause a greater or lesser amount of damage to the hair. There has therefore been a need for a colouring method which does not have the mentioned disadvantages or which has them to an insignificant degree.
The present invention relates to a process of colouring porous material, which comprises

    a) applying to the material being coloured at least one capped diazonium compound, and
    b) then causing the capped diazonium compound present on the material to react with the hair.


The colorations obtained are distinguished by outstanding fastness to washing properties, and there is virtually no damage to the hair. Moreover, there is no staining of the scalp, because the dye components do not penetrate into the skin and non-fixed dye can be washed off readily.
Suitable capped diazonium compounds include, for example, compounds of formula (1), (2), (3), (4) or (5)




    wherein
    Q is a radical of an organic compound, preferably an unsubstituted or substituted non-ionic, cationic, amphoteric, zwitterionic or anionic radical of an organic compound,
    R is the radical of an unsubstituted or substituted, water-soluble aliphatic or aromatic amine,
    and
    T is an unsubstituted or substituted, aliphatic or aromatic residue,
    wherein at least one of the groups must contain a radical imparting water solubility.


Suitable radicals R imparting water solubility include, for example, SO3H, COOH, OH, a quaternised ammonium radical of formula




    wherein R1, R2 and R3 are each independently of the others unsubstituted or substituted alkyl, and An is an anion;
    or
    a quaternised nitrogen radical, which is part of a cationic heterocycle.


According to the invention, alkyl groups R, R1, R2, R3 and R4 are to be understood as being generally open-chain or branched alkyl radicals, for example methyl, ethyl, n- or iso-propyl and n-, sec- or tert-butyl.
Such alkyl radicals may be mono- or poly-substituted, for example by hydroxy, carboxy, halogen, cyano or by C1–C4alkoxy.
Preferably, the alkyl groups are unsubstituted and each has from 1 to 4, especially 1 or 2, carbon atoms.
According to the invention aryl is for example substituted or unsubstituetd phenyl or naphthyl. Preferably aryl is phenyl.
Aralkyl is for example (C1–C4alkyl)phenyl, preferably benzyl.
Suitable anions An are both inorganic and organic anions, for example halide, such as chloride, bromide or iodide, sulfate, hydrogen sulfate, methyl sulfate, formate, acetate and lactate.
The anion is generally determined by the preparation process. Preferably, the chlorides, hydrogen sulfates, sulfates, methosulfates or acetates are present.
Q is for example an unsubstituted or substituted aromatic or heterocyclic or not heterocyclic residue, which is a neutral, or inonic residue, such as a cationic, anionic, zwitterionic or amphotheric residue. For example, unsubstituted or substituted phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl are suitable.
Q as a cationic radical of an organic compound encompasses for example the radicals A+ as defined below in formula (40).
Suitable cationc heterocycles of Q containing for example quaternized nitrogen are for example 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl.
Preferred cationc heterocycles containing quaternized nitrogen are an imidazolyl, pyridinyl or thiazolyl.
More, preferred cationc heterocycles containing quaternized nitrogen are an imidazolyl residue of formula




wherein

    R4 is substituted or unsubstituted C1–C4alkyl, aryl or aralkyl, preferably methyl, ethyl, propyl, and more prefarbly methyl.


Such radicals may be mono- or poly-substituted, for example by C1–C4alkyl, C1–C4alkoxy, C1–C4alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro, trifluoromethyl, CN, SCN, C1–C4alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C1–C4alkylaminosulfonyl, C1–C4alkyl-carbonylamino, C1–C4alkoxysulfonyl or by di-(hydroxy-C1–C4alkyl)-aminosulfonyl.
Further, suitable cationic aromatic radicals of Q are radicals of formulae




    wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and
    preferably, cationic aromatic radicals of Q are radicals of formulae






    and more preferably, cationic aromatic radicals of Q are radicals of formulae






    Q most more preferably, cationic aromatic radicals of Q are radicals of formulae






In addition, suitable radicals Q are as follows:






















Further in the context of the present invention,

    R is the radical of an unsubstituted or substituted, water-soluble aliphatic or aromatic amine.


Preferably, R is a radical of formula —NR16R17, wherein R16 is H; unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH.
More preferably R is a radical of formula —NR16R17, wherein R16 is unsubstituted linear or branched C1–C6alkyl and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent, preferably by onesubstituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH.
Most preferably R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH.
R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH.
Example for suitable amine compounds (R—H) are methylaminoacetic acid (sarcosine), methylaminobutyric acid, methylaminopropionic acid, ethylaminoacetic acid, dimethylamine, diethylamine, dieproylamine, diisopropylamin, dibutylamin, di-sec-butylamine, di-tert.-butylamine, ethylaminobutyric acid, 1-methylamino-ethane-2-sulfonic acid, 1-ethylamino-ethane-2-sulfonic acid and 1-methylamino-propane-3-sulfonic acid.
Preferably, R also signifies the radical of unsubstituted aniline; the radical of unsubstituted aminonaphthalene; the radical of aniline or aminonaphthalene, wherein the phenyl or the naphthyl ring is substituted by one or more identical or different substituent selected from the group consisting of COOH, SO3H, CN, halogen, SO2C1–C2alkyl, unsubstituted linear or branched C1–C4alkyl, linear or branched C1–C4alkyl, substituted by OH, carboxy, COC1–C2alkyl or SO2—N(C1–C4alkyl)-(CH2)1-4SO3H and wherein the amino radical is substituted by H, unsubstituted linear or branched C1–C4alkyl or linear or branched C1–C4alkyl, substituted by OH or carboxy.
Suitable radicals of such aromatic amines are, for example, as follows:




T is an unsubstituted or substituted, water-soluble aliphatic or aromatic residue.
Preferably, T is a linear or branched unsubstituted C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, NH(C1–C2alkyl), N(C1–C2alkyl)2, CN, halogen and OH.
More preferably, T is a linear or branched C1–C6alkyl, which is substituted by one or two identical or different substituent selected from the group consisting of COOH, NH2, NH(C1–C2alkyl), N(C1–C2alkyl)2 and SO3H.
Examples for such suitable radicals are —CH2COOH, —(CH2)2COOH, —(CH2)3COOH, —CH(NHCH2CH3)COOH, —CH2CH2SO3H and —CH2CH2CH2SO3H.
Preferably, T is also unsubstituted phenyl; unsubstituted naphthyl; phenyl or naphthyl, which are substituted by one or more identical or different substituents selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, NH(C1–C2alkyl), N(C1–C2alkyl)2, CN, halogen and OH.
Such suitable aromatic residues of T are, for example, as follows:




A preferred embodiment of the present invention is a process of colouring porous material, which comprises

    a) applying to the material being coloured at least one capped diazonium compound of formula (1), (2), (3), (4) or (5)






    wherein
    Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl; or
    Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which is mono- or poly-substituted by C1–C4alkyl, C1–C4alkoxy, C1–C4alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro, trifluoromethyl, CN, SCN, C1–C4alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C1–C4alkylaminosulfonyl, C1–C4alkyl-carbonylamino, C1–C4alkoxysulfonyl or by di-(hydroxy-C1–C4alkyl)-aminosulfonyl; or Q is a cationic radical of an organic compound, especially Q is a radical of formula






    wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and
    preferably, Q is a radical of formula






    and more preferably, Q is a radical of formula






    and most more preferably, Q is a radical of formula






    and
    R is a radical of formula —NR16R17, wherein R16 is H; unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, or
    R is the radical of unsubstituted aniline; the radical of unsubstituted aminonaphthalene; the radical of aniline or aminonaphthalene, wherein the phenyl or the naphthyl ring is substituted by one or more identical or different substituent selected from the group consisting of COOH, SO3H, CN, halogen, SO2C1–C2alkyl, unsubstituted linear or branched C1–C4alkyl, linear or branched C1–C4alkyl, substituted by OH, carboxy, COC1–C2alkyl or SO2—N(C1–C4alkyl)-(CH2)1-4SO3H and wherein the amino radical is substituted by H, unsubstituted linear or branched C1–C4alkyl or linear or branched C1–C4alkyl, substituted by OH or carboxy;
    most preferably R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    especially most preferably R is a radical of formula —NR16R17, wherein R16 and R17 are unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; or,


R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;

    T is a linear or branched unsubstituted C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, NH(C1–C2alkyl), N(C1–C2alkyl)2, CN, halogen and OH, or
    T is unsubstituted phenyl; unsubstituted naphthyl; phenyl or naphthyl, which are substituted by one or more identical or different substituents selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, NH(C1–C2alkyl), N(C1–C2alkyl)2, CN, halogen and OH,
    and
    b) then causing the capped diazonium compound present on the material to react with the hair.


A more preferred embodiment of the present invention is a process of colouring porous material, which comprises applying to the material being coloured,

    a) at least one capped diazonium compound of formula (1)






    and/or at least one compound of formula (2)






    and/or at least one compound of formula (3)






    and/or at least one compound of formula (4)






    and/or at least one compound of formula (5)






    wherein
    Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or
    Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which is mono- or poly-substituted by C1–C4alkyl, C1–C4alkoxy, C1–C4alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro, trifluoromethyl, CN, SCN, C1–C4alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C1–C4alkylaminosulfonyl, C1–C4alkyl-carbonylamino, C1–C4alkoxysulfonyl or by di-(hydroxy-C1–C4alkyl)-aminosulfonyl; or Q is a cationic radical of an organic compound, especially Q is a radical of formula






    wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and
    preferably, Q is a radical of formula






    and more preferably, Q is a radical of formula






    and most more preferably, Q is a radical of formula






    and
    R is a radical of formula —NR16R17, wherein R16 is H; unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    most preferably R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; especially most preferably R is a radical of formula —NR16R17, wherein R16 and R17 are unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; or,
    R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    T is a linear or branched C1–C6alkyl, which is substituted by one or two identical or different substituent selected from the group consisting of COOH, SO3H, NH2, NH(C1–C2alkyl) and N(C1–C2alkyl)2, or
    T is unsubstituted phenyl; unsubstituted naphthyl; phenyl or naphthyl, which are substituted by one or more identical or different substituents selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, NH(C1–C2alkyl), N(C1–C2alkyl)2, CN, halogen and OH,
    and
    b) then causing the capped diazonium compound present on the material to react with the hair.


An especially preferred embodiment of the present invention is a process of colouring porous material, which comprises applying to the material being coloured,

    a) at least one capped diazonium compound of formula (1)






    wherein
    Q is an unsubstituted phenyl; naphthyl; thiophenyl; 1,3-thiazolyl; 1,2-thiazolyl; 1,3-benzothiazolyl; 2,3-benzothiazolyl; imidazolyl; 1,3,4-thiadiazolyl; 1,3,5-thiadiazolyl; 1,3,4-triazolyl; pyrazolyl; benzimidazolyl; benzopyrazolyl; pyridinyl; quinolinyl; pyrimidinyl; isoxazolyl; aminodiphenyl; aminodiphenylether and azobenzenyl or
    Q is a phenyl, naphthyl, thiophenyl, 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl, aminodiphenyl, aminodiphenylether and azobenzenyl which is mono- or poly-substituted by C1–C4alkyl, C1–C4alkoxy, C1–C4alkylthio, halogen, e.g. fluorine, bromine or chlorine, nitro, trifluoromethyl, CN, SCN, C1–C4alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C1–C4alkylaminosulfonyl, C1–C4alkyl-carbonylamino, C1–C4alkoxysulfonyl or by di-(hydroxy-C1–C4alkyl)-aminosulfonyl; or Q is a cationic radical of an organic compound, especially Q is a radical of formula






    wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and
    preferably, Q is a radical of formula






    and more preferably, Q is a radical of formula






    and most more preferably, Q is a radical of formula






    and
    R is a radical of formula —NR16R17, wherein R16 is H; unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    most preferably R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    and
    b) then causing the capped diazonium compound present on the material to react with the hair.


A further especially preferred embodiment of the present invention is a process of colouring porous material, which comprises applying to the material being coloured,

    a) at least one capped diazonium compound of formula (1)






    wherein
    or Q is a cationic radical of an organic compound, especially Q is a radical of formula






    wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and
    preferably, Q is a radical of formula






    and more preferably, Q is a radical of formula






    and most more preferably, Q is a radical of formula






    and
    R is a radical of formula —NR16R17, wherein R16 is H; unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    most preferably R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; especially most preferably R is a radical of formula —NR16R17, wherein R16 and R17 are unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl;
    and
    b) then causing the capped diazonium compound present on the material to react with the hair.


A further embodiment of the present invention is a process of colouring porous material, which comprises a) applying to the material being coloured,
at least two capped diazonium compounds as defined above and


    and
    b) then causing the capped diazonium compound present on the material to react with the hair.


An important embodiment of the present invention is a process of colouring porous material, which comprises applying to the material being coloured,

    a) at least one capped diazonium compound of formula (1)






    and/or at least one compound of formula (2)






    and/or at least one compound of formula (3)






    and/or at least one compound of formula (4)






    and/or at least one compound of formula (5)
























    or Q is a cationic radical of an organic compound, especially Q is a radical of formula






    wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and
    preferably, Q is a radical of formula






    and more preferably, Q is a radical of formula






    and most more preferably, Q is a radical of formula









    and
    b) then causing the capped diazonium compound present on the material to react with the hair.


The amines of formulae Q-NH2 and R—H are known or can be synthesised in a manner known per se.
The compounds of formulae (2) and (3) are also known or can be synthesised in a manner known per se.
The compounds of formula (6) and (7),




wherein R80 and R81 are independently from each other are hydrogen; unsubstituted or substituted linear or branched C1–C6alkyl, OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; and

    preferably






    and more preferably






    most more preferably






    are novel, wherein
    R is a radical of formula —NR16R17, wherein R16 is H; unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    most preferably R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH;
    R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH; especially most preferably R is a radical of formula —NR16R17, wherein R16 and R17 are unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl.


Example for suitable amine compounds (R—H) are methylaminoacetic acid (sarcosine), methylaminobutyric acid, methylaminopropionic acid, ethylaminoacetic acid, ethylaminobutyric acid, 1-methylamino-ethane-2-sulfonic acid, 1-ethylamino-ethane-2-sulfonic acid and 1-methylamino-propane-3-sulfonic acid.
Especially preferred are compounds of formulae




Preferably, R also signifies the radical of unsubstituted aniline; the radical of unsubstituted aminonaphthalene; the radical of aniline or aminonaphthalene, wherein the phenyl or the naphthyl ring is substituted by one or more identical or different substituent selected from the group consisting of COOH, SO3H, CN, halogen, SO2C1–C2alkyl, unsubstituted linear or branched C1–C4alkyl, linear or branched C1–C4alkyl, substituted by OH, carboxy, COC1–C2alkyl or SO2—N(C1–C4alkyl)-(CH2)1-4SO3H and wherein the amino radical is substituted by H, unsubstituted linear or branched C1–C4alkyl or linear or branched C1–C4alkyl, substituted by OH or carboxy.
Suitable radicals of such aromatic amines are, for example, as follows:




Most preference is given to compounds of formulae (6) and (7), wherein R is a radical of formula —NR16R17, wherein R16 unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH.
Especially most preference is given to compounds of formulae (6) and (7), wherein R is a radical of formula —NR16R17, wherein R16 and R17 are unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl; or,

    wherein R16 is unsubstituted linear or branched C1–C6alkyl, preferably methyl or ethyl, most preferred methyl, and R17 is unsubstituted linear or branched C1–C6alkyl or linear or branched C1–C6alkyl, which is substituted by one or more identical or different substituent, preferably by one substituent selected from the group consisting of OC1–C4alkyl, COOH, COOC1–C2alkyl, SO3H, NH2, CN, halogen and OH.


The compounds of formula (1) can likewise be prepared in a manner known per se; for example, an amine of formula q-NH2 is, in customary manner, diazotised and coupled to an amine of formula R—H.
A further preferred embodiment of the process of the present invention concerns a cationic capped diazonium compound, of formula




wherein

    A+ is a subgroup of Q as defined above; and is a cationic radical of an organic compound, R is the radical of an unsubstituted or substituted, water-soluble aliphatic or aromatic amine, with the same definitions and preferences as described in this application for R.


Suitable cationic radicals A+ are substituted or unsubstituted cationic heterocyclic compounds; or non-heterocyclic compounds having a cationc substitutent; or cationc azo compounds, comprising cationic heterocyclic compounds.
Suitable cationic heterocyclic compounds are for example derivatives of 1,3-thiazolyl, 1,2-thiazolyl, 1,3-benzothiazolyl, 2,3-benzothiazolyl, imidazolyl, 1,3,4-thiadiazolyl, 1,3,5-thiadiazolyl, 1,3,4-triazolyl, pyrazolyl, benzimidazolyl, benzopyrazolyl, pyridinyl, quinolinyl, pyrimidinyl and isoxazolyl. Preferred cationic heterocyclic compounds are imidazolyl, pyridinyl, 1,3,4-triazolyl and 1,3-thiazolyl.
Suitable cationic substituents of the aromatic compounds are for example quaternised ammonium radicals of formula




    wherein R37, R38 and R39 are each independently of the others unsubstituted or substituted alkyl and An is an anion; or
    a quaternised nitrogen radical, which is part of a cationic heterocyclic compound, which have the same meaning as described above.


Suitable anions, An, are both inorganic and organic anions, for example halide, such as chloride, bromide or iodide, hydroxid, sulfate, hydrogen sulfate, C1–C6alkyl sulfonate, such as methyl sulfonate or ethy sulfonate, C1–C6alkyl sulfate, C1–C6alkyl substituted or unsubstituted arylsulfonate, such as 4-toluylsulfonate, formate, such as methyl sulfate or ethy sulfate, acetate, tartrate, oxalate, and lactate.
Preferred anions are chloride, hydrogen sulfate, sulfate, methosulfate or acetate.
Preferably, the further preferred embodiment of the process of the present invention relates to a cationic capped diazonium compound of formulae

[D+-N═N-M-]-N═N—R An  (42a)

or

(T-N═N-Q+-)-N═N—R An  (42b)

wherein

[D+-N═N-M] or (T-N═N-Q+)

are each a subgroup of Q of formula (1) as defined above;

    D+ is a radical of a cationic, aromatic, substituted or unsubstituted heterocyclic compound,
    M is a biradical of an aromatic substituted or unsubstituted compound,
    T is a radical of an aromatic substituted or unsubstituted compound,
    Q+ is a biradical of a cationic, aromatic, substituted or unsubstituted heterocyclic compound,
    and
    R is the radical of an unsubstituted or substituted, water-soluble aliphatic or aromatic amine,
    An is an anion.


Preferably,

    D+ is a radical of a cationic aromatic heterocyclic compound of formulae (43) or (44),






wherein p is 0, and

    (d1) is a bond of the five-membered ring of formula (43) with an azo group of formulae (42a),
    (d2) is a bond of the six-membered ring of formula (44) with an azo group of formulae (42a); and
    Q+ is a biradical of a cationic aromatic heterocyclic compound of formulae (43) or (44), wherein p is 1
    (d1) is a bond of the five-membered ring of formula (43) with an azo group of formulae (42b),
    (q1) is a bond of the five-membered ring of formula (43) with an azo group of formulae (42b); and
    (d2) is a bond of the six-membered ring of formula (44) with an azo group of formulae (42b),
    (q2) is a bond of the six-membered ring of formula (44) with an azo group of formulae (42b); and
    M is a biradical of formulae (45) or (46),






    wherein q is 1, and
    (d3) and (q3) are bonds of the aromatic compound of formula (45) with the azo group of formula (42a);
    (d4) and (q4) are bonds of the aromatic compound of formula (46) with the azo group of formula (42a); and
    T is a radical of formulae (45) or (46),
    wherein q is 0; and
    (d3) is a bond of the aromatic compound of formula (45) with the azo group of formula (42b);
    (d4) is a bond of the aromatic compound of formula (46) with the azo group of formula (42a);
    wherein
    X1 is N or a radical of CR66,
    X2 is N or a radical of CR67,
    X3 is N or a radical of CR68,
    X4 is N or a radical of CR69,
    X5 is N or a radical of CR70,
    X6 is N or a radical of CR71,
    X7 is N or a radical of CR72,
    X8 is N or a radical of CR73,
    Z1 is O or S or a radical of NR46,
    Z2 is N or a radical of CR47,
    Z3 is N or a radical of CR48,
    Z4 is N or a radical of CR49,
    n is 0 or 1,
    E is —O—, —S—, —(SO2)—, CR62 or a radical of —(NR63)—;
    G is —O—, —S—, —(SO2)—, CR64 or a radical of —(NR65)
    R42, R43, R44, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73 and R74 are independently from each other hydrogen, C1–C16alkyl, which is saturated or unsaturated, linear or branched, substituted or unsubstituted, or interrupted or uninterrupted with heteroatoms, such as, by hydroxy, nitril, amino, C1–C2 alkoxy, (poly)-hydroxy-C2–C4-alkoxy, di-C1–C2 alkylamino, carboxylic acid, sulfonic acid; a radical of phenyl, which substituted or unsubstituted; a radical of carboxylic acid; a radical of sulfonylamino, S, NH or N(C1–C4alkyl), O, SO2, COO, OCO, NHCO, CONH, CON(C1–C4alkyl) or N(C1–C4alkyl)CO; or are independently from each other an aliphatic or aromatic, substituted, preferably halogen substituted, or unsubstituted C3–C6carbon cycle, wherein the carbon atoms of the ring can be replaced by oxygen, nitrogen, sulfur or SO2;
    R42 with R47, R43 with R44 and R48 with R49 can build up an aromatic carbon cycle, such as phenyl;
    R42 and R47 are independently from each other hydrogen; C1–C4alkyl, which is saturated or unsaturated, linear or branched, unsubstituted or substituted by hydroxy, nitril, amino, C1–C2 alkoxy, (poly)-hydroxy-C2–C4-alkoxy, di-C1–C2 alkylamino, carboxylic acid, sulfonic acid; a radical of phenyl, which substituted or unsubstituted; a radical of carboxylic acid; a radical of sulfonylamino;
    R42 with R47, R43 with R44 and R48 with R49 can build up an aromatic carbon cycle, such as phenyl.


Preferably R42, R43, R44, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73 and R74 are independently from each other hydrogen, C1–C4alkyl, which is saturated or unsaturated, linear or branched, unsubstituted or substituted by hydroxy, nitril, C1–C2alkoxy, (poly)-hydroxy-C2–C4-alkoxy, amino, di-C1–C2 alkylamino, carboxy, sulfonyl, halogen such as chloride, fluoride or bromide;

    a radical of carboxylic acid; or a radicals of sulfonylamino; a radical of sulfonic acid; a radical of C1–C2 alkoxy; a (poly)-hydroxy-C1–C2-alkoxy; a radical of amino; a radical of di-C1–C2 alkylamino; (poly)-hydroxy-C2–C4-alkoxy; or are independently from each other an aromatic, substituted, prefereably halogen substituted, or unsubstituted C6carbon ring.


More preferably R2, R3, R4, R7, R8, R9, R10, R11, R12, R13, R14R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32 and R33 are independently from each other hydrogen, C1–C4alkyl, which is saturated or unsaturated, linear or branched, unsubstituted or substituted by hydroxy, nitril, nitrilamino, di-C1–C2 alkylamino; a radical of carboxylic acid; a radical of C1–C2 alkoxy; a radical of amino; a radical of di-C1–C2 alkylamino; a (poly)-hydroxy-C2–C4-alkoxy; or are independently from each other an aromatic, substituted, preferably halogen substituted, or unsubstituted C6ring.
Most preferred R42, R43, R44, R47, R48, R49, R50, R51, R52, R53, R54, R55, R56, R57, R58, R59, R60, R61, R62, R63, R64, R65, R66, R67, R68, R69, R70, R71, R72, R73 and R74 are independendently from each other hydrogen, methyl, phenyl, 2-hydroxymethyl, nitril, carboxylic acid, methoxy, ethoxy, 2-hydroxyethyloxy, a radical of amino, methylamiono, dimethylamino, 2-hydroxyethylamino.
Preferably R42 and R47 are independently from each other hydrogen; radical of phenyl; a radical of C1–C4alkyl, which is unsubstituted or substituted by hydroxy, nitril, amino, di-C1–C2 alkylamino, carboxylic acid.
More preferably R42 and R47 are independently from each other hydrogen, methyl, phenyl, 2-hydroxymethyl, nitril or a carboxylic acid.
R41, R45 and R46 are independently from each other a radical of C1–C8alkyl, which is saturated or unsaturated, linear or branched, unsubstituted or substituted by hydroxy, amino, C1–C2 alkoxy, (poly)-hydroxy-C2–C4-alkoxy, di-C1–C2 alkylamino, carboxylic acid, sulfonic acid; a radical of phenyl, which substituted or unsubstituted; a radical of carboxylic acid; a radical of sulfonylamino.
Preferably R41, R45 and R46 are independently from each other a radical of C1–C4alkyl, which is saturated or unsaturated, linear or branched, unsubstituted or substituted by hydroxy, amino, C1–C2 alkoxy, di-C1–C2 alkylamino, carboxylic acid, sulfonic acid.
More preferably R41, R45 and R46 are independently from each other methyl, ethyl, 2-hydroxyethyl, 1-carboxymethyl, 2-carboxyethyl, 2-sulfonylethyl.
More preferably D+ is a radical of a cationic compound of the following formulae




wherein R41, R42, R45, R46 and R47 have the same meaning and preferencesas described above.

Most preferably, D+ is a radical of a cationic compound of the following formulae




Preferably M is a biradical of the below given formulae




wherein E, R50, R51, R52 have the same definition and preferences as given above; and

    more preferably M is a biradical of the below given formulae






Preferably, Q+ is a biradical of a cationic compound of the following formulae




Suitable compounds of T are radicals of the below given formulae




wherein E, R50 and R56 have the same definition and preferences as described above; and

    preferably, T is a radical of the below given formulae






They are, for example, acylacetarylamides, phenols, naphthols, pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines, aminopyridines, pyrimidones, naphthylamines, aminothiazoles, thiophenes or hydroxypyridines.
More preferred is the further preferred embodiment of the process of the present invention, which relates to cationic capped diazonium compound elected from the group of compounds of the following formulae




wherein

    E, R41, R42, R46, R47, R50, B, An and n have the same definition and preferences as described before.


Most preferred is the further preferred embodiment of the process of the present invention, which relates to cationic capped diazonium compound elected from the group of compounds of the following formulae




wherein

    E, R41, R42, R46, R47, R50, B, An and n have the same definition and preferences as described before, and especially most preferred n is 0.


Especially preferred is the further preferred embodiment of the process of the present invention, which relates to cationic capped diazonium compound elected from the group of compounds of the following formulae













Further,
preferred is a process of the present invention for the coloration of keratin fiber with capped diazotised compounds of formulae (1), (2), (3), (4) and/or (5) comprising


    
    
        a) applying, under alkaline conditions, at least one with capped diazotised compound of formulae (1), (2), (3), (4) and/or (5) and optionally at least one direct dye and optionally at least one developer compound and optionally a coupler; and optionally an oxidizing agent, which optionally contains at least one direct dye, and
        b) then contacting the keratin fibers with the mixture as prepared in step a),
        c) then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye.
    
    


More preferred is a process for dyeing keratin fibres with at least one capped diazotized compound of formulae (1), (2), (3), (4) and/or (5), which comprises

    
    
        a) applying, under alkaline conditions, at least one capped diazotized compound of formulae (1), (2), (3), (4) and/or (5) and at least one direct dye, a base and an oxidizing agent, and
        b) then contacting the keratin fibers with the mixture as prepared in step a),
        c) then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye.
    
    


Further, preferred is a process for the coloration of keratin fiber with capped diazotised compounds of formulae (1), (2), (3), (4) and/or (5) comprising

    
    
        a) applying, under alkaline conditions, at least one with capped diazotised compound of formulae (1), (2), (3), (4) and/or (5) and optionally at least one direct dye and optionally at least one developer compound, and optionally at least one autooxidable compound, and
        b) then contacting the keratin fibers with the mixture prepared in step a),
        c) then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye.
    
    


A further suitable process for the two-step direct dyeing of keratin fibres, which can be used in combination with the method of colouring according to the present invention, is characterized in that,

    
    
        a) contacting the keratin fibers with an oxidizing agent or an oxidizing agent containing composition,
        b) then contacting the keratin fibers with at least one capped diazotised compound of formulae (1), (2), (3), (4) and/or (5) and optionally a direct dye or/and optionally an oxidizing agent free composition,
        c) then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye.

or

        a) contacting the keratin fibers with at least one capped diazotised compound of formulae (1), (2), (3), (4) and/or (5) and optionally a direct dye or/and optionally an oxidizing agent free composition,
        b) then contacting the keratin fibers with an oxidizing agent or an oxidizing agent containing composition,
        c) then adjusting the pH in the range of 5 to 2 by treatment with acid, optionally in the presence of a further dye.
    
    


The present invention relates also to the colouration of hair with a dye, which results by the method according to the present invention, and at least one other dye.
The multiplicity of shades of the dye, which results by the method according to the present invention, can be increased by combination with other dyes.
The present invention relates also to the coloration of hair with a dye of formula (1), (2), (3), (4) and/or (5) according to the present invention, and at least a single further dye.
The dye of formula (1), (2), (3), (4) and/or (5) of the present invention can be combined with dyes of the same or different class of dyes, especially with direct dyes, oxidation dyes; dye precursor combinations of a coupler compound and a diazotized compound; and/or cationic reactive dyes.
Direct dyes are natural or synthetic; they are uncharged, cationic or anionic, such as acid dyes.
Oxidation dye denotes also for oxidation dye precursors, which are from the group of the developer and coupler compounds. Wherein the coupler compounds denotes also to the addition salts thereof with an acid.
In the context of the present invention the single classes of dyes comprise the dyes defined in the Color Index of the Society of Textile Chemist and Colorist.
Further, in the context of the present invention, combinations, compositions, formulation, methods and processes comprise at least a single compound of formula (1), (2), (3), (4) and/or (5)
One preferred embodiment of the present invention is the combination of at least a single compound of formula (1), (2), (3), (4) and/or (5) with a direct dye, which are described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248–250, and in “Europäisches Inventar der Kosmetikrohstoffe”, 1996, published by The European Commission, obtainable in diskette form from the Bundesverband der deutschen Industrie-und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim.
Further preferred cationic dyes for the combination with a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention are described in the following references

    in WO 95/01772, especially on page 2, line 7 to page 4, line 1, and especially on page 4, line 35 to page 8, line 21 and on pages 11 to 27, or
    in WO 01/66646, especially on page 1, line 18 to page 3, line 16, and preferred from page 16, line 20 to page 22, and cationic dyes as described on pages 10 to 17, or
    in EP 970 685, especially on page 2, line 44 to page 9, line 56 and preferably on page 9, line 58 to page 48, line 12.


More preferred for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are cationic dyes, such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or cationic dyes as described in WO 01/66646, especially cationic dye of example 4, or cationic dyes as described in WO 02/31056, especially cationic dye of example 6, compound of formula 106, or cationic dye of formula (3) as described in EP-A-714,954 or yellow cationic dyes of formula (I) as described in WO 03/060015.
Further preferred for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are cationic nitroaniline and anthraquinone dyes for the combination a compound of formula (1), (2), (3), (4) and/or (5) according to the invention, for example those described in the following patent specifications: U.S. Pat. No. 5,298,029, especially in column 2, line 33 to column 5, line 38; U.S. Pat. No. 5,360,930, especially in column 2, line 38 to column 5, line 49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 to column 5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line 23 to column 5, line 15; U.S. Pat. No. 5,135,543, especially in column 4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2, line 40 to page 3, line 26; U.S. Pat. No. 5,486,629, especially in column 2, line 34 to column 5, line 29; and EP-A-758 547, especially on page 7, line 48 to page 8, line 19.
In addition, preferred are combinations of a compound of formula (1), (2), (3), (4) and/or (5) according to the invention with further cationic dyes or with other dyes. Preferred are mixtures as given in the below references, with the proviso that one cationic dye is replaced by a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention.

    mixtures of at least two cationic dyes as described in WO 95/01772, especially on page 8, line 34 to page 10, line 22 with the given preferences, or
    combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one cationic dye as described in EP 998,908, especially on page 2, line 34 to line 42, with preferred Pyrazolo-[1,5-a]-pyrimidines as described in EP 998,908, especially on page 2, line 48 to page 4, line 3, and with preferred cationic direct dyes as described in EP 998,908, especially on page 4, line 22 to page 47, line 24, or
    combinations of cationic dyes as described in FR-2788432, especially on page 53, line 1 to page 63, line 23, especially a combination of cationic dyes with Arianors in FR-2788432, especially on pages 51 to 52, or especially a combination with at least one Basic Brown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or at least one Basic Yellow 57, and/or at least one Basic Blue 99, or
    combinations of direct dyes and/or an oxidation dye and oxidizing agents in the form of permanent-wave fixing solution, especially with direct dyes as described in DE-A-19 713 698, especially page 4, line 65 to page 35, line 59, or
    combinations of cationic dyes and an oxidation dye of the developer compound type and oxidizing agents as described in EP 850 638, especially on page 2, line 27 to page 7, line 46 and preferred on page 7, line 20 to page 9, line 26, or
    combinations of an extemporaneous mixture of a composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, and of a composition (B), in powder form, containing one or more direct dye, preferably cationic, optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agent as described in U.S. Pat. No. 6,190,421, especially in column 2, lines 2 to 1, and preferably with oxidation dye precursors as described in column 2, line 35 to column 5, line 13, and preferably with direct dyes as described in column 5, line 30 to column 7, line 14, or
    a ready-to-use composition comprising, at least one oxidation base, at least one cationic direct dye and at least one enzyme of 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme as described in U.S. Pat. No. 6,228,129, especially in column 26, line 26 to column 27, line 9 with cationic direct dyes as described in column 8, line 17 to column 13, line 65, especially those as described in column 20, line 11 to line 19, in column 23, line 61 to column 24, line 25, or
    compositions of at least one direct cationic dye and at least one nitrated benzene dye as described in WO 99/20235 on page 2, line 1 to page 7, line 9, and on page 39, line 1 to page 40b line 11, with cationic direct dyes as described on page 8, line 12 to page 25 line 6, and nitro benzene direct dyes as described on page 26, line 7 to page 30, line 15, or
    compositions of at least one direct cationic dye and at least one autooxidisable oxidation dye, especially benzene, indol and indoline derivatives as described in WO 99/20234, with in preferred direct dyes as given on page 2, line 17 to page 26, line 4, and autooxidisable oxidation dye as described especially on page 26, line 10 to page 28, line 15, or
    oxidation dyeing compositions of at least one direct dye and at least one meta-Aminophenol derivative and at least one developer compound and an oxidizing agent as described in EP 850 636, especially on page 5, line 41 to page 7, line 52, and preferably on page 19, line 50 to page 22, line 12, with preferred direct dye as described on page 18, lines 1 and 2 in connection with page 7, line 53 to page 17, line 55, and with preferred meta-Aminophenol derivatives as described on page 7, line 47 to line 52, and with preferred developer compounds as described on page 6, line 10 to page 7, line 46, or
    oxidation dyeing compositions of at least one direct dye and at least one developer compound selected from the group of para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, and at least one coupler compound selected from the group of meta-Diphenols and an oxidizing agent, as described in EP-A-850 637, especially on page 6, line 50 to page 8, line 44,
    oxidation dyeing compositions with cationic couplers, as described in WO 99/48856, especially on page 9, line 16 to page 13, line 8, and page 11, line 20 to page 12, line 13, or cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives, as described in EP 998 908, especially on page 2, line 34 to page 4, line 23, or
    arianoren and/or oxidative dyes, as described in FR-2 788 432, especially on page 2, line 16 to page 3, line 16, and page 5, line 19 to page 14, line 8, and combinations with cationic dyes as described on page 14, line 23 and following, or
    oxidative dye precursors (unsaturated aldehyde and coupler compounds), as described in German Patent Application 197 172 24, especially unsaturated aldehydes as described on page 2, line 50 to line 66 and page 3 line 8 to line 12 are used as developer compounds, and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptids, aromatic hydroxy compounds, CH-active compounds as described on page 3, line 42 to page 5 line 25 are used as coupler compounds.


Further preferred for the combination with a compound of formula (1), (2), (3), (4) and/or (5) are cationic azo dyes, e.g. according to GB-A-2 319 776, as well as the oxazine dyes described in DE-A-29 912 327 and mixtures thereof with the other direct dyes mentioned therein.
More preferred for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or as described in WO 01/66646, especially cationic dye of example 4, or as described in WO 02/31056, especially cationic dye of example 6, compound of formula 106.
Especially preferred for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are direct dye mixtures comprising a dye of formula (1), (2), (3), (4) and/or (5) of WO 01/66646, especially a direct dye of example 4, and/or or a dye of formula (2) of WO 02/31056, especially a direct dye of example 6, and/or Basic Yellow 87, and/or Basic Red 51, and/or Basic Orange 31.
No particular limitation is imposed on the acid dye used in the present invention so far as it is a water-soluble acid dye.
A further embodiment of the present invention concerns the combination of a compound of formula (1), (2), (3), (4) and/or (5) according to the invention with acid dyes, for example from the group of the compounds known by the international names (Color index), or trade names.
Preferred acid dyes for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are described in U.S. Pat. No. 6,248,314, they include Red Color No. 120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green Color No. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401 and Purple Color No. 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205.
These acid dyes may be used either single or in any combination thereof.
Preferably they are incorporated in dyeing composition for human hair in a proportion of 0.001–5% by weight (hereinafter indicated merely by “%”), particularly 0.005–4%, more particularly 0.2–3% based on the total weight of the composition, from the viewpoint of practical use in that a sufficient hair-dyeing effect is achieved, and the hand skin is scarcely smeared.
A further embodiment of the present invention concerns the combination of a compound of formula (1), (2), (3), (4) and/or (5) according to the invention with uncharged dyes, for example from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols, phenazines, phenothiazines, bispyrazolons or bispyrazol aza derivatives or methines.
In addition, the present invention concerns the combination of a compound of formula (1), (2), (3), (4) and/or (5) according to the invention with oxidation dyes.
Suitable oxidation dyes are described for example in

    German Patent Application 19 94 450, especially on page 6, line 6 to line 64, or
    German Patent Application 19 959 479, especially in column 2, line 6 to column 3, line 11, or
    in the series “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 8, on pages 264–267 (oxidation dyes), or
    in German Patent Application 19 717 224; unsaturated aldehydes as described on page 2, line 50 to line 66 and on page 3 line 8 to line 12 are used as developer compounds, and primary and secondary amino group compounds, nitrogen-containing heterocyclic compounds, amino acids, oligopeptids, aromatic hydroxy compounds, CH-active compounds as described on page 3, line 42 to page 5 line 8 are used as coupler compounds.


Preferred oxidation dye precursors of the developer type for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are for example primary aromatic amines, which are substituted in the para- or ortho-position with a substituted or unsubstituted hydroxy- or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives, 2,4,5,6-tetraaminopyrimidin derivatives, or unsaturated aldehydes as described in German Patent Application 19 717 224, especially on page 2, line 50 to line 66 and on page 3 line 8 to line 12, or cationic developer compounds as described in WO 00/43367, especially on page, 2 line 27 to page 8, line 24, in particular on page 9, line 22 to page 11, line 6.
Also very suitable for a combination with a compound of formula (1), (2), (3), (4) and/or (5) according to the invention are developer dyes in their physiological compatible acid addition salt form, such as hydrochloride or sulfate. Developer dyes, which have aromatic OH substituents are also suitable in their salt form with base, such as alkalimetalphenolates.
Preferred developer compounds are:

    1,4-diamino-benzene (p-phenylendiamine), 1,4-diamino-2-methyl-benzene (p-toluylen-diamine), 1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene, 1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene, 4-phenylamino-aniline, 4-di-methylamino-aniline, 4-diethylamino-aniline, hydroxyethyl-p-phenylendiamine, 1-(2′-hydroxy-ethyl)-2,5-diaminobenzene, N,N-bis-(2-hydroxyethyl)-p-phenylendiamine, 4-[(2-methoxyethyl-)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine)hydrochloride, 1,4-diamino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 2-(2,5-diaminophenoxy)-ethanol, 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctan, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, hydroxyethyl-3,4-methylenedioxyaniline, p-aminophenol, o-aminophenol, m-aminophenol, 2-amino-6-methyl-phenol, 4-methylaminophenol sulfate, 4-amino-m-cresol, 6-amino-m-cresol, 6-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 2-amino-5-methyl-phenol, 4-amino-3-methylphenol, 4-methylamino-phenol, 2-aminomethyl-4-aminophenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-amino-2-(2-hydroxyethoxy)-phenol, 4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 2-hydroxymethylamino-4-aminophenol, bis-(4-aminophenyl)amine, 4-amino-3-fluorphenol, 2-hydroxymethyl-4-aminophenol, 4-amino-2-(diethylamino)-methyl)-phenol, 5-amino-salicylsäure, 2,5-diamino-pyridine, 2-amino-3-hydroxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, further 4,5-diaminopyrazol derivatives as described in EP 0 740 741 or WO 94/08970, especially 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4,5-diamino-1-(1-methylethyl)-1H-pyrazol, 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazol, 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazol, 4,5-diamino-1-methyl-1H-pyrazol.


More preferred developer dyes are p-phenylendiamine, p-toluylendiamine, p-aminophenol, m-aminophenol, o-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylendiamine sulfate, 2-amino-4-hydroxyethylaminoanisole sulfate, hydroxyethyl-3,4-methylenedioxyaniline, 1-(2′-hydroxyethyl)-2,5-diaminobenzene, 2,6-dimethoxy-3,5-diamino-pyridine, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine)hydrochloride, hydroxyethyl-p-phenylendiamine sulfate, 4-amino-3-methylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol, 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4-amino-m-cresol, 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine sulfate.
Preferred oxidation dye precursors of the coupler type for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are for example m-phenylendiamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives.
Especially preferred coupler compounds for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are N-(3-dimethylamino-phenyl)-urea, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, 2,4-diaminophenoxyethanol, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, p-aminophenol, m-aminophenol and its derivatives, especially 5-amino-2-methylphenol, 5-(3-hydroxypropylamino)-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2′-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene, 3-(ethyl-amino)-4-methylphenol and 2,4-dichloro-3-aminophenol, or

    o-aminophenol and its derivatives, such as 5-methyl-2-(1-methylamino)-phenol, 3-di-methylamino-phenol, 3-diethylamino-phenol, 5-amino-2-methyl-phenol, 5-amino-4-fluor-2-methyl-phenol, 5-amino-4-methoxy-2-methyl-phenol, 5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlor-phenol, 5-amino-2,4-dichlor-phenol, 3-amino-2-methyl-phenol, 3-amino-2-chlor-6-methyl-phenol, 3-amino-phenol, 2-[(3-hydroxyphenyl)amino]-acetamide, 5-[(2-hydroxyethyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-phenol, 3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol, 2-(4-amino-2-hydroxyphenoxy)-ethanol, 5-[(3-hydroxypropyl)amino]-2-methyl-phenol, 3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol, 3-[(2-hydroxyethyl)amino]-2-methyl-phenol, m-diaminobenzene and its derivatives such as 2,4-diaminophenoxyethanol, 1,3-bis-(2,4diaminophenoxy)-propane, 1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene, 1,3-bis-(2,4-diaminophenyl)-propane, 3-[(2-aminoethyl)amino]-aniline, 1,3-di(2,4-diaminophenoxy)-propane, 1,3-diamino-2,4-dimethoxy-benzene, 2,6-bis(2-hydroxyethyl)amino-toluene, di(2,4-diaminophenoxy)-methane, 3-[di(2-hydroxyethyl)amino]-aniline, 2,6-bis-(2-hydroxyethyl-amino)-1-methylbenzene and 1-amino-3-bis-(2′-hydroxyethyl)-aminobenzene,
    o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene, 2,4-diamino-1-fluor-5-methyl-benzene, 2,4-diamino-1-methoxy-5-methyl-benzene, 1-(2-aminoethoxy)-2,4-diaminobenzene, 2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene, 2,4-diaminophenoxy-acetic acid, 2,4-diamino-1-ethoxy-5-methyl-benzene, 3-[(2-hydroxyethyl)amino]-aniline, 3,4-diamino-benzoic acid, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benzoxazine, 2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene, 2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene, 4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene 2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene, 3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine, 6-amino-3,4-dihydro-1,4(2H)-benz-oxazine,
    di- or trihydroxybenzene derivatives such as resorcine, resorcinmonomethylether, 2-methylresorcine, 5-methylresorcine, 2,5-dimethylresorcine, 1-chloro-2,4-dihydroxy-benzene, 2-chlororesorcine, 4-chlororesorcine, 2,6-dihydroxyethylaminotoluene, 1,2-dichlor-3,5-dihydroxy-4-methyl-benzene, 1,5-dichlor-2,4-dihydroxy-benzene, 1,3-dihydroxy-2-methyl-benzene, pyrogallol and 1,2,4-trihydroxybenzene,
    pyridine derivatives such as 2,6-diamino-pyridine, 2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 5-amino-4-chloro-2-methyl-phenol, 3-diamino-6-methoxy-pyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2,6-diamino-3,5-dimethoxy-pyridine, and 3,5-diamino-2,6-dimethoxypyridine,
    naphthaline derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthaline, 1,6-dihydroxynaphthaline, 1,7-dihydroxynaphthaline, 1,8-dihydroxynaphthaline, 2,7-dihydroxynaphthaline and 2,3-dihydroxynaphthaline, 2-methyl-1-naphthol-acetat,
    morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,
    chinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydrochinoxaline,
    pyrazol derivatives such as -phenyl-3-methylpyrazol-5-one, 3-methyl-1-phenyl-5-pyrazolone,
    indol derivatives such as 4-hydroxyindol, 5-hydroxy-indol, 6-hydroxyindol and 7-hydroxyindol, 2,3-indolindione, 5,6-dihydroxy-indol, 5,6-dihydroxy-indoline,
    methylendioxybenzene derivates such as 1-hydroxy-3,4-methylendioxybenzene, 1-amino-3,4-methylendioxybenzene and 1-(2′-hydroxyethyl)-amino-3,4-methylendioxybenzene, 3,4-methylendioxy-phenol, 3,4-methylendioxy-aniline, 5-[(2-hydroxyethyl)amino]-1,3-benzodioxol, 6-brom-1-hydroxy-3,4-methylendioxy-benzene, or
    cationic coupler compounds as described in FR 2 794 644, especially on page 11, line 20 to page 15, line 34, and on page 17, lines 4 to 12, page 178, line 33 to page 18, line 24.


More especially preferred coupler compounds for a combination with a cationic dye of formula (1), (2), (3), (4) and/or (5) are toluene-2,5-diamine sulfate, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthaline, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcine, 2-chloro-6-methyl-3-aminophenol, 2,6-di-hydroxyethylaminotoluene, 2-methyl-5-dihydroxyethylaminophenol, 2,4-diaminophenoxy-ethylol hydrochloride, 2-methylresorcine, 5-methylresorcine, 2,5-dimethylresorcine, 3,4-methylenedioxyphenol, 2-amino-4-hydroxyethylaminoanisole sulfate, 2,6-di-(beta-hydroxy-ethylamino)-toluene, 4-amino-2-hydroxytoluene, 6-hydroxyindol, 2-amino-3hydroxypyridine, 2,6-dimethoxy-3,5-pyridinediamine hydrochloride and 2,6-dihydroxy-3,4-dimethylpyridine.
Most preferred coupler compounds for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are 2-chloro-6-methyl-3-aminophenol, 5-amino-2-methylphenol, 2-amino -3-hydroxypyridine, 2,6-di-(beta-hydroxyethylamino)-toluol, 2-methylresorcine and 1-naphthol.
Further, preferred for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are:

    the developer/-coupler combination 2,4,5,6-Tetraaminopyrimidine and 2-Methylresorcine are preferred for assessing of red shades, or
    p-Toluenediamine and 4-Amino-2-hydroxytoluene for assessing of blue-violet shades, or
    p-Toluenediamine and 2-Amino-4-hydroxyethylaminoanisole for assessing of blue shades, or
    p-Toluenediamine and 2,4-Diamino-phenoxyethynol for assessing of blue shades, or
    3-Methyl-4-aminophenol and 4-Amino-2-hydroxytlouene for assessing of orange shades, or
    p-Toluenediamine and resorcine for assessing of brown-green shades, or
    p-Toluenediamine and 1-Naphthol for assessing of blue-violet shades, or
    p-Toluenediamine and 2-methylresorcine for assessing of brown-gold shades.


Further, one preferred embodiment of the present invention concerns the combination of a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention with autooxidizable compounds, such as, for example benzene, indol, or indoline, especially 5,6-dihydroxyindol or 5,6-dihydroxyindoline derivatives as described in WO 99/20234, especially on page 26, line 10 to page 28, line 15, or in WO 00/28957 on page 2, third paragraph.
Preferred autooxidizable benzene derivatives for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are:

    1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene, 2,4-diamino-6-methylphenol, 2-amino-4-methylaminophenol, 2,5-diamino-4-methyl-phenol, 2,6-diamino-4-diethylamino-phenol, 2,6-diamino-1,4-dihydroxybenzen, and the salts of these compounds, which are accessible with acid.


Preferred autooxidizable indol derivatives for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are:

    5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol, 3-methyl-5,6-dihydroxyindole, 1-methyl-5,6-dihydroxyindol, 2,3-dimethyl-5,6-dihydroxyindol, 5-methoxy-6-dihydroxyindol, 5-acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of 5,6-dihydroxyindol-2-carbonacid, and the salts of these compounds, which are accessible with acid.


Preferred autooxidizable indoline derivatives for a combination with a compound of formula (1), (2), (3), (4) and/or (5) are:

    5,6-dihydroxyindoline, 1-methyl-5,6-dihydroxyindoline, 1-ethyl-5,6-dihydroxyindoline, and the salts of these compounds, which are accessible with acid.


A compound of formula (1) according to the present invention can also be combined with at least two different developers and at least one coupler compound, or with at least two different couplers and at least one developer compound. Such combinations are for example described in German Patent Application 197 172 24, especially on page 3, line 31 to page 5, line 8.
In addition, a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention may also be combined with naturally occurring dyes, such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedre and alkanet root. Such coloring methods are described, for example, in EP-A-404 868, especially on page 3, line 55 to page 4, line 9.
Further, a compound of formula (1), (2), (3), (4) and/or (5) may also be combined with capped diazotised compounds.
The present invention also describes formulations, which are used for the coloration of keratin fibers, especially human hair.
The formulations are applicable on human hair in different technical forms. The specific technical form may be chosen in view of the envisaged application and/or dye or dye composition. Technical forms of formulation are for example a solution, especially a thickened watery or watery alcoholic solution, a cream, foam, shampoo, powder, a gel, or an emulsion.
Preferred forms of formulations are ready to use compositions or a multi-compartment dyeing device or ‘kit’ or any of the multi-compartment packaging systems with compartments as described for example as described in U.S. Pat. No. 6,190,421, column 2, lines 16 to 31.
It is of advantage to prepare compositions of dyes or cooresponding precursors, which are not stable to reduction, with oxidizing agent free compositions just before the dyeing process.
One preferred embodiment of the present invention concerns the formulation of compounds, especially those of formula (1), (2), (3), (4) and/or (5) in powder form.
The compositions, which are used for the coloration of keratin fibers, especially human hair, according to the invention may furthermore comprise any active ingredient, additive or adjuvant known for such preparations.
Adjuvants that are suitable for such formulations are in general customary in the field hair-coloring, such as for example surfactants or tensides, solvents, bases, acids, perfumes, polymeric adjuvant, thickeners and light stabilisers.
Preferred combinations of the compositions according to the invention with adjuvant used in the coloring of hair, are

    combination of direct dyes with oxidizing agents to achieve lightened coloration; wherein oxidizing agents especially described in WO 97/20545, especially page 9, lines 5 to 9,
    combination of direct dyes and/or an oxidation dye and oxidizing agents in the form of permanent-wave fixing solution, especially oxidizing agents as described in DE-A-19 713 698, especially page 4, lines 52 to 55, or EP-A-1 062 940, especially page 6, lines 41 to 47, (and in the equivalent WO 99/40895),
    oxidation dyes in the presence of oxidoreductase enzyme, as described in WO 99/17730, especially page 4, line 11 to page 13, line 28, and WO 99/36034, especially pages 3 to 15, combination of cationic dyes with polyols or polyethers; polyols or polyethers as described in EP-A-962 219, especially page 27, lines 14 to 38,
    thickening polymers, as described in EP-A-970 684, especially page 48, line 16 to page 51, line 4,
    sugar-containing polymers, as described in EP-A-970 687, especially page 28, line 17 to page 29, line 23,
    quaternary ammonium salts, as described in WO 00/10517, especially page 44, line 16 to page 46, line 23,
    anionic surfactants, as described in WO 00/10518, especially page 45, line 11 to page 48, line 3,
    non-ionic surfactants, as described in WO 00/10519, especially page 45, line 11 to page 50, line 12, or
    silicones, as described in WO 00/12057, especially page 45, line 9 to page 55, line 2. oxidative agent or laser and direct dyes, as described in EP-920 856, especially on page 2, line 31 to page 53 line 36, and on page 49, line 38 to page 50, line 41, with direct dyes as described on page 3, line 54 to page 48, line 52, or
    direct dyes in the presence of cationic amphotere, substantive polymer, as described in EP-953 334, especially on page 2, line 39 to page 7, line 44, with direct dyes as described on page 8, line 54 to page 27, line 16, and polymers as described on page 27, line 17 to page 30, line 14, or
    direct dyes formulations with polymer thickener on the basis of acrylic acid, as described in EP-970 685, especially on page 2, line 39 to page 10, line 1, with direct dyes as described on page 10, line 7 to page 48, line 15, with polymers as described on page 48, line 17 to page 49, line 28.


The coloring composition according to the invention in many cases comprises at least one surfactant. Suitable surfactants are anionic, zwitterionic, ampholytic, non-ionic and cationic surfactants. In many cases, however, it has proved advantageous to select the surfactants from anionic, zwitterionic and non-ionic surfactants.
Anionic surfactants suitable for use in the coloring compositions according to the invention include all anionic surface-active substances that are suitable for use on the human body. Such substances are characterised by an anionic group that imparts water solubility, for example a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic alkyl group having approximately from 10 to 22 carbon atoms. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and also hydroxy groups may be present in the molecule. The following are examples of suitable anionic surfactants, each in the form of sodium, potassium or ammonium salts or mono-, di- or tri-alkanolammonium salts having 2 or 3 carbon atoms in the alkanol group:

    linear fatty acids having from 10 to 22 carbon atoms (soaps),
    ether carboxylic acids of formula R—O—(CH2—CH2—O)x—CH2—COOH, in which R is a linear alkyl group having from 10 to 22 carbon atoms and x=0 or from 1 to 16,
    acyl sarcosides having from 10 to 18 carbon atoms in the acyl group,
    acyl taurides having from 10 to 18 carbon atoms in the acyl group,
    acyl isothionates having from 10 to 18 carbon atoms in the acyl group,
    sulfosuccinic mono- and di-alkyl esters having from 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in the alkyl group and from 1 to 6 oxyethyl groups,
    linear alkane sulfonates having from 12 to 18 carbon atoms,
    linear α-olefin sulfonates having from 12 to 18 carbon atoms,
    α-sulfo fatty acid methyl esters of fatty acids having from 12 to 18 carbon atoms,
    alkyl sulfates and alkyl polyglycol ether sulfates of formula R′—O(CH2—CH2—O)x′—SO3H, in which R′ is a preferably linear alkyl group having from 10 to 18 carbon atoms and x′=0 or from 1 to 12,
    mixtures of surface-active hydroxysulfonates according to DE-A-3 725 030, especially page 3, lines 40 to 55,
    sulfated hydroxyalkylpolyethylene and/or hydroxyalkylenepropylene glycol ethers according to DE-A-3 723 354, especially page 4, lines 42 to 62,
    sulfonates of unsaturated fatty acids having from 12 to 24 carbon atoms and from 1 to 6 double bonds according to DE-A-3 926 344, especially page 2, lines 36 to 54,
    esters of tartaric acid and citric acid with alcohols which are addition products of approximately from 2 to 15 molecules of ethylene oxide and/or propylene oxide with fatty alcohols having from 8 to 22 carbon atoms, or
    anionic surfactants, as described in WO 00/10518, especially page 45, line 11 to page 48, line 3.


Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having from 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C8–C22carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.
Surface-active compounds that carry at least one quaternary ammonium group and at least one —COO(−) or —SO3(−) group in the molecule are termed zwitterionic surfactants. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name cocoamidopropyl betaine.
Ampholytic surfactants are to be understood as meaning surface-active compounds that, in addition to a C8–C18-alkyl or -acyl group, contain at least one free amino group and at least one —COOH or —SO3H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference is given are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12–C18acylsarcosine.
Non-ionic surfactants are described in WO 00/10519, especially page 45, line 11 to page 50, line 12.
Non-ionic surfactants contain as the hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups.
Such compounds are, for example:

    addition products of from 2 to 30 mol of ethylene oxide and/or from 0 to 5 mol of propylene oxide with linear fatty alcohols having from 8 to 22 carbon atoms, with fatty acids having from 12 to 22 carbon atoms and with alkylphenols having from 8 to 15 carbon atoms in the alkyl group,
    C12–C22 fatty acid mono- and di-esters of addition products of from 1 to 30 mol of ethylene oxide with glycerol,
    C8–C22alkyl-mono- and -oligo-glycosides and ethoxylated analogues thereof,
    addition products of from 5 to 60 mol of ethylene oxide with castor oil and hydrogenated castor oil,
    addition products of ethylene oxide with sorbitan fatty acid esters,
    addition products of ethylene oxide with fatty acid alkanolamides.


Examples of cationic surfactants that can be used in the coloring compositions according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethy-lammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants that can be used in accordance with the invention are quaternised protein hydrolysates.
Also suitable in accordance with the invention are cationic silicone oils, such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilised trimethylsilylamodimethicone), Dow Corning 929 emulsion (comprising a hydroxylamino-modified silicone, which is also referred to as amodimethicone), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and also Abil®-Quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80), or silicones, as described in WO 00/12057, especially page 45, line 9 to page 55, line 2.
Alkylamidoamines, especially fatty acid amidoamines, such as the stearylamidopropyl-dimethylamine obtainable under the name Tego Amid® 18, are distinguished not only by a good conditioning action but also especially by their good biodegradability.
Quaternary ester compounds, so-called “esterquats”, such as the methyl hydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketed under the trademark Stepantex®), are also very readily biodegradable.
An example of a quaternary sugar derivative that can be used as cationic surfactant is the commercial product Glucquat® 100, according to CTFA nomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimonium chloride”.
The alkyl-group-containing compounds used as surfactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used.
The surfactants that are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of such addition products may either be products having a “normal” homologue distribution or products having a restricted homologue distribution. “Normal” homologue distribution is to be understood as meaning mixtures of homologues obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Restricted homologue distributions, on the other hand, are obtained when, for example, hydrotalcites, alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts. The use of products having restricted homologue distribution may be preferred.
Further preferred active ingredients of formulation according to thepresent invention, adjuvants and additives are as follows:

    non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate copolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl acetate copolymers and polysiloxanes,
    cationic polymers, such as quaternised cellulose ethers, polysiloxanes having quaternary groups, dimethyldiallylammonium chloride polymers, copolymers of dimethyldiallylammonium chloride and acrylic acid, as available commercially under the name Merquat® 280 and the use of which in hair coloring is described, for example, in DE-A-4 421 031, especially page 2, lines 20 to 49, or EP-A-953 334, especially page 27, line 17 to page 30, line 11, acrylamide/dimethyidiallylammonium chloride copolymers, diethyl-sulfate-quaternised dimethylaminoethyl methacrylate/vinylpyrrolidone copolymers, vinylpyrrolidone/imidazolinium methochloride copolymers,
    quaternised polyvinyl alcohol,
    zwitterionic and amphoteric polymers, such as, for example, acrylamido-propyl-trimethylammonium chloride/acrylate copolymers and octylacrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers,
    anionic polymers, such as, for example, polyacrylic acids, crosslinked polyacrylic acids, vinyl acetate/crotonic acid copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl acrylate/N-tert-butyl acrylamide terpolymers,
    thickeners, such as agar, guar gum, alginates, xanthan gum, gum arabic, karaya gum, locust bean flour, linseed gums, dextrans, cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl cellulose and carboxymethyl cellulose, starch fractions and derivatives, such amylose, amylopectin and dextrins, clays, e.g. bentonite or fully synthetic hydrocolloids such as, for example, polyvinyl alcohol,
    structuring agents, such as glucose and maleic acid,
    hair-conditioning compounds, such as phospholipids, for example soya lecithin, egg lecithin, and cephalins, silicone oils, and also conditioning compounds, for example such as those described in DE-A-19 729 080, especially page 2, lines 20 to 49, EP-A-834 303, especially page 2, line 18 to page 3, line 2, or EP-A-312 343, especially page 2, line 59 to page 3, line 11,
    protein hydrolysates, especially elastin, collagen, keratin, milk protein, soya protein and wheat protein hydrolysates, condensation products thereof with fatty acids and also quaternised protein hydrolysates,
    perfume oils, dimethyl isosorbitol and cyclodextrins,
    solubilisers, such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol,
    anti-dandruff active ingredients, such as piroctones, olamines and zinc Omadine,
    further substances for adjusting the pH value,
    active ingredients such as panthenol, pantothenic acid, allantoin, pyrrolidonecarboxylic acids and salts thereof, plant extracts and vitamins,
    cholesterol,
    light stabilisers and UV absorbers, as described, for example, in EP-A-819 422, especially page 4, lines 34 to 37,
    consistency regulators, such as sugar esters, polyol esters or polyol alkyl ethers,
    fats and waxes, such as spermaceti, beeswax, montan wax, paraffins, fatty alcohols and fatty acid esters,
    fatty alkanolamides,
    polyethylene glycols and polypropylene glycols having a molecular weight of from 150 to 50 000, for example such as those described in EP-A-801 942, especially page 3, lines 44 to 55,
    complexing agents, such as EDTA, NTA and phosphonic acids,
    swelling and penetration substances, such as polyols and polyol ethers, as listed extensively, for example, in EP-A-962 219, especially page 27, lines 18 to 38, for example glycerol, propylene glycol, propylene glycol monoethyl ether, butyl glycol, benzyl alcohol, carbonates, hydrogen carbonates, guanidines, ureas and also primary, secondary and tertiary phosphates, imidazoles, tannins, pyrrole,
    opacifiers, such as latex,
    pearlising agents, such as ethylene glycol mono- and di-stearate,
    propellants, such as propane-butane mixtures, NO2O, dimethyl ether, CO2 and air, and also
    antioxidants,
    polyols or polyethers, as described in EP-A-962 219, especially page 27, lines 14 to 38,
    
        thickening polymers, as described in EP-A-970 684, especially page 48, line 16 to page 51, line 4,
    
    
    sugar-containing polymers, as described in EP-A-970 687, especially page 28, line 17 to page 29, line 23,
    quaternary ammonium salts, as described in WO 00/10517, especially page 44, line 16 to page 46, line 23.


In the context of the present invention, oxidizing agents are understood to be any oxidizing agent customarily used for oxidative hair coloring, for example dilute hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic peroxides, such as urea peroxides, melamine peroxides, or alkalimetalbromat fixations are also applicable if a shading powder on the basis of semi-permanent, direct hair dyes is used.
Preferred oxidizing agent is hydrogen peroxide, preferred in about 2 to 30% by weight, more preferred in 3 to 20% by weight, and most preferred in 6 to 12% by weight of the total weight of a watery composition such as a solution, dispersion, a gel or emulsion.
The watery composition can comprise all customary components, which are used for the different applications of oxidizing agent compositions as described in K. Schrader, “Grundlagen und Rezepturen der Kosmetika”, 2. Aufl. (1989), page 832–840.
Further preferred oxidizing agents are

    oxidizing agents to achieve lightened coloration, as described in WO 97/20545, especially page 9, lines 5 to 9,
    oxidizing agents in the form of permanent-wave fixing solution, as described in DE-A-19 713 698, especially page 4, lines 52 to 55, and lines 60 and 61 or EP-A-1 062 940, especially page 6, lines 41 to 47, (and in the equivalent WO 99/40895).


An oxidizing agents may be present in the coloring compositions according to the invention preferably in an amount of from 0.01% to 6%, especially from 0.01% to 1%, based on the total dyeing composition.
Preferred catalysts are metal ions, such as for example Zn2+, Cu2+, Fe2+, Fe3+, Mn2+, Mn4+, Li+, Mg2+, Ca2+ and Al3+, preferably Zn2+, Cu2+ and Mn2+.
The metal ions are applicable in any physiological suitable salts form. Preferred salts are acetate, sulfate, halogenide, lactate and tartrate.
Alkalimetalsulfits, such as sodium-, potassium-, lithium-sulfite, Alkalimetaldisulfits, such as sodium-, potassium-, lithium-disulfite, ascorbic acid, tert.-Butylhydrochinon and Ammoniumthiolactat.
In general, the coloration with an oxidative agent is conducted in the presence of a base. Bases are for example ammonia, alkali metal carbonates, earth metal carbonates, alkanol amines, such as for example mono-, di- or triethanolamine, alkali metal hydroxides, earth metal hydroxides, compounds of the formula




wherein,

    R is a propyl residue, which substituted with OH or C1–C4-alkyl,
    R3, R4, R5 and R6 are independently or dependently from each other hydrogen, C1–C4-alkyl or hydroxy-(C1–C4)-alkyl.


Alkali metal is for example sodium, potassium or lithium.
Earth metal is for example magnesium or calcium.
Acids are inorganic or organic acids, such as hydrochloride, tartrat acid, citric acid, ascorbic acid and phosphor acid.
The use of UV absorbers can effectively protect natural and dyed hair from the damaging rays of the sun and increase the wash fastness of dyed hair.
Preferred UV absorbers the coloring compositions according to the invention are:

    cationic benzotriazole UV absorbers as for example described in WO 01/36396 especially on page 1, line 20 to page 2, line 24, and preferred on page 3 to 5, and on pages 26 to 37, or
    cationic benzotriazole UV in combination with antioxidants as described in WO 01/36396, especially on page 11, line 14 to page 18, or
    UV absorbers in combination with antioxidants as described in U.S. Pat. No. 5,922,310, especially in column 2, lines 1 to 3,
    UV absorbers in combination with antioxidants as described in U.S. Pat. No. 4,786,493, especially in column 1, 42 to column 2, line 7, and preferred in column 3, 43 to column 5, line 20, or
    combination of UV absorbers as described in U.S. Pat. No. 5,830,441, especially in column 4, lines 53 to 56, or
    combination of UV absorbers as described in WO 01/36396, especially on page 11, lines 9 to 13, or
    triazine derivatives provide effective UV protection as described in WO 98/22447, especially on page 1, line 23 to page 2, line 4, and preferred on page 2, line 11 to page 3, line 15 and most preferred on pages 6 to 7, and 12 to 16, or
    combination of the cosmetic formulations as described in WO 98/22447 with one or more than one further UV filter as described in the following patents:
    (Abbreviations T: table, R: row, Comp: compound, Ex: compound(s) of patent example, p=page; pp=pages)















EP 895776
Comp. in Rows 48–58, p 3; R 25 + 33, p 5


WO 9220690
Polymeric comp in Examples 3–6


EP 1000950
Comp. in Table 1, pp 18–21


EP 1060734
T 1–3, pp 11–14


EP 1059082
Ex 1; T 1, pp 9–11


EP 1008586
Ex 1–3, pp 13–15


EP 1005855
T 3, p 13


EP 1129695
Ex 1–7, pp 13–14


EP 967200
Ex 2; T 3–5, pp 17–20


EP 945125
T 3 a + b, pp 14–15


EP 924246
T 2, p 9


EP 911020
T 2, p 11–12


EP 916335
T 2–4, pp 19–41


EP 852137
T 2, pp 41–46


EP 858318
T 1, p 6


EP 826361
T 1, pp 5–6


EP 503338
T 1, pp 9–10


WO 9301164
T 1 + 2, pp 13–22


EP 823418
Ex 1–4, pp 7–8


WO 9714680
Ex 1–3, p 10


EP 1027883
Compound VII, p 3


EP 832641
Ex 5 + 6 p 7; t 2, p 8


US 5338539
Ex 1–9, pp 3 + 4


EP 517103
Ex 3, 4, 9, 10 pp 6–7


EP 1123934
T 3, p 10


EP 1027883
Comp 1–VI, p 3


EP 969004
Ex 5, T 1, pp 6–8


US 5801244
Ex 1–5, pp 6–7


EP 832642
Ex 22, T 3 pp, 10–15; T 4, p 16


US 5346691
Ex 40, p 7; T 5, p 8


(EP 570838)


EP 517104
Ex 1, T 1, pp 4–5; Ex 8, T 2, pp 6–8


WO 200149686
Ex 1–5, pp 16–21


EP 944624
Ex 1 + 2, pp 13–15


EP 933376
Ex 1–15, pp 10–21


EP 863145
Ex 1–11, pp 12–18


EP 780382
Ex 1–11, pp 5–7


EP 626950
All examples


EP 1081140
Ex 1–9, pp 11–16


WO 9217461
Ex 1–22, pp 10–20


WO 0168047
Tables on pp 85–96


EP 613893
Ex 1–5 +  15, T 1, pp 6–8


EP 1064922
Compounds 1–34, pp 6–14


EP 1028120
Ex 1–5, pp 5–13


EP 1008593
Ex 1–8, pp 4–5


EP 669323
Ex 1–3, p 5


EP 1108712
4,5-Dimorpholino-3-hydroxypyridazine


JP 2000319629
CAS Regno. 80142-49-0, 137215-83-9, 307947-82-6


EP 420707 B1
Ex 3, p 13 (80142-49-0)


US 5635343
All examples


EP 1167358
All examples









A preferred embodiment of the present invention concerns the combination of a compound of formula (1), (2), (3), (4) and/or (5) with UV absorbers.
Preferred UV absorbers are described in WO 98/22447.
Preferred cosmetic formulations contain a combination of a compound of formula (1) with UV absorbers and one or more than one further UV protective of the following substance classes:

    p-aminobenzoic acid derivatives, for example 4-dimethylaminobenzoic acid 2-ethylhexyl ester;
    salicylic acid derivatives, for example salicylic acid 2-ethylhexyl ester;
    benzophenone derivatives, for example 2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid derivative;
    dibenzoylmethane derivatives, for example 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;
    diphenylacrylates, for example 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl) 2-cyanoacrylate;
    3-imidazol-4-ylacrylic acid and esters;
    benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran derivatives, described in EP-A-582 189, U.S. Pat. No. 5,338,539, U.S. Pat. No. 5,518,713 and EP-A-613 893;
    polymeric UV absorbers, for example the benzylidene malonate derivatives described in EP-A-709 080;
    cinnamic acid derivatives, for example the 4-methoxycinnamic acid 2-ethylhexyl ester and isoamyl ester or cinnamic acid derivatives described in U.S. Pat. No. 5,601,811 and WO 97/00851;
    camphor derivatives, for example 3-(4′-methyl)benzylidene-bornan-2-one, 3-benzylidene-bornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer, 3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl sulfate, 3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1]heptane-1-methanesulfonic acid) and salts, 3-(4′-sulfo)benzylidene-bornan-2-one and salts; camphorbenzalkonium methosulfate;
    hydroxyphenyltriazine compounds, for example 2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine; 2,4-bis([4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl)-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(2′′-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2′′-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine; 2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;
    benzotriazole compounds, for example 2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;
    trianilino-s-triazine derivatives, for example 2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and the UV absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517 104, EP-A-507 691, WO 93/17002 and EP-A-570 838;
    2-phenylbenzimidazole-5-sulfonic acid and salts thereof;
    methyl o-aminobenzoates;
    physical sunscreens coated or not as titanium dioxide, zinc oxide, iron oxides, mica, MnO, Fe2O3, Ce2O3, Al2O3, ZrO2. (surface coatings: polymethylmethacrylate, methicone (methylhydrogenpolysiloxane CAS 9004-73-3), dimethicone, isopropyl titanium triisostearate (CAS 61417-49-0), metal soaps as magnesium stearate (CAS 4086-70-8), perfluoroalcohol phosphate as C9-15 fluoroalcohol phosphate (CAS 74499-44-8; JP 5-86984, JP 4-330007)). The primary particle size is an average of 15 nm-35 nm and the particle size in dispersion is in the range of 100 nm–300 nm.
    aminohydroxy-benzophenone derivatives disclosed in DE 10011317, EP 1133980 and EP 1046391
    phenyl-benzimidazole derivatives as disclosed in EP 1167358
    The UV absorbers described in “Sunscreens”, Eds. N. J. Lowe, N. A. Shaath, Marcel Dekker, Inc., New York and Basle or in Cosmetics & Toiletries (107), 50ff (1992) also can be used as additional UV protective substances.


Synergistic effects are observed when UV absorbers are used in combination with antioxidants. Examples of antioxidants that can be used are listened in WO 01/36396 (pages 11–18), U.S. Pat. No. 5,922,310 and U.S. Pat. No. 4,786,493.
Further preferred UV absorbers used in addition to the uncharged and cationic benzotriazole UV absorbers in the formulations without limitation to those listed in the following are benzophenone-type substances such as benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, benzophenone-5 (sodium salt) or benzotriazol-type substances such as benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-, monosodium salt; 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl-phenol; 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol, branched and linear.
Typical ingredients in the oil phase of emulsions (water in oil, oil in water or triple emulsion) or used in hair oils can be chosen from the following substance groups without limiting the kind of lipophilic ingredients to those substances:
Suitable cosmetic preparations may contain usually from 0.05 to 40% by weight, preferably from 0.1 to 20% by weight, based on the total weight of the composition, of one or more UV absorbers.
Preferred are the cosmetic preparations contain at least one triazine derivative UV absorber, for example, from 0.1 to 40% by weight, preferably from 0.1 to 20% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, and the cosmetic preparations contain at least one cationic benzotriazole from 0.05–20% by weight, preferred from 0.1–20% by weight, based on the total weight of the composition. Typical cosmetic formulations containing uncharged and/or cationic benzotriazoles and/or antioxidants alone or in combinations are rinse-off products (e.g. shampoos, hair rinses, conditioners etc.),
Suitable cosmetic formulations are:

    cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations or leave-on products such as sprays, creams, gels, lotions, mousses and oils, or
    hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hair-setting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile.


The final formulations listed may exist in a wide variety of presentation forms, for example:

    in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions,
    in the form of a gel,
    in the form of an oil, a cream, milk or lotion,
    in the form of a powder, a lacquer, a tablet or make-up,
    in the form of a stick,
    in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol,
    in the form of a foam, or
    in the form of a paste.


Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.
A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocoamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.
A further embodiment of the present invention concerns micronised UV absorbers, for example:

    wet-grinding with a hard grinding medium, for example zirconium silicate and a protective surfactant or a protective polymer in water or in a suitable organic solvent;
    spray-drying from a suitable solvent, for example aqueous suspensions or suspensions containing organic solvents, or true solutions in water, ethanol, dichloroethane, toluene or N-methylpyrrolidone etc.;
    by the expansion according to the RESS process (Rapid Expansion of Supercritical Solutions) of supercritical fluids (e.g. CO2) in which the UV filter or filters is/are dissolved, or the expansion of fluid carbon dioxide together with a solution of one or more UV filters in a suitable organic solvent;
    by reprecipitation from suitable solvents, including supercritical fluids (GASR process=Gas Anti-Solvent Recrystallisation/PCA process=Precipitation with Compressed Anti-solvents).


As grinding apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. The grinding is preferably carried out with a grinding aid, for example an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid.
The micronised UV absorbers so obtained usually have an average particle size that is from 0.02 to 2 μm, preferably from 0.05 to 1.5 μm, and more especially from 0.1 to 1.0 μm.
The UV absorbers can also be used dry in powder form. For that purpose the UV absorbers are subjected to known grinding methods, such as vacuum atomization, countercurrent spray-drying etc. Such powders have a particle size of from 0.1 μm to 2 μm. To avoid the occurrence of agglomeration, the UV absorbers can be coated with a surface-active compound prior to the pulverisation process, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, or an acrylate. The coloring compositions according to the invention may further comprise antimicrobial agents.
Preferred antimicrobial preservatives and antimicrobial actives used in formulations (in most cases the INCI name of the antimicrobial substances is mentioned):

    formaldehyde and paraformaldehyde, hydroxy biphenyls and its salts such as ortho-phenylphenol, zinc pyrithion, chlorobutanol, hydroxy benzoic acids and their salts and esters such as methyl paraben, ethyl paraben, propyl paraben, butyl paraben, dibromo hexamidine and its salts including isothionate (4,4′-hexamethylenedioxy-bis(3-bromo-benzamidine) and 4,4′-hexamethylenedioxy-bis(3-bromo-benzamidinium 2-hydroxyethanesulfonate), mercury, (aceto-O)phenyl (especially phenyl mercuric acetate) and Mercurate(2-),(orthoborate(3-)-O)phenyl, dihydrogene (especially phenyl mercuric borate), 1,3-bis(2-ethylhexyl)-hexahydro-5-methyl-5-pyrimidine (Hexetidin), 5-bromo-5-nitro-1,3-dioxan, 2-bromo-2-nitro-1,3-propandiol, 2,4-dichlorobenzyl alcohol, 3,4,4′ trichlorocarbanilide (Trichlorcarban), p-chloro-m-cresol, 2,4,4′-trichloro 2-hydroxy diphenylether (triclosan), 4,4′-dichloro 2-hydroxy diphenylether, 4-chloro-3,5-dimethylphenol (Chloroxylenol), imidazolidinyl urea, poly-(hexamethylene biguanide)hydrochloride, 2-phenoxy ethanol (phenoxyethanol), hexamethylene tetramine (Methenamine), 1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantanchloride (Quaternium 15), 1-(4-chlorophenyoxy)-1-(1-imidazolyl)3,3-dimethyl-2-butanone (Climbazole), 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione (DMDM hydantoin), benzyl alcohol, 1,2-dibromo-2,4-dicyano butane, 2,2′ methylene-bis(6-bromo-4-chloro phenol) (bromochlorophene), methylchloroisothiazolone, methylisothiazolone, octylisothiazolone, benzylisothiazolone, 2-benzyl-4-chlorophenol (Chlorophenone), chloracetamide, chlorhexidine, chlorhexidine acetate, chlorhexidine gluconate, chlorhexidine hydrochloride, 1-phenoxy-propane-2-ol (phenoxyisopropanol), 4,4-dimethyl-1,3-oxazolidine (dimethyl oxazolidine), diazolidinyl urea, 4,4′-hexamethylenedioxybisbenzamidine and 4,4′-hexamethylenedioxybis(benzamidinium-2-hydroxyethanesulfonate), glutaraldehyde (1,5-pentanedial), 7-ethylbicyclooxazolidine, 3-(4-chlorophenoxy)-1,2-propandiol (chlorophenesin), phenylmethoxymethanol and ((phenylmethoxy)methoxy)-methanol (benzylhemiformal), N-alkyl(C12–C22)trimethyl ammoniumbromide and -chloride (cetrimonium bromide, cetrimonium chloride), benzyl-dimethyl-(4-(2-(4-(1,1,3,3-tetramethylbutyl)-phenoxy)-ethoxy)-ethyl)-ammoniumchloride (benzethonium chloride), Alkyl-(C8–C18)-dimethyl-benzylammonium chloride, -bromide and saccharinate (benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate), benzoic acid and its salts and esters, propionic acid and its salts, salicylic acid and its salt, sorbic acid and its salts, sodium iodiate, inorganic sulfites and bisulfites such as sodium sulfite, dehydroacetic acid , formic acid, mercurate(1-ethyl)2-mercaptobenzoate(2-)—O,S—, hydrogene (Thiomersal or Thiomerosal), 10-undecylenic acid and its salts, octopirox (piroctone olamine), sodium hydroxy methyl-aminoacetate (sodium hydroxymethylglycinate), 3-iodo-2-propynyl butylcarbamate, 10-undecylenic acid, sulfur.


Combinations with natural antimicrobials or chemically modified natural substances with antimicrobial activities such as chitosans and chitosan derivatives, farnesol, plant extracts such as clove oil, blue cypres oil etc. can be also used.
For use on human hair, the dyeing compositions can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example, creams, sprays, emulsions, gels, powders and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibers. Such forms of use are described in detail in Research Disclosure 42448 (August 1999). If necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3, line 55. The dyeing compositions according to the invention are also excellently suitable for the coloring method described in DE-A-3 829 870 using a coloring comb or a coloring brush.
Further carriers for dying compositions are for example described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248–250, especially on page 243, line 1 to page 244, line 12.
Suitable formulations of cationic dyes, which can be used in the coloring compositions according to the invention, are described for example in

    in WO 95/01772, especially on page 11, line 29 to page 12, line 7, or
    in WO 01/66646, especially on page 7, line 1 to page 22, and preferred from page 16, line 20 to page 22, or
    direct dyes as described in DE-A-19 713 698, especially page 3, line 51 to page 4, line 29 and page 4, line 65 to page 5, line 60, or
    direct dyes and oxidizing agent as described in WO 97/20545, especially on page 9, line 1 to page 11, line 4, in particular on page 11, line 6 to page 13, line 19.


Preferred formulations of cationic dyes with other dyes, which can be used in the coloring compositions according to the invention, are:

    combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one cationic dye as described in EP 998,908, especially on page 47, line 3 to page 49, line 26, and preferred on page 51, line 4 to page 52, line 5, or
    combinations of cationic dyes as described in FR-2788432, especially on page 53, line 1 to page 63, line 23, especially a combination of cationic dyes with Arianors in FR-2788432, especially on pages 51 to 52, or especially a combination with at least one Basic Brown 17, Basic brown 16, Basic Red 76 and Basic Red 118, and/or at least one Basic Yellow 57, and/or at least one Basic Blue 99, or
    combinations of direct dyes and/or an oxidation dye and oxidizing agents in the form of permanent-wave fixing solution, especially with direct dyes as described in DE-A-19 713 698, especially page 4, line 65 to page 35, line 59, or
    combinations of cationic dyes and an oxidation dye of the developer compound type and oxidizing agents as described in EP 850 638, especially on page 2, lines 3 to 12 and line 30 to page 14, and page 28, line 35 to page 30, line 20, preferred on page 30, line 25 to page 32, line 30, or
    ready-to-use dyeing compositions and multicompartment device for dyeing keratin fibers comprising combinations of an extemporaneous mixture of a composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, and of a composition (B), in powder form, containing one or more direct dye, preferably cationic, optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agent as described in U.S. Pat. No. 6,190,421, especially in column 2, line 20 to line 31 in column 7, line 15 to column 8, line 43, and preferably in column 8, line 55 to column 9, line 56, and preferably with direct dyes as described in column 5, line 30 to column 7, line 14, or
    a ready-to-use composition comprising, at least one oxidation base, at least one cationic direct dye and at least one enzyme of 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme as described in U.S. Pat. No. 6,228,129, especially in column 2, line 16 to column 25, line 55, and a multi-compartment dyeing device as described in column 26, lines 13 to 24, especially in column 26, line 26 to column 27, line 9, or
    a ready-to-use composition comprising compositions of at least one direct cationic dye and at least one nitrated benzene dye as described in WO 99/20235 especially on page 1, line 25 to page 8, line 5, and on page 30, line 17 to page 34 line 25, with cationic direct dyes as described on page 8, line 12 to page 25 line 6, and a multi-compartment dyeing device as described on page 35, lines 21 to 27, especially on page 36, line 1 to page 37, or
    a ready-to-use composition or a multi-compartment dyeing device comprising compositions of at least one direct cationic dye and at least one autooxidisable oxidation dye, especially benzene, indol and indoline derivatives as described in WO 99/20234, especially on page 26, line 5 to page 32, line 18, or
    oxidation dyeing compositions of at least one direct dye and at least one meta-Aminophenol derivative and at least one developer compound and an oxidizing agent as described in EP 850 636, especially on page 18, line 1 to page 22, line 11, or
    oxidation dyeing compositions of at least one direct dye and at least one developer compound selected from the group of para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, and at least one coupler compound selected from the group of meta-Diphenols and an oxidizing agent, as described in EP-A-850 637, especially on page 19, line 24 to page 22, line 57,
    cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives, as described in EP 998 908, especially on page 47, line 25 to page 50, line 29, or
    oxidative dye precursors (unsaturated aldehyde and coupler compounds), as described in German Patent Application 197 172 24, especially on page 3, line 36 to page 9 line 64.


Cationic compounds may be present in the coloring compositions according to the invention preferably in an amount of from 0.001% to 5%, especially from 0.01% to 1%, based on the total dyeing composition.
The pH value of the ready-to-use dyeing preparations is usually from 2 to 11, preferably from 5 to 10.
The constituents of the aqueous carrier are used in the coloring compositions to the invention in the amounts customary for that purpose; for example emulsifiers may be used in concentrations of from 0.5 to 30% by weight and thickeners in concentrations of from 0.1 to 25% by weight of the total dyeing composition.
If direct dyes are used together with oxidation dyes and/or the addition salts thereof with an acid, they may be stored separately or together.
It is preferred to store the oxidation dyes and direct dyes, which are not stable to reduction, separately.
They may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder.
When the dyes and adjuvants are stored together in a liquid preparation, the preparation should be substantially anhydrous in order to reduce reaction of the compounds.
When they are stored separately, the reactive components are intimately mixed with one another only immediately before use. In the case of dry storage, before use a defined amount of hot (from 50 to 80° C.) water is usually added and a homogeneous mixture prepared.
One preferred method of applying direct dyes containing formulations on hair is by using a multi-compartment dyeing device or “kit” or any other multi-compartment packaging system, as described for example in WO 97/20545 on page 4, line 19 to line 27.
The coloring compositions according to the invention may combined with a suitable ready-to-use composition for the oxidation dyeing of keratin fibers, in particular human keratin, comprising an oxidizing agent, at least one direct dye, and at least one oxidation dye precursor, as described in U.S. Pat. No. 6,190,421, in column 1, line 65 to column 3, line 65, especially in column 10, line 62 to column 12, line 65.
Preferably, such a ready-to-use composition is prepared according to a first preferred embodiment by a process which comprises a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler, especially selected from meta-phenylenediamines and the acid-addition salts thereof, and at least one cationic direct dye, especially compound of formula (I), on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing them together at the time of use before applying this mixture to the keratin fibers.
According to a second preferred embodiment for the preparation of the ready-to-use dye composition, the process includes a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler compound, especially selected from meta-phenylenediamines and the acid-addition salts thereof; on the other hand, a composition (A′) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye, especially compound of formula (I), and, lastly, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent as defined above, and mixing them together at the time of use before applying this mixture to the keratin fibers.
The composition (A′) used according to this second variant of the process in accordance with the invention can optionally be in powder form, the cationic direct dye(s) in accordance with the invention itself (themselves) constituting, in this case, all of the said composition (A′) or optionally being dispersed in an organic and/or inorganic pulverulent excipient.
When it is present in the composition A′, the organic excipient can be of synthetic or plant origin and is selected in particular from crosslinked and non-crosslinked synthetic polymers, polysaccharides such as celluloses and modified or unmodified starches, as well as natural products containing them such as sawdust and plant gums (guar gum, carob gum, xanthan gum, etc.).
When it is present in the composition (A′), the inorganic excipient can contain metal oxides such as titanium oxides, aluminium oxides, kaolin, talc, silicates, mica and silicas.
An very suitable excipient in the coloring compositions according to the invention is sawdust. The powdered composition (A′) can also contain binders or coating products in an amount, which preferably does not exceed approximately 3% by weight relative to the total weight of the said composition (A′).
These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant origin.
The composition (A′) may optionally also contain other adjuvants, in powdered form, in particular surfactants of any kind, hair conditioners such as, for example, cationic polymers, etc.
Another subject of the invention is a multi-compartment dyeing device or “kit” or any other multi-compartment packaging system, as described for example in U.S. Pat. No. 6,228,129, especially in column 26, lines 13 to 24, especially in column 26, line 26 to column 27, line 9, or. A first compartment which contains the composition (A) as defined above, an optional second compartment contains the composition (A′) as defined above, when it is present, and a third compartment contains the oxidizing composition (B) as defined above. These devices can be equipped with means which allow the desired mixture to be applied to the hair, such as the devices described in French patent FR-2,586,913, the disclosure of which is specifically incorporated by reference herein.
An oxidizing agent, which may be added to the coloring compositions according to the invention containing composition, comprises an oxidizing agent and a base.
Further, this composition comprises for this oxidizing agent containing composition customary adjuvant and additives.
The formulations are for example a solution, especially a thickened watery or watery alcoholic solution, a cream, foam, a gel, a powder or an emulsion.
In general, preference is given to a cream formulation, a gel formulation or a foam formulation, and especially a foam formulation.
But, if stability- or solubility-problems arise it may of advantage to use powder formulation as for example described in DE 197 13 698, page 2, line 26 to 54 and page 3, line 51 to page 4, line 25, and page 4, line 41 to page 5 line 59.
The oxidizing agent (calculated as hydrogen peroxide) is present in this composition in 0.5 to 12% by weight, in particular from 1 to 6% by weight based on the totals weight of the oxidizing agent containing composition.
The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in particular about 3 to 6.
An oxidizing agent free composition, which may be added to the coloring compositions according to the invention, comprises a developer compound and a coupler compound and a reduction agent, or

    a developer compound or/and optionally a reduction agent, or
    a coupler compound and a reduction agent.


Further, an oxidizing agent free composition may additionally comprise a direct dye as for example described in German Patent Application 199 59 479, column 3, line 12 to line 16.
Additionally, the oxidizing agent free composition usually comprises customary adjuvant and additives. Preferred are those, which are described in German Patent Application, in column 3, line 17 to line 41.
The pH-value of the oxidizing agent free composition is usually about 3 to 11, and in particular about 5 to 10, and most particular about 9 to 10.
For adjusting the pH-value organic or inorganic acids, as for example described in German Patent Application 199 59 479, column 3, line 46 to line 53 are suitable.
The coloring compositions according to the invention may also be combined with hair dye compositions comprising an acid dye. Hair dye compositions comprising an acid dye are known. For example, they are described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248–250, especially on page 253 and 254.
The hair dye compositions comprising an acid dye have a pH of 2–6, preferably 2–5, more preferably 2.5–4.0. If the pH is too low, the resulting composition may roughen the hair, scalp and hand skin due to an acid component in some cases. If the pH is too high, the penetration accelerating effect on the acid dye is lowered.
A compound of formula (1), (2), (3), (4) and/or (5) according to the present invention may also readily be used in combination with other dyes and/or adjuvants used in the coloring of hair, for example

    acid dye and an alkylene carbonate, as described in U.S. Pat. No. patent 6,248,314, especially in examples 1 and 2, or
    acid hair dye compositions comprise various kinds of organic solvents represented by benzyl alcohol as a penetrant solvent have good penetrability into hair, as described in Japanese Patent Application Laid-Open Nos. 210023/1986 and 101841/1995, or
    acid hair dye compositions with a water-soluble polymer or the like to prevent the drooping of the hair dye composition, as described for example in Japanese Patent Application Laid-Open Nos. 87450/1998, 255540/1997 and 245348/1996, or
    acid hair dye compositions with a water-soluble polymer of aromatic alcohols, lower alkylene carbonates, or the like as described in Japanese Patent Application Laid-Open No. 53970/1998 and Japanese Patent Invention No. 23911/1973.


Preferred keratin fibers are human hair.
The dyes or dye precursors are suitable for all-over coloring of the hair, that is to say when coloring the hair on a first occasion, and also for re-coloring subsequently, or coloration of locks or parts of the hair.
The dyes or dye precursors are applied to hair for example through massage in by hand, a comb, a brush, or a bottle, or a bottle, which is combined with a comb or a nozzle.
In general, the dyes or dye precursors are applied to the hair in a formulation with further components, like adjuvants or additional dyes or dye precursors.
After the application of the dyeing composition the dyed hair is customary rinsed. Customary, the rinsing is conducted with water.
In a suitable embodiment of the processes of the present invention for dyeing human hair, the dyeing composition is not rinsed off, but washed off with a commercially available hair shampoo.
In general, the dyed hair is dried after rinsing and/or washing.
Customary, drying is conducted with hot air by means of a drier or the like, since color migration to clothes and the like becomes scarcely caused.
A very suitable process for dyeing keratin fibers comprises contacting the keratin fibers under alkaline conditions with at least one capped diazotized compound and a coupler compound, with the proviso that the pH is adjusted in the range from 2 to 6 in the last process step. Adjusting the pH is achieved in conventional manner by adding an acid as described for example in EP 962218, especially on page 3, lines 12 to 16.
In the context of the present invention, acids are for example tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.
Preferred technical forms of acids are a solution, a gel, a cream, foam, a conditioner, a emulsion, a shampoo and more preferred a shampoo or a conditioner.
In the context of the present invention, the expression “alkaline condition”, denotes to all process steps without those wherein acid conditions are explicitly described.
In the processes for coloring according to the invention, whether or not coloring is to be carried out in the presence of a further dye will depend upon the color shade to be obtained.
In the context of the present invention, the expression “a further dye”, denotes preferably an oxidation dye, a diazotised compound, a capped diazotised compound and/or coupler compound, or acid dye, especially selected a cationic, anionic or uncharged direct dye, especially a cationic dye selected from the group of the cationic dyes as described in WO 95/01772, especially on page 2, line 7 to page 4, line 1, and preferred on page 4, line 35 to page 8, line 21 with the given preferences, and as described in WO 01/66646, especially on page 1, line 18 to page 3, line 16, or a mixture of at least two cationic dyes as described in WO 95/01772, especially on page 8, line 34 to page 10, line 22.
The processes of the present invention for dyeing keratin fibers, in particular human hair, comprise after contacting the keratin fiber with at least a compound of formula (1) and/or (1a), and then

    leaving the fibers to stand, and
    then rinsing the fibers.


The process for dyeing is for example described in WO 01/66646 on page 15, line 32 to page 16, line 2.
Usually, the dyeing compositions are usually applied to the hair in an amount of from 50 to 100 g.
This composition is left on the fiber at 15 to 45° C. for 5 to 30 minutes, and in particular for 10 to 20 minutes at 20 to 30° C.
Further preferred does a process for dyeing keratin fibers comprises contacting the keratin fibers with at least one direct dye, a base and an oxidizing agent.
Compositions comprising at least one direct dye, especially compound of formula (1), (2), (3), (4) and/or (5) and an oxidizing agent, are for example described in WO 97/20545, on page 3, line 24 to page 11, line 4, and especially on page 4, line 9 to 17.
The composition comprising at least one direct dye, a base and an oxidizing agent is prepared by mixing at least one direct dye and a base, and then just before the dyeing of the hair, adding an oxidizing agent.
Alternatively, the oxidizing agent can be applied simultaneously with a composition comprising at least one dye, and a base.
Preferably, the process for dyeing keratin fibers with at least on direct dye comprises using a multi-compartment dyeing device or ‘kits’ as described for example in WO 97/20545, especially on page 4, line 19 to line 27.
Suitable processes for enlightening dyeing, according to the invention can be used in combination with an oxidative agent are described in WO 97/20545, on page 11 to page 13.
Further preferred are processes for dyeing keratine fibers, especially compound of formula (1), (2), (3), (4) and/or (5) with further cationic dyes, according to processes as described in WO 95/01772, especially on page 10, line 24 to page 11, line 16, and especially on page 11, line 29 to page 28, or

    in WO 01/66646, especially on page 1, line 18 to page 3, line 16, and preferred from page 16, line 20 to page 22, or
    in EP 970 685, especially on page 50, lines 15 to 43, and preferred from page 50, line 46 to page 51, line 40, or
    in DE-A-19 713 698, especially page 5, lines 26 to 60, or
    a process of dyeing with direct dyes and oxidizing agent is described in WO 97/20545, especially on page 10, line 10 to page 11, line 55 and preferably on page 11, line 6 to page 13, line 19.


Further preferred are processes for dyeing keratine fibers, especially compound of formula (1), (2), (3), (4) and/or (5) with other dyes, which can be combined with a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention, are:

    mixtures of at least two cationic dyes as described in WO 95/01772, especially on page 11, lines 1 to 15, or
    combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one cationic dye as described in EP 998,908, especially on page 50, lines 15 to 28, or
    combinations of cationic dyes as described in FR-2788432, especially on page 49, line 28 to page 52, and preferred on page 50, lines 16 to 28, or
    combinations of direct dyes and/or an oxidation dye and oxidizing agents in the form of permanent-wave fixing solution, especially with direct dyes as described in DE-A-19 713 698, especially on page 2, lines 12 to 23, especially on page 4, line 65 to page 5, line 59, or
    combinations of cationic dyes and an oxidation dye of the developer compound type and oxidizing agents as described in EP 850 638, especially on page 29, line 42 to page 30, line 20 and preferred on page 30, line 25 to page 32, line 30, or
    combinations of an extemporaneous mixture of a composition (A) containing one or more oxidation dye precursors and optionally one or more couplers, and of a composition (B), in powder form, containing one or more direct dye, preferably cationic, optionally dispersed in an organic pulverulent excipient and/or a mineral pulverulent excipient, and a composition (C) containing one or more oxidizing agent as described in U.S. Pat. No. 6,190,421, especially in column 8, lines 43 to 52, and preferably in column 8, line 55 to column 9, line 55, or
    a ready-to-use composition comprising, at least one oxidation base, at least one cationic direct dye and at least one enzyme of 2-electron oxidoreductase type in the presence of at least one donor for the said enzyme as described in U.S. Pat. No. 6,228,129, especially in column 25, line 56 to column 27, line 9, or
    a ready-to-use composition or multi-compartment dyeing device comprising compositions of at least one direct cationic dye and at least one nitrated benzene dye as described in WO 99/20235 on page 34, line 27 to page 37, or
    a ready-to-use composition or multi-compartment dyeing device comprising compositions of at least one direct cationic dye and at least one autooxidisable oxidation dye, especially benzene, indol and indoline derivatives as described in WO 99/20234, especially on page 32, line 20 to page 35, oxidation dyeing compositions of at least one direct dye and at least one meta-Aminophenol derivative and at least one developer compound and an oxidizing agent as described in EP 850 636, especially on page 18, line 1 to page 22, line 11, or
    oxidation dyeing compositions of at least one direct dye and at least one developer compound selected from the group of para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine and, and at least one coupler compound selected from the group of meta-Diphenols and an oxidizing agent, as described in EP-A-850 637, especially on page 19, line 24 to page 22, line 57,
    cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives, as described in EP 998 908, especially on page 47, line 25 to page 50, line 29, or
    arianors and/or oxidative dyes, as described in FR-2 788 432, especially on page 2, line 16 to page 3, line 16, and page 5, line 19 to page 14, line 8, and combinations with cationic dyes as described on page 14, line 23 and following, or
    oxidative dye precursors (unsaturated aldehyde and coupler compounds), as described in German Patent Application 197 172 24, especially on page 3, line 36 to page 9 line 64.


The processes of coloring of keratin fibers, especially human hair, with a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention may be combined with other direct dyes and oxidative dyes.
In a preferred embodiment of the present invention the process for dyeing keratin fibers with direct dyes and oxidative dyes, in particular human hair, comprises

    a) contacting the keratin fibers with an oxidizing agent, optionally containing at least a compound of formula (1), (2), (3), (4) and/or (5),
    b) then contacting the keratin fibers with an oxidizing agent free composition, optionally containing at least a compound of formula (1), (2), (3), (4) and/or (5),
    or
    a) contacting the keratin fibers with an oxidizing agent free composition, optionally containing at least a compound of formula (1), (2), (3), (4) and/or (5),
    b) then contacting the keratin fibers with an oxidizing agent, optionally containing least a compound of formula (1), (2), (3), (4) and/or (5), with the proviso that at least in one of the process steps a) or b) a compound of formula (1), (2), (3), (4) and/or (5), is present.


The process of coloring with a compound of formula (1), (2), (3), (4) and/or (5) according to the present invention may combined with a process for dyeing keratin fibers with direct dyes and oxidative dyes, which comprises

    contacting the keratin fibers with least a compound of formula (1), (2), (3), (4) and/or (5), then contacting the keratin fibers with an oxidizing agent free composition.


Such process is for example described in DE 199 41 450, especially on page 5, lines 50 to 58, and on page 8, line 31 to 46.
Oxidizing agent is usually applied in form of an oxidizing agent containing composition.
Oxidizing agent free composition containing at least one coupler compound, at least one developer compound, a base and a reduction agent.
Customary, the oxidizing agent containing composition is evenly applied in a sufficient amount related to the amount of hair, usually with 30 to 200 g.
In general, the oxidizing agent containing composition is left on the fiber at 15 to 45° C. for 0 to 15 minutes, and in particular for 0 to 5 minutes.
Then the oxidizing agent free composition is applied to the hair.
In general, the direct dye and oxidizing agent free composition is left on the fiber at 15 to 50° C. for 5 to 45 minutes, and in particular for 10 to 25 minutes.
The coupler and developer compounds of the oxidizing agent free composition can be applied simultaneously or in succession. Preferred is a simultaneous application.
One preferred embodiment of the process is to wash the hair with shampoo and or a weak acid, such as citric acid or tartrate acid.
The direct dyes, which are stable to reduction can stored together with the oxidizing agent free compositions and are applicable as composition.
It is of advantage to prepare compositions of direct dyes, which are not stable to reduction, with oxidizing agent free compositions just before the dyeing process.
Further, a direct dye and an oxidizing agent free composition can be applied simultaneously or in succession.
A further process for the coloration of keratin fiber with direct dyes and oxidation dyes, which can be used in combination with a compound of formula (1), (2), (3), (4) and/or (5) according to the invention, comprises

    a) mixing at least a compound of formula (1), (2), (3), (4) and/or (5) and optionally at least one coupler compound and at least one developer compound, and an oxidizing agent, which optionally contains at least one further direct dye, and
    then contacting the keratin fibers with the mixture as prepared in step a).


In addition, the present invention relates to a careful method of dyeing hair or strands in intensive brillant color shades, which method comprises

    a) contacting the keratin fiber, especially hair, with a composition having a pH in the range from pH 8 to pH10, preferably 9–10, especially 9.5–10, which composition comprises at least a single developer compound, at least a single coupler compound and at least an oxidating agent and optionally a cationic direct dye, and
    b) then, contacting the keratin fiber, especially hair, with an acid and optionally a cationic direct dye or a composition comprising a cationic direct dye, with the proviso that in at least one of the steps a) or b) a single cationic direct dye; preferably the cationic direct dye is at least a single compound of formula (1) and/or (1a).


Furthermore, the present invention relates to a further careful method of dyeing hair or strands in intensive brillant color shades, which method comprises

    a) contacting the keratin fiber, especially hair, with a composition having a pH in the range from pH 8 to pH10, preferably 9–10, especially 9.5–10, which composition comprises at least a single developer compound, at least a single coupler compound and at least an oxidating agent and optionally a cationic direct dye, and
    b) then, contacting the keratin fiber, especially hair, with a composition having a pH in the range from pH 2 to pH7, preferably 3–6, especially 4–5.5, which composition comprises at least a single developer compound, at least a single coupler compound and at least an oxidating agent and optionally a cationic direct dye, with the proviso that in at least one of the steps a) or b) a single cationic direct dye; preferably the cationic direct dye is at least a single compound of formula (1) and/or (1a).


In addition, the present invention relates to a further careful method of dyeing hair or strands with special potential for the accenturation of hair or stands in intensive brillant color shades, which method comprises

    a) contacting the keratin fiber, especially hair, with a composition having a pH in the range from pH 8 to pH10, preferably 9–10, especially 9.5–10, or having a pH in the range from pH 2 to pH7, preferably 3–6, especially 4–5.5, which composition comprises at least a single developer compound, at least a single coupler compound and at least an oxidating agent and optionally a cationic direct dye, and
    b) then, contacting the keratin fiber, especially hair, with a composition having a pH in the range from pH 8 to pH10, preferably 9–10, especially 9.5–10, or having a pH in the range from pH 2 to pH7, preferably 3–6, especially 4–5.5, which composition comprises at least a cationic direct dye; or
    then, contacting the keratin fiber, especially hair, with a composition having a pH in the range from pH 8 to pH10, preferably 9–10, especially 9.5–10, or having a pH in the range from pH 2 to pH7, preferably 3–6, especially 4–5.5, which composition comprises at least a single developer compound and at least coupler compound and optionally a cationic direct dye, with the proviso that in at least one of the steps a) or b) a single cationic direct dye; preferably the cationic direct dye is at least a single compound of formula (1) and/or (1a).


The dyeing compositions are usually applied to the keratin fiber in an amount of from 50 to 100 g.
After applying the dyeing composition on keratin fiber, after method step a), usally, this composition is left on the keratin fiber at 15 to 45° C. for 5 to 30 minutes, and in particular for 10 to 20 minutes at 20 to 30° C.
Customary, the keratin fiber is rinsed after dyeing.
A further suitable process for the coloration of keratin fiber with direct dyes and oxidation dyes, which can be used in combination with a compound of formula (1), (2), (3), (4) and/or (5) according to the invention, comprises

    mixing at least one autooxidable compound and at least one developer compound and at least one compound of formula (1) and/or (1a), and
    then contacting the keratin fibers with the mixture prepared in step a).


The present invention relates also to a process, in which a dye of formula (1), (2), (3), (4) and/or (5), or cationic dye of formula (1), (2), (3), (4) and/or (5) prepared according to a process according to the invention, or a composition according to the invention, and,

    in succession in any desired order, or simultaneously,
    a capped diazonium compound and
    a water-soluble coupling component,
    are applied to the material to be dyed under conditions in which coupling does not take place initially, and then the capped diazonium compound disposed on the material is caused to react with the coupling component.


The first step of the dyeing method according to the invention comprises applying to the material to be dyed, in succession in any order or simultaneously, a capped diazonium compound and a water-soluble coupling component and, optionally, a cationic direct dye, the application being carried out under such conditions that coupling does not take place initially. This is effected, for example, by immersing the material in a solution comprising the capped diazonium compound or the coupling component and, optionally, a cationic direct dye, and then, if desired after rinsing and intermediate drying, immersing the material in a solution of the second component. Preferably, however, the capped diazonium compound and the coupling component and, optionally, a cationic direct dye, are present together in one solution. Such solutions can also be applied to the material by spraying or by similar measures, care having to be taken that penetration is adequate unless it is desired to dye only the upper layers. In that first step, the diazonium compound and the coupling component should not yet react with each other, and that is preferably achieved by maintaining a pH value of from 8 to 12, preferably from 9 to 11.
In the second step, the diazonium compound and the coupling component are then caused to react, preferably by lowering the pH to a value of from 5 to 2, especially from 3 to 4. The pH value is lowered in customary manner by addition of an acid or a suitable buffer solution, especially citric acid or citric acid gel. If desired, a cationic direct dye may be used in the second step. In any event, it is necessary for a cationic direct dye to be used in one of steps 1 and 2 of the process according to the invention.
The dyed material is then finished in conventional manner, for example by rinsing with water and subsequently drying.
Further, in the present invention especially preferred is a process for dyeing keratin fibers, in particular human hair, with capped diazotised compounds, which comprises,

    contacting the keratin fibers, under alkaline conditions, with at least one capped diazotised compound and a coupler compound, and optionally an oxidizing agent, and optionally in the presence of a further dye, and optionally with at least a compound of formula (1) and/or (1a),
    then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye, especially with, and optionally at least a compound of formula (1) and/or (1a), with the proviso that at least in one step d) or e) at least a compound of formula (1), (2), (3), (4) and/or (5) is present.


The capped diazotised compound and coupler compound and optionally the oxidizing agent, can be applied in any desired order successively, or simultaneously.
Preferably, however, the capped diazotised compound and the coupler compound are applied simultaneously, in a single composition.
Customary the dyeing composition is applied to the hair in an amount of from 50 to 100 g.
In the context of the present invention, the expression “alkaline conditions” denotes a pH in the range from 8 to 10, preferably 9–10, especially 9.5–10.
Adding bases, for example sodium carbonate, ammonia or sodium hydroxide, to the hair or to the dye precursors, the capped diazotised compound and/or the water-soluble coupling component, or to coloring compositions comprising the dye precursors, customarily achieve the alkaline conditions.
In the second stage, the diazotised compound and the coupler compound are then caused to react, preferably by lowering the pH by adding an acid to a value of from 6 to 2, especially from 3 to 4.
Acids are for example tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.
Preferred technical forms of acids are a solution, a gel, a cream, foam, a conditioner, a emulsion, a shampoo and more preferred a shampoo or a conditioner.
The ratio of the amount of alkaline coloring composition applied in the first stage to that of acid coloring composition applied in the second stage is preferably about from 1:3 to 3:1, especially about 1:1.
This first alkaline and then acid dyeing compositions each are left on the fiber at 15 to 45° C. for 5 to 60 minutes, and in particular for 5 to 45 minutes at 20 to 30° C.
A preferred embodiment of the process for dyeing keratin fibers with capped diazotised compounds and a coupler compound, comprises contacting the keratin fibers with more than one capped diazotised compound and/or more than one coupler compound.
Preferred is a process of the present invention for the coloration of keratin fiber with capped diazotised compounds and at least a compound of formula (1), (2), (3), (4) and/or (5), comprises

    mixing, under alkaline conditions, at least one with capped diazotised compound and at least one coupler compound and, optionally with at least a compound of formula (1), (2), (3), (4) and/or (5),
    and optionally at least one developer compound; and an oxidizing agent, and, optionally with at least a compound of formula (1), (2), (3), (4) and/or (5), and
    then contacting the keratin fibers with the mixture as prepared in step a), and
    then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye,
    with the proviso that at least in one of the process a compound of formula (1), (2), (3), (4) and/or (5) is present.


More preferred is a process for dyeing keratin fibers with at least one capped diazotized compound, which comprises

    mixing under alkaline conditions, at least one capped diazotized compound and at least a compound of formula (1), (2), (3), (4) and/or (5),a base and an oxidizing agent, and
    then contacting the keratin fibers with the mixture as prepared in step a),
    then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye.


Further, preferred is a process for the coloration of keratin fiber with capped diazotised compounds comprising

    mixing under alkaline conditions, at least one with capped diazotised compound and at least one coupler compound and optionally at least a compound of formula (1), (2), (3), (4) and/or (5),and optionally at least one developer compound, and optionally at least one autooxidable compound, and
    then contacting the keratin fibers with the mixture prepared in step a),
    then adjusting the pH in the range of 6 to 2 by treatment with acid, and and optionally at least a compound of formula (1), (2), (3), (4) and/or (5), and optionally in the presence of a further dye, with the proviso that at least in one of the process a compound of formula (1), (2), (3), (4) and/or (5), is present.


A further preferred process for the two-step direct dyeing of keratin fibers, which can be used in combination with a compound of formula (1), (2), (3), (4) and/or (5) according to the invention, is characterized in that,

    contacting the keratin fibers with an oxidizing agent or an oxidizing. agent containing composition,
    then contacting the keratin fibers with at least one capped diazotised compound and at least a coupler compound and a compound of formula (1), (2), (3), (4) and/or (5), and optionally an oxidizing agent free composition,
    then adjusting the pH in the range of 6 to 2 by treatment with acid, optionally in the presence of a further dye.
    or
    contacting the keratin fibers with at least one capped diazotised compound and a coupler compound and a compound of formula (1), (2), (3), (4) and/or (5), and optionally an oxidizing agent free composition,
    then contacting the keratin fibers with an oxidizing agent or an oxidizing agent containing composition,
    then adjusting the pH in the range of 5 to 2 by treatment with acid, optionally in the presence of a further dye.


The present invention also concerns a process for the coloration of keratin fibers, especially human hair, with acid dyes, which can be used in combination with a compound of formula (1), (2), (3), (4) and/or (5) according to the invention.
The process comprises

    contacting the keratin fiber with an acid dye and at least a compound of formula (1), (2), (3), (4) and/or (5).


Customary, the dyeing composition comprising an acid dye is applied to the hair in an amount of from 50 to 100 g.
This in a composition is left on the fiber at 15 to 45° C. for 1 to 30 minutes, and in particular for 0 to 15 minutes at 20 to 30° C.
Preferably the hair is rinsed and than washed with shampoo and more preferably not rinsed, but washed with shampoo.
The shampoo used herein includes a shampoo comprising 5–20% of a usual anionic surfactant such as an alkylsulfate or polyoxyethylene alkylsulfate.
Further, the present invention relates to a method of dyeing keratin-containing fibers with the cationic reactive dyes, which comprises treating the fibers with the cationic reactive dyes defined at the beginning or with the dye compositions according to the invention.
A preferred embodiment of the method according to the invention for dyeing keratin-containing fibers comprises treating the fibers with a dyeing solution, prepared according to the process of the invention, comprising a tinctorially effective amount of a cationic reactive dye of formula (1), (2), (3), (4) and/or (5).
The cationic reactive dyes defined at the beginning are present in the dye compositions according to the invention preferably in a tinctorially effective amount of from 0.001% to 5%, especially from 0.01% to 1%, based on the total dyestuff.
The keratin-containing fibers are usually treated with the dyeing solution for about 30 minutes at 20–25° C.
A further preferred embodiment of the present invention relates to a method of dyeing hair, which comprises treating the hair with

    a) an acidic or alkaline permanent-wave solution, and
    b) then with a dyeing solution, prepared according to the process of the invention, comprising a cationic reactive dye of formula (1), (2), (3), (4) and/or (5).


Usually the keratin-containing fibers are treated with the permanent-wave solution for about 3–10 minutes, preferably for 4–6 minutes, at 20–25° C.
It is generally advisable to rinse the hair after treatment with the dyeing solution and/or permanent-wave solution.
The present invention relates also to the use of the cationic reactive dyes defined at the beginning or of the dye compositions according to the invention for dyeing keratin fibers, wool, leather, silk, cellulose or polyamides, especially for dyeing hair.
A preferred embodiment of the process according to the invention for dyeing keratin-containing fibers comprises treating the fibers with a dyeing solution, prepared according to the process of the invention, comprising a tinctorially effective amount of a cationic reactive dye.
The cationic reactive dyes are present in the dye compositions according to the invention preferably in a tinctorially effective amount of from 0.001% to 5%, especially from 0.01% to 1%, based on the total dyestuff.
The keratin-containing fibers are usually treated with the dyeing solution for about 30 minutes at 20–25° C.
A further preferred embodiment of the present invention relates to a method of dyeing hair, which comprises treating the hair with

    a) an acidic or alkaline permanent-wave solution, and
    b) then with a dyeing solution, prepared according to the process of the invention, comprising a cationic reactive dye.


Usually the keratin-containing fibers are treated with the permanent-wave solution for about 3–10 minutes, preferably for 4–6 minutes, at 20–25° C.
A preferred embodiment of the present invention relates to a method of dyeing hair, which comprises treating the hair with a mixture of

    a) an acidic or alkaline permanent-wave solution comprising a thiol derivative, and
    b) a dyeing solution comprising a cationic dichlorotriazine reactive dye or a cationic monofluoromonochloropyrimidine reactive dye.


The dyes according to the invention are distinguished by brilliant shades. They are suitable for dyeing organic material, such as keratin, wool, leather, silk, cellulose or polyamides, especially keratin-containing fibers, cotton or nylon, and preferably human hair. The dyeing obtained is distinguished by their depth of shade and their good fastness to washing properties, such as, for example, fastness to light, shampooing and rubbing. The stability and storage stability of the dyes according to the invention are excellent. They are accordingly especially suitable for dyeing under oxidizing and reducing conditions. The advantage of the new dyes according to the present invention, especially those of formula (1), (2), (3), (4) and/or (5), is their stability against reduction agents e. g. sodium sulfite and ascorbic acid. Therefore, they can be combined with oxidation dyes in one emulsion.
The following Examples serve to illustrate the processes for coloration without limiting the processes thereto. Unless specified otherwise, parts and percentages relate to weight. The amounts of dye specified are relative to the material being colored.


EXAMPLES
Example 1 
Preparation of a Compound of Formula (10)




Diazotation:

1 mol 4-Fluoroaniline (114.6 g) is added to a stirred solution of water, 70 ml, and concentrate chlorhidric acid, 250 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 188.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.
Coupling
Sarcosine, 109, 1 g is dissolved in 100 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 1 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The solution is then distillated completely dry and extracted with 2*500 ml water free ethanol. The sodium chloride salt is filtrated off. The filtrate is concentrated by rotavapor distillation. By cooling at 4–5° C., the product precipitates. The suspension is then filtrated, washed twice with 50 ml of ethanol. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 95 g dry product is obtained.
Example 2 
Preparation of a Compound of Formula (11)




1. Diazotation

1 mol 4-methoxy-aniline (125.7 g) is added to a stirred solution of water, 70 ml, and concentrate chlorhidric acid, 250 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 188.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.
2. Coupling
Sarcosine, 109, 1 g is dissolved in 100 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 2 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The product precipitates. The suspension is then filtrated, washed twice with 50 ml of ethanol. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 251 g dry product is obtained.
Example 3 
Preparation of a Compound of Formula (12)




Diazotation

1 mol 4-Nitroaniline (140 g) is added to a stirred solution of water, 400 ml, and concentrate chlorhidric acid, 250 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 188.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.
Coupling
Sarcosine, 109, 1 g is dissolved in 100 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 3 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The suspension is then filtrated, washed twice with 50 ml of salt solution. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 247 g dry product is obtained.
The product is a mixture of 2 isomers characterized by 1H-NMR Data
Example 4 
Preparation of a Compound of Formula (13)




Diazotation

1 mol 2-Fluoroaniline (111.3 g) is added to a stirred solution of water, 250 ml, and concentrate chlorhidric acid, 250 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 188.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.
Coupling
Sarcosine, 109, 1 g is dissolved in 150 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 4 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The product precipitates. The suspension is then filtrated, washed twice with 50 ml of salt solution. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 247 g dry product is obtained.
Example 5 
Preparation of a Compound of Formula (14)




Diazotation

1 mol 2,4-Difluoroaniline (130 g) is added to a stirred solution of water, 200 ml, and concentrate chlorhidric acid, 250 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 188.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.
Coupling
Sarcosine, 109,1 g is dissolved in 150 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 5 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The suspension is then distillated to dryness, dissolved in ethanol, separated from the salts, concentrated,filtrated, washed twice with 50 ml of ethanol. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 172 g dry product is obtained.
Example 6 
Preparation of a Compound of Formula (15)




Diazotation

0.5 mol (125 g) of the compound of the below formula




is added to a stirred solution of water, 100 ml, and concentrate chlorhidric acid, 125 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 94.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.

Coupling

Dimethylamine 40%, 70 g is dissolved in 200 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 6 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The solution is then distillated. The humid product is dried at 50–55° C., under vacuum (40–50 mbar). About 233 g dry product is obtained.
The product is characterized by
1H-NMR Data in deuterated methanol (128 scans)/360 MHz



















Compound (15)
8,105
dd
J = 9.0;
2.03






j = 1.8




7,768
s

2.00




7,645
dd
J = 9.0
1.97






J = 1.8




4,165
s

6.06




3,655
s, breit

3.01




2,715
s

3.5










Example 7 
Preparation of a Compound of Formula (16)




Diazotation

0.3 mol (113 g) of the compound of the below formula




is added to a stirred solution of water, 300 ml, and concentrate chlorhidric acid, 84 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 94.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.

Coupling

Dimethylamine 40%, 79 g is dissolved in 200 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 7 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The suspension is then filtrated, washed twice with 50 ml of salt solution. The humid product is dried at 50–55° C., under vacuum (40–50 mbar). About 92 g product is obtained.
The product is characterized by
1H-NMR Data in deuterated methanol (128 scans)/360 MHz



















Compound (16)
7,9641
d
J = 9.4;
2.00




7,568
s

2.01




7,446
d
J = 8.6
1.98




7,255
d
J = 8.6
1.95




7,136
d
J = 9.5
2.01




4,056
s

6.04




3,566
S, breit

4.76










Example 8 
Preparation of a Compound of Formula (17)




Diazotation

0.5 mol (125 g) of the compound of the below formula




is added to a stirred solution of water, 100 ml, and concentrate chlorhidric acid, 125 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 94.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.

Coupling

Sacrosine, 55 g is dissolved in 100 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 8 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The solution is then distillated completely dry and extracted with 2*500 ml water free ethanol. The sodium chlorides salt is filtrated off. The filtrate is concentrated by rotavapor distillation. By cooling at 4–5° C., the product precipitates. The suspension is then filtrated, washed twice with 50 ml of ethanol. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 210 g dry product is obtained.
The product is characterized by
1H-NMR Data in deuterated methanol (128 scans)/360 MHz



















Compound (17)
8,028
dd
J = 9.0;
2.0






j = 1.4




7,758
s

2.00




7,601
m
J = 8.8
1.98






J = 1.4




4,482
s

2.06




4,404




4,116
s

5.24




3,396
s

3.01




3,375










Example 9 
Preparation of a Compound of Formula (18)




Diazotation

0.3 mol (113 g) of the compound of the below formula




is added to a stirred solution of water, 300 ml, and concentrate chlorhidric acid, 84 ml (ca. 32%) at 20–30° C. Then, sodium nitrite, 94.4 g of a solution of 37%, is added at 0° C. in such a rate that the temperature is maintained at 0–3° C. After the addition, the mixture is stirred for one other hour, and the excess of nitrite is controlled with KI starch paper. If the KI starch paper does not show any reaction more nitrite is added. At the end of reaction the excess of nitrite is destroyed with sulfamic acid. The diazo-solution is ready for coupling and is stored at temperature of 0° C.

Coupling

Sacrosine 36 g is dissolved in 200 ml water, and then cooled to 0° C. The diazo solution as prepared above in example 8 and 36% solution of sodium hydroxide are added slowly (ca. 1 hour) into this solution in such a rate that the pH value is maintained in the range of pH 9–10. The reaction temperature is mainteained at 0–3° C. till completing of the diazo addition. Then, the suspension is warmed up to room temperature and the pH is adjusted to 10.0 with sodium hydroxide solution.
The suspension is then filtrated, washed twice with 50 ml of salt solution. The humid product is, dried at 50–55° C., under vacuum (40–50 mbar). About 156 g dry product is obtained.
The product is characterized by 1H-NMR Data in deuterated methanol (128 scans)/360 MHz



















Compound (18)
7,921
d
J = 9.0;
2.05




7,512
s

2.00




7,407
d
J = 8.6
2.11




7,193
d
J = 8.1
2.20




7,091
d
J = 9.0
2.02




4,352
s, breit

1.96




4,017
s

6.18




3,278
s, breit

3.01










Example 10 
A) Preparation of Triazenes
43.4 g of 4-chloro-2-amino-1-methylbenzene are mixed with 81 g of 32% hydrochloric acid and cooled to 0° C. Then, over the course of one hour, 75 ml of 4N aqueous sodium nitrite solution are added dropwise, with stirring, the temperature being maintained at from 0 to 5° C. The resulting solution is then added dropwise, over the course of 15 minutes, to an aqueous solution of 30 g of sarcosine and 90 g of sodium carbonate in 250 ml of water at a temperature of 0–5° C. The resulting brown suspension is filtered, the residue is recrystallised from ethanol and dried in air. 66.2 g of 3-methyl-1-(5-chloro-2-methylphenyl)-3-(carboxylmethyl)triazene are obtained in the form of brownish-yellow powder. (Yield: 91%). The compound has the following formula and its 1H-NMR spectrum exhibits the chemical shifts indicated.
Using the procedure analogeous to that described in Example 10, the following compounds of formula (19)–(31) as given below are prepared.
Example 11/applikation
Colouring Method A:
A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous solution containing 0.2M triazene which has been adjusted to pH 10.0 using sodium carbonate, ammonia or NaOH. The strand is removed, excess solution is wiped off and the strand is immersed for 5 minutes in a pH 3 buffer solution containing 4% sodium citrate and 2% citric acid. The strand is then thoroughly rinsed using water and, where appropriate, a shampoo solution and is dried. Hair coloured in the shades mentioned is obtained, with outstanding fastness properties, especially fastness to washing properties.
Colouring method B:
A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous solution that contains 0.2M triazene, 0.2M of hydrogen peroxide (6%) and that has been adjusted to a pH in the range pH 9.8–10 using sodium carbonate, ammonia or NaOH. After contact for 5–30 minutes, there is applied to the strand, without its being rinsed, an amount, corresponding to the weight of triazene originally used, of a mixture comprising 12.5% strength aqueous citric acid gel, which contains 0.1% by weight of a cationic dye selected from the group of the cationic dyes as disclosed in WO 95/01772 and in WO 01/66646. The strand is then combed through thoroughly, a pH of about 7 being obtained. After contact for 15 minutes, the treated strand is treated again with the above mixture comprising 12.5% strength citric acid gel and 0.1% by weight of a cationic dye selected from the group of the cationic dyes as disclosed in WO 95/01772 and in WO 01/66646 at pH 4 for 5 minutes, rinsed thoroughly with water and then dried. Hair is obtained with outstanding fastness properties, especially fastness to washing and fastness to shampooing properties.
Colouring Method C:
A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous solution that contains 0.2M triazene and 0.2 mol of hydrogen peroxide (6%) and that has been adjusted to a pH in the range pH 9.8–10 using sodium carbonate, ammonia or NaOH. After contact for 5–30 minutes, there is applied to the hair, without its being rinsed, an amount, corresponding to the weight of triazene originally used, of a 12.5% strength aqueous citric acid gel containing 0.1% by weight of a cationic dye selected from the group of the cationic dyes as disclosed in WO 95/01772 and in WO 01/66646 and 4% sodium citrate; the hair is combed through thoroughly, a pH of about 3 being obtained. Then, after a contact time of 5–30 minutes, the hair is rinsed thoroughly with water and dried. Hair is obtained with outstanding fastness properties, especially good fastening to washing properties.
Colouring Method D:
A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous solution containing 0.2M triazene and 0.2 mol of hydrogen peroxide (6%) and from 0.1 to 1% by weight, based on the weight of the triazene and coupling component, of a cationic dye selected from the group of the cationic dyes as described in WO 95/01772 and in WO 01/66646. The strand is then adjusted to a pH in the range pH 9.8–10 using sodium carbonate, ammonia or NaOH. After contact for 5–30 minutes, there is applied to the hair, without its being rinsed, an amount, corresponding to the weight of triazene and coupling component originally used, of a 12.5% strength aqueous citric acid gel and 4% sodium citrate and the hair is combed through thoroughly, a pH of about 3 being obtained. Then, after a contact time of 5–30 minutes, the hair is rinsed thoroughly with water and dried. Hair is obtained with outstanding fastness properties, especially good fastness to washing properties.
Examples 11 to 31 
The hair is dyed with triazens according to colouring method A as given in examples to and the given shades















Hair



Triazene
colour


















Example 11




orange


 


Example 12






 


Example 13




yellow


 


Example 14




red/brown/black


 


Example 15




beige


 


Example 16






 


Example 17




darklbrownviolette


 


Example 18






 


Example 19






 


Example 20




orange


 


Example 21




beige


 


Example 22




beige


 


Example 23






 


Example 24




orange


 


Example 25




brightbrown


 


Example 26




brightbrown


 


Example 27




brightbrown


 


Example 28




orange


 


Example 29




brightbrown


 


Example 30




beige


 


Example 31




brightbrown









Example 32 
A strand of bleached human hair is treated with a mixture of equal parts by weight—5 g in each case—of 6% hydrogen peroxide solution and of composition A.
Composition A:
















cetyl stearyl alcohol
11.00



oleth-5
5.0



oleic acid
2.5



stearic acid
2.5



monoethanolamide



coconut fatty acid
2.5



monoethanolamide



sodium lauryl sulfate
1.7



1,2-propanediol
1.0



ammonium chloride
0.5



EDTA, tetrasodium salt
0.2



Perfume
0.4



wheat protein hydrolysate
0.2



Silica
0.1



2,5-diaminotoluene sulfate
0.7



4-amino-2-hydroxytoluene
0.5



2,5,6-triamino-4-
0.2



hydroxypyrimidine sulfate



sodium sulfite
1.0



ascorbic acid
0.5



triazene of Example 1
9.32



Composition A: pH
9.8



water
ad 100










After contact for 15 minutes at room temperature, about 22° C., 10 g of a mixture of a 12.5% strength aqueous citric acid gel containing 0.1% by weight of a violet dye of the following formula




which is prepared analogously to WO 01/66646, Example 4, is applied to the strand. The strand is then combed through, whereupon a pH of about 7 is achieved. After contact for a further 15 minutes, the strand is again treated with 10 g of the above mixture of citric acid gel and violet dye, whereupon a pH of about 4 is achieved. The mixture is allowed to act for 5 minutes at pH 4 and the strand is then washed with water and shampoo and then again with water. The strand is then dried.

A strong, intense, striking coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 32, with the proviso that triazene of Example 1 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 33 
A strand of medium-blond human hair is coloured with a mixture of equal parts by weight—5 g in each case—of 6% hydrogen peroxide solution and of composition A according to Example 32.
The mixture is allowed to act on the strand for 30 minutes at room temperature, about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing 0.1% by weight of a violet dye according to the above formula in Example 32, and 4% sodium citrate, are then applied to the strand. The strand is then combed through, whereupon a pH of about 3 is achieved. After contact for 5 minutes, the strand is thoroughly rinsed and then dried.
A strong, intense, striking . . . coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 33, with the proviso that triazene of composition A in Example 32 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 34 
A strand of bleached human hair is coloured with a mixture of equal parts by weight—5 g in each case—of 6% hydrogen peroxide solution and of composition B.
Composition B:
















cetyl stearyl alcohol
11.00



oleth-5
5.0



oleic acid
2.5



stearic acid
2.5



monoethanolamide



coconut fatty acid
2.5



monoethanolamide



sodium lauryl sulfate
1.7



1,2-propanediol
1.0



ammonium chloride
0.5



EDTA, tetrasodium salt
0.2



Perfume
0.4



wheat protein hydrolysate
0.2



Silica
0.1



triazene of Example 1
9.32



composition B: pH
9.8



water
ad 100










The mixture is allowed to act on the strand for 30 minutes at about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing 0.1% by weight of a violet dye according to the above formula in Example 27, and 4% sodium citrate, are then applied to the strand. The strand is then combed through, whereupon a pH of about 3 is achieved. After contact for 5 minutes, the strand is thoroughly rinsed and then dried.
A strong, intense, striking . . . coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 34, with the proviso that triazene of composition B in Example 34 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 35 
A strand of blond undamaged human hair is coloured with a mixture of equal parts by weight—5 g in each case—of 6% hydrogen peroxide solution and of composition C.
Composition C:
















cetyl stearyl alcohol
11.00



oleth-5
5.0



oleic acid
2.5



stearic acid
2.5



monoethanolamide



coconut fatty acid
2.5



monoethanolamide



sodium lauryl sulfate
1.7



1,2-propanediol
1.0



ammonium chloride
0.5



EDTA, tetrasodium salt
0.2



Perfume
0.4



wheat protein hydrolysate
0.2



Silica
0.1



violet dye of Example 27
0.2



triazene of Example 1
9.32



composition C: pH
9.8



Water
ad 100










The mixture is allowed to act on the strand for 30 minutes at about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing 0.1% by weight of a violet dye according to the above formula in Example 27, and 4% sodium citrate, are then applied to the strand; the latter is then combed through, whereupon a pH of about 3 is achieved. After contact for 5 minutes, the strand is thoroughly rinsed and then dried.
A strong, intense, striking violet coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 35, with the proviso that triazene of composition C in Example 35 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 36 
A strand of blond undamaged human hair is coloured with 10 g of composition D.
Composition D:
















cetyl stearyl alcohol
11.00



oleth-5
5.0



oleic acid
2.5



stearic acid
2.5



monoethanolamide



coconut fatty acid
2.5



monoethanolamide



sodium lauryl sulfate
1.7



1,2-propanediol
1.0



ammonium chloride
0.5



EDTA, tetrasodium salt
0.2



perfume
0.4



wheat protein hydrolysate
0.2



silica
0.1



violet dye of Example 27
0.2



triazene of Example 1 . . .
4.66



composition D: pH
10



water
ad 100










The mixture is allowed to act on the strand for 30 minutes at about 22° C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing 4% sodium citrate are then applied to the strand; the latter is then combed through, whereupon a pH of about 3 is achieved. After contact for 5 minutes, the strand is thoroughly rinsed and then dried.
A strong, intense, striking coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 36, with the proviso that triazene of composition D in Example 36 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 37 
A strand of blond undamaged human hair is coloured with 10 g of composition E.
Composition E
















cetyl stearyl alcohol
11.00



oleth-5
5.0



oleic acid
2.5



stearic acid
2.5



monoethanolamide



coconut fatty acid
2.5



monoethanolamide



sodium lauryl sulfate
1.7



1,2-propanediol
1.0



ammonium chloride
0.5



EDTA, tetrasodium salt
0.2



Perfume
0.4



wheat protein hydrolysate
0.2



Silica
0.1



triazene of Example 1 . . .
4.66



composition E: pH
10



water
ad 100










The mixture is allowed to act on the strand for 30 minutes at about 22° C. Then 10 g of a mixture of a 2% strength aqueous citric acid gel containing 0.1% by weight of a red dye of the following formula




which can be prepared, for example, as described in WO 01/11708, according to Preparation Example 6, compound of formula 106,

and 4% sodium citrate, are applied to the strand and then combed through, whereupon a pH of about 3 is achieved. After contact for 5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 37, with the proviso that triazene of composition E in Example 37 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 38
A strand of blond undamaged human hair is coloured with 10 g of composition F.
Composition F
















cetyl stearyl alcohol
11.00



oleth-5
5.0



oleic acid
2.5



stearic acid
2.5



monoethanolamide



coconut fatty acid
2.5



monoethanolamide



sodium lauryl sulfate
1.7



1,2-propanediol
1.0



ammonium chloride
0.5



EDTA, tetrasodium salt
0.2



Perfume
0.4



wheat protein hydrolysate
0.2



Silica
0.1



triazene of Example 1
5.3



composition F: pH
10



water
ad 100










After contact for 30 minutes, without being washed out, a dye mixture known from U.S. Pat. No. 6,248,314 and having the following composition:
















Black Color No. 401
0.1



Purple Color 401
0.05



Orange Color No. 205
0.1



benzyl alcohol
2.0



ethylene carbonate
10



propylene carbonate
15



ethanol
10



lactic acid
3.5



sodium carbonate solution
of pH 2.9



hydroxyethyl cellulose
1.5



water
ad 100










is applied to the hair. The hair is then combed through thoroughly, whereupon its pH becomes about 3. Then, after a contact period of 15 minutes, the hair is rinsed thoroughly with water and dried.

A strong, intense, striking . . . coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 35, with the proviso that triazene of composition C in Example 35 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 38 
A strand of blond undamaged human hair is coloured with 10 g of a composition comprising compositions A and C.














Compositions











A
C















cetyl stearyl alcohol
11.00
11.00



oleth-5
5.0
5.0



oleic acid
2.5
2.5



stearic acid
2.5
2.5



monoethanolamide



coconut fatty acid
2.5
2.5



monoethanolamide



sodium lauryl sulfate
1.7
1.7



1,2-propanediol
1.0
1.0



ammonium chloride
0.5
0.5



EDTA, tetrasodium salt
0.2
0.2



Perfume
0.4
0.4



wheat protein hydrolysate
0.2
0.2



Silica
0.1
0.1



2,5-diaminotoluene sulfate

0.7



4-amino-2-hydroxytoluene

0.5



2,5,6-triamino-4-

0.2



hydroxypyrimidine sulfate



sodium sulfite

1.0



ascorbic acid

0.5



triazene of Example 1 . . .
9.32



Composition: pH
10
10



Water
ad 100
ad 100










The colouring mixture is allowed to act on the hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueous citric acid gel are then applied to the strand. After contact for 5 minutes, the strand is rinsed thoroughly, shampooed and then dried. A strong, intense, striking coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 38, with the proviso that triazene of composition A in Example 38 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Example 39 
A strand of blond undamaged human hair is coloured with a mixture of 15 g of 6% hydrogen peroxide solution and a composition consisting of 5 g each of compositions A, and C according to Example 34.
The colouring mixture is allowed to act on the hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueous citric acid gel are then applied to the strand. After contact for 5 minutes, the strand is rinsed thoroughly, shampooed and then dried.
A strong, intense, striking coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example 38, with the proviso that triazene of composition A in Example 38 is replaced by a single triazene selected from the triazens of Examples 2 to 31 the hair is dyed.
Examples G (Application)
Compositions A, B, C, D, E, F and G for coloring human hair according to the following table below.



















D1–
E-11

G4–


Compositions
A
C
D19**
E19****
F*
G12***





















cetyl stearyl alcohol
11.00
11.00
11.00
11.00

11.00


Oleth-5
5.0
5.0
5.0
5.0

5.0


oleic acid
2.5
2.5
2.5
2.5

2.5


stearic acid
2.5
2.5
2.5
2.5

2.5


monoethanolamide


coconut fatty acid
2.5
2.5
2.5
2.5

2.5


monoethanolamide


sodium lauryl sulfate
1.7
1.7
1.7
1.7

1.7


1,2-propanediol
1.0
1.0
1.0
1.0

1.0


ammonium chloride
0.5
0.5
0.5
0.5

0.5


EDTA, tetrasodium salt
0.2
0.2
0.2
0.2

0.2


Perfume
0.4
0.4
0.4
0.4

0.4


wheat protein hydrolysate
0.2
0.2
0.2
0.2

0.2


Silica
0.1
0.1
0.1
0.1

0.1


2,5-diaminotoluene sulfate

0.7

0.7


4-amino-2-

0.5

0.5


hydroxytoluene


2,5,6-triamino-4-

0.2

0.2


hydroxypyrimidine sulfate


sodium sulfite

1.0

1.0


ascorbic acid

0.5

0.5


triazene of Example 1
9.33


coupler of Example 15


Direct dye**


0.4


Direct dye***





0.4


Direct dye****



0.4


Black Color No. 401




0.1


Purple Color 401




0.05


Orange Color No.205




0.1


benzyl alcohol




2.0


ethylene carbonate




10


propylene carbonate




15


Ethanol




10


Lactic acid




3.5


sodium carbonate




of pH


solution




2.9


hydroxyethyl




1.5


cellulose


Ammonia (25 %)
9.2
9.2
9.2
9.2

9.2


composition: pH
9.8
9.8
9.8
9.8

9.8


Water
ad 100
ad 100
ad 100
ad 100
ad 100
ad 100










*F: dye mixture known from U.S. Pat. No. 6,248,314


**D1–D10 comprise the following dyes:


in D1 the direct dye** is Basic Yellow 87;


in D2 the direct dye** is Basic Orange 31;


in D3 the direct dye** is or Basic Red 51;


in D4 the direct dye** is the cationic dye of example 4 as described in WO 01/66646;


in D5 the direct dye** is the cationic dye of example 6, compound of formula 106, as


described WO 02/31056;


in D6 the direct dye** has the following formula (I)








wherein


R1 is methyl, R2 is benzyl, R3 is hydrogen;


in D7 the direct dye** is a compound of formula (I)


wherein


R1is benzyl, R2is benzyl, R3 is hydrogen;


in D8 the direct dye** is a compound of formula (I)


wherein


R1is benzyl, R2is methyl, R3 is hydrogen.


In D10 the direct dye** is a cationic dye of formula (3) as described in EP-A-714,954.


**D11–D19 and ***G1–G9 comprise the following direct dyes:


in D11 the direct dye** and in G1 direct dye*** is a compound of formula (4),


wherein X− is acetate;


in D12 the direct dye** and in G2 direct dye*** is a compound of formula (5),


wherein X− is chloride;


in D13 the direct dye** and in G3 direct dye*** is a compound of formula (6),


wherein X− is chloride;


in D14 the direct dye** and in G4 direct dye*** is a compound of formula (7),


wherein X− is chloride;


in D15 the direct dye** and in G8 direct dye*** is a compound of formula (8),


wherein X− is chloride;


in D16 the direct dye** and in G9 direct dye*** is a compound of formula (9),


wherein X− is bromide;


in D17 the direct dye** and in G10 direct dye*** is a compound of formula (10),


wherein X− is bromide;


in D18 the direct dye** and in G11 direct dye*** is a compound of formula (11),


wherein X− is chloride;


in D19 the direct dye** and in G12 direct dye*** is a compound of formula (12),


wherein X− is chloride;


****E6–E19: In E6 the direct dye**** is identical the direct dye** of D6;


in E7 the direct dye**** is identical the direct dye** of D7;


in E8 the direct dye**** is identical the direct dye** of D8;


E9 comprises as direct dye Basic Yellow 87.


in E10 the direct dye**** is identical the direct dye** of D10;


in E11 the direct dye**** is identical the direct dye** of D11;


in E12 the direct dye**** is identical the direct dye** of D12;


in E13 the direct dye**** is identical the direct dye** of D13;


in E14 the direct dye**** is identical the direct dye** of D14;


in E15 the direct dye**** is identical the direct dye** of D15;


in E16 the direct dye**** is identical the direct dye** of D16;


in E17 the direct dye**** is identical the direct dye** of D17;


in E18 the direct dye**** is identical the direct dye** of D18;


in E19 the direct dye**** is identical the direct dye** of D19;






Example G/3 
A strand of middle blond undamaged human hair is colored

    3a) with a mixture of 20 g of 6% hydrogen peroxide solution and a composition consisting of 5 g each of compositions A, C and G5, and alternatively
    3b) first with 20 g of 6% hydrogen peroxide solution and then with 5 g of a composition A, and then 5 g of composition C and 5 g of composition G5, or
    3c) first with 5 g of a composition A, 5 g of composition C and 5 g of composition G5, and then with 20 g of 6% hydrogen peroxide solution.


The coloring mixture is allowed to act on the hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueous citric acid gel are then applied to the strand. After contact for 5 minutes, the strand is rinsed thoroughly, shampooed and then dried.
A strong, intense, striking red coloration having good fastness to washing and fastness to rubbing properties is obtained.
Using the procedure analogeous to that described in Example G/3, with the proviso that triazene of composition A is replaced by a single triazene selected from the triazens of Examples 2 to 31, the hair is dyed.
Example G/4 
A strand of blond undamaged human hair is colored

    4a) with a composition consisting of 5 g each of compositions A and G9, and alternatively the coloring mixture is allowed to act on the hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueous citric acid gel are then applied to the strand. After contact for 5 minutes, the strand is rinsed thoroughly, shampooed and then dried.


A strong, intense, striking red coloration having good fastness to washing and fastness to rubbing properties is obtained.
Example (4a/G9) is identical to Example 4a with the proviso that G9 is replaced by G8.
Example (4a/G1) is identical to Example 4a with the proviso that G9 is replaced by G7.
Using the procedure analogeous to that described in Example G/4, with the proviso that triazene of composition A is replaced by a single triazene selected from the triazens of Examples 2 to 31, the hair is dyed.
Example G/5 
A strand of middle blond undamaged human hair is colored

    5a) with a mixture of 15 g of 6% hydrogen peroxide solution and a composition consisting of 5 g each of compositions A and G6, and alternatively
    5b) first with 15 g of 6% hydrogen peroxide solution, and then with 5 g of a composition A and 5 g of composition G6.
    5c) first with 5 g of a composition A and 5 g of composition G6, and then with 15 g of 6% hydrogen peroxide solution.


The coloring mixture is allowed to act on the hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueous citric acid gel are then applied to the strand. After contact for 5 minutes, the strand is rinsed thoroughly, shampooed and then dried.
A strong, intense, striking red coloration having good fastness to washing and fastness to rubbing properties is obtained.
Example (5a/G5) is identical to Example 5a with the proviso that G6 is replaced by G5.
Example (5a/G10) is identical to Example 5a with the proviso that G6 is replaced by G9.
Example (5b/G9) is identical to Example 5b with the proviso that G6 is replaced by G8.
Example (5b/G1) is identical to Example 5b with the proviso that G6 is replaced by G3.
Example (5c/G5) is identical to Example 5c with the proviso that G6 is replaced by G4.
Example (5c/G1) is identical to Example 5c with the proviso that G6 is replaced by G7.
Using the procedure analogeous to that described in Example G/5, with the proviso that triazene of composition A is replaced by a single triazene selected from the triazens of Examples 2 to 31, the hair is dyed.
Example G/6 
A strand of middle blond undamaged human hair is colored

    6a) with a mixture of 15 g of 6% hydrogen peroxide solution and a composition consisting of 5 g each of compositions A and G6, and alternatively
    6b) first with 15 g of 6% hydrogen peroxide solution, and then with 5 g of a composition A and 5 g of composition G6, or
    6c) first with 5 g of a composition A and 5 g of composition G6, and then with 15 g of 6% hydrogen peroxide solution.


The coloring mixture is allowed to act on the hair for 30 minutes at about 22° C. 10 g of a 2% strength aqueous citric acid gel are then applied to the strand. After contact for 5 minutes, the strand is rinsed thoroughly, shampooed and then dried.
A strong, intense, striking red coloration having good fastness to washing and fastness to rubbing properties is obtained.
Example (6a/G5) is identical to Example 6a with the proviso that G6 is replaced by G5.
Example (6a/G1) is identical to Example 6a with the proviso that G6 is replaced by G12.
Example (6b/G9) is identical to Example 6b with the proviso that G6 is replaced by G11.
Example (6b/G10) is identical to Example 6b with the proviso that G6 is replaced by G10.
Example (6c/G5) is identical to Example 6c with the proviso that G6 is replaced by G4.
Example (6c/G1) is identical to Example 6c with the proviso that G6 is replaced by G7.
Using the procedure analogeous to that described in Example G/6, with the proviso that triazene of composition A is replaced by a single triazene selected from the triazens of Examples 2 to 31, the hair is dyed.

## Claims

1. Process for colouring porous material, which comprises
a) applying to the material being colored a capped diazonium compound of formula (15),




b) then causing the capped diazonium compound present on the material to react with said material.

2. A process according to claim 1, which comprises
further applying at least one capped diazonium compound of formula (1),


Q-N═N—R  (1)


 wherein Q is a radical of an organic compound and R is the radical of an unsubstituted or substituted, water-soluble aliphatic or aromatic amine, and causing the capped diazonium compounds present on the material to react with said material.

3. A process according to claim 1, which comprises
applying to the material being coloured, said capped diazonium compound of formula 15 under alkaline conditions, optionally in the presence of an oxidising agent and optionally in the presence of a further dye, and
b) then subjecting the material being coloured to treatment with acid.