US20090249564A1

US20090249564A1 - Hair dye compositions

Info

Publication number: US20090249564A1
Application number: US12/278,715
Authority: US
Inventors: Roxana Barbieru; Werner Russ; Dominic Pratt; Hartmut Moehring
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG; Kao Corp
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG; Kao Corp
Priority date: 2006-02-09
Filing date: 2007-02-02
Publication date: 2009-10-08
Also published as: WO2007090799A2; EP1820826A1; TW200732427A; US20090217466A1; EP1984458A2; KR20080094674A; CN101379144B; US7776106B2; RU2008136053A; CA2641863A1; KR20080093115A; WO2007090800A2; JP2009531285A; TWI412565B; WO2007090800A3; TW200731994A; AU2007213797A1; WO2007090799A3; AU2007213796A1; JP5176026B2

Abstract

The present invention refers to hair dye compositions comprising one or more dyestuffs of the general formula (I) wherein R, X, Y and Z are defined as given in claim 1 and a process for colouring hair.

Description

The present invention relates to hair dye compositions containing anthraquinone hair dyes.
Hair dyes can be classified by the dye to be used therefore, or by whether they have bleaching action of melanin or not. Typical examples include a two-part permanent hair dye composed of a first part containing an alkali agent, an oxidation dye and optionally a direct dye such as a nitro dye and a second part containing an oxidizing agent; and a one-part semi-permanent hair dye containing an organic acid or an alkali agent, and an acid dye, basic dye or direct dye such as a nitro dye. The above-described permanent hair dye is however accompanied by the drawback that the color tone imparted by an oxidation dye is not so vivid and that they damage the hair. Use of a nitro dye or cationic dye for a two-component hair dye containing an oxidizing agent has been attempted in order to produce various color tones (refer to, for example, Japanese Patent Laid-Open No. 1994-271435 and EP 1 133 976 A2). A permanent hair dye formulation containing current direct dyes typically develop a vivid color just after dyeing, but the color fades away quickly over time and which leads to a dull end result. Also the use of many direct dyes involves such problems as decomposition when mixed with a peroxide serving as an oxidizing agent and incompatibility with the formulation.
The above described semi-permanent hair dye formulations are accompanied by the drawback that the color imparted typically displays low durability. In addition, it is difficult to achieve violet, blue and ash tones since the number of dyes which can deliver these tones is extremely limited. Such dyes must be high performing and toxicologically safe.
It is known to use quaternized anthraquinone dyes to dye hairs, see for example DE 1 203 915, DE 1 248 865, DE 1 492 066, GB 1 205 365, U.S. Pat. No. 3,531,502, EP 0 818 193 A2 and EP 0 852 136 A1. In addition, U.S. Pat. No. 3,657,213, GB 1,270,107, GB 1,248,652, U.S. Pat. No. 2,888,467, U.S. Pat. No. 2,737,517, U.S. Pat. No. 4,246,172, CH 14851/71, DE 16 19 365, CH 463666, FR 1,363,216, U.S. Pat. No. 5,486,629 and GB 807241 teach to dye textile materials with quaternized anthraquinone dyes.
However, there is still a need for hair dyes which can effectively deliver blue, ash, violet or red tones to the hair without damaging and are toxicologically safe.
It was now surprisingly found that specific anthraquinone dyes according to the definition given below provide the required properties.
Accordingly, the present invention provides hair dye compositions comprising one or more dyestuffs of the general formula (I)
wherein
R is hydrogen, alkyl, alkyl substituted by —OR²—, —SR³or —NR⁵R⁴, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —R¹³, —N¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸or —SO₂R⁹;
X is hydrogen, —OR²³⁰, —SR²⁴⁰, —NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰, —SO₂OR³¹⁰, —C(O)OR³²⁰, —C(O)R³³⁰, —SO₂R³⁴⁰, alkyl substituted by Q, —OR²⁰¹, —SR³⁰⁰or —NR⁵⁰⁰R⁴⁰⁰, aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰OR¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰or —SO₂R²²⁰, —NHSO₂R³⁶⁰R³⁷⁰or —CH═NR³⁵⁰;
T is hydrogen, alkyl substituted by Q or aryl substituted by —OR²³⁰;
Y is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂₀R⁵⁷, —NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;
Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶—SO₂OR⁵⁷, NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;
R¹is hydrogen, —OH, —NH₂, —NHalkyl or NO₂;
each of R²to R⁸, R⁶⁰and R⁶¹, independently, is hydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;
R⁹is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;
each of R¹⁰to R²¹independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;
R²²is alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;
each of R⁵¹to R⁵⁴, independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, cycloalkyl substituted by —C(O)R⁶, —SO₂R⁹or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²²;
each of R⁵⁵to R⁵⁷independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²²;
each R⁵⁸and R⁵⁹, independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²²;
each of R²³⁰, R²⁴⁰and R³⁵⁰, independently, is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q, —C(O)R⁶⁰⁰or —SO₂R⁹⁰⁰, or aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰or —SO₂R²²⁰;
each of R²⁰¹, R²⁰⁰, R⁶⁰⁰R⁹⁰⁰, independently, is alkyl substituted by Q, aryl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q,
each of R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁷⁰, R²⁰⁰, R²¹⁰, R²²⁰, independently, is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q,
each of R¹⁴⁰R¹⁵⁰R¹⁶⁰R¹⁸⁰and R¹⁹⁰is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, with the proviso that each the groups —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰and —SO₂—NR¹⁸⁰R¹⁹⁰must contain one group Q;
is each of R³¹⁰, R³²⁰, R³³⁰and R³⁴⁰independently, is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q or aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —N¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰or —SO₂R²²⁰;
each of R³⁶⁰and R³⁷⁰is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, with the proviso that the group —NHSO₂R³⁶⁰R³⁷⁰must contain one group Q;
each of R²⁵⁰R²⁶⁰R²⁷⁰R²⁸⁰R²⁹⁰and R³⁰⁰, independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, —C(O)R⁶⁰¹, —SO₂R⁹⁰¹, or aryl substituted by R¹⁰¹, R¹¹¹O-alkyl, —OR¹²¹, —SR¹³¹—NR¹⁴¹R¹⁵¹, —CONR¹⁵¹R¹⁶¹, —C(O)OR¹⁷¹, —SO₂—NR¹⁸¹R¹⁹¹, —SO₂OR²⁰², —C(O)R²¹¹or —SO₂R²²¹, with the proviso that each of the groups —NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰and —CONR²⁹⁰R³⁰⁰must contain one group Q;
each of R¹¹¹, R¹²¹, R¹³¹, R¹⁴¹, R¹⁵¹, R¹⁶¹, R¹⁷¹, R¹⁸¹, R¹⁹¹, R²⁰²and R²¹¹, independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q;
R²²¹is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q;
R⁶⁰¹is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; and
R⁹⁰¹is alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; and
Q is a group of the general formula (II)
wherein
each of R′, R″ and R′″, independently, is alkyl, aryl, arylalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl, heterocycloalkyl, heterocycloalkyl-alkyl, either of which can be substituted by heteroatom containing groups or R′ and R″ form together with the nitrogen to which they are bonded a 5- or 6-membered heterocyclic ring; and
A⁻ is a cosmetically acceptable anion;
whereby the dyestuff of the formula (I) contains exactly one group Q;
whereby at least one of the groups Y and Z are groups other than hydrogen; and whereby T and R¹are hydrogen if X is different from hydrogen.
Alkyl groups may be straight-chain or branched and are preferably (C₁-C₆)-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, isopentyl or n-hexyl.
Cycloalkyl is preferably (C₃-C₈)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl.
Aryl groups are preferably phenyl or naphthyl groups.
Halogen is preferably chlorine, bromine and fluorine.
A 5- or 6-membered heterocyclic ring which is formed by R′ and R″ is preferably a pyrrolidine, piperidine, morpholine or piperazine ring. R′, R″ and R′″ are preferably benzyl or (C₁-C₆)-alkyl and especially preferably benzyl, methyl and ethyl.
The dyestuffs of the general formula (I) may be salts of an organic or inorganic acid. Consequently, A⁻ may be for example chloride, bromide, iodide, hydroxide, hydrogenphosphate, phosphate, carbonate, hydrogencarbonate, hydrogensulfate, perchlorate, fluoroborate, chlorozincate, methylsulfate, ethylsulfate, acetate, propionate, lactate or citrate or mixtures thereof.
The meaning of A⁻ is generally given by the preparation method of the dyestuff of the general formula (I). Preferred meanings of A⁻ are chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate and lactate.
Especially preferred dye compositions of the present invention comprise one or more dyestuffs of the general formula (I) in which
Z, T and R¹are hydrogen;
R is hydrogen or (C₁-C₆)-alkyl;
Y is —NR⁵¹R⁵², —NHSO₂R⁵⁸or —OR⁵⁸, wherein R⁵¹is hydrogen and R⁵²is hydrogen, (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl; R⁵³is hydrogen, (C₁-C₆)-alkyl or phenyl; and R⁵⁸is (C₁-C₆)-alkyl or phenyl;
X is —OR²³⁰or —SR²⁴⁰, wherein R²³⁰and R²⁴⁰are (C₁-C₆)-alkyl substituted by Q, phenyl substituted by Q, (C₁-C₆)-alkyl-SO₂-phenyl wherein the alkyl group is substituted by Q or (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl group is substituted by Q;
Q is a tris-(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and
A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.
Examples of dyestuffs of this type are the dyestuffs of the formulae (Ic), (Ig), (Ih), (Ii), (Ir), (Is), (Idd), (Iee and (Iff)
Further especially preferred dye compositions of the present invention comprise one or more dyestuffs of the general formula (I) in which
R is hydrogen or (C₁-C₆)-alkyl;
Z, T and R¹are hydrogen;
Y is —NR⁵¹R⁵²or OR⁵³, wherein R⁵¹and R⁵³are hydrogen, R⁵²is (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl;
X is —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰, —SO₂OR³¹⁰, —C(O)OR³²⁰, wherein R²⁷⁰and R²⁹⁰are hydrogen or (C₁-C₆)-alkyl; R²⁸⁰, R³⁰⁰, R³¹⁰and R³²⁰are (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q or phenyl substituted by Q;
Q is a tris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and
A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.
Examples of dyestuffs of this type are the dyestuffs of the formulae (Igg) to (Ijj):
Still further especially preferred dye compositions of the present invention comprise one or more dyestuffs of the general formula (I) in which
R is hydrogen or (C₁-C₆)-alkyl;
T and R¹are hydrogen;
Z is —NR⁵¹R⁵²or —NHC(O)R⁵⁶, wherein R⁵¹is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl and R⁵⁶is (C₁-C₆)-alkyl or phenyl;
Y is —NR⁵¹R⁵², wherein R⁵¹is hydrogen, R⁵²is (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl;
X is —OR²³⁰, —SO₂NR²⁷⁰R²⁸⁰or —SO₂OR³¹⁰, wherein R²³⁰and R³¹⁰are (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, phenyl substituted by Q; R²⁷⁰is hydrogen, R²⁸⁰is (C₁-C₆)-alkyl substituted by Q or hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q;
Q is a tris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and
A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.
Examples of dyestuffs of this type are the dyestuffs of the formulae (Ix) and (Iy):
Still further especially preferred dye compositions of the present invention comprise one or more dyestuffs of the general formula (I) in which
Y, T and R¹are hydrogen;
R is hydrogen or (C₁-C₆)-alkyl;
Z is —NR⁵¹R⁵²or —NHC(O)R⁵⁶, wherein R⁵¹is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl and R⁵⁶is (C₁-C₆)-alkyl or phenyl;
X is —OR²³⁰, —SO₂NR²⁷⁰R²⁸⁰, —SO₂OR³¹⁰or —NR²⁵⁰R²⁶⁰wherein R²³⁰and R³¹⁰are (C₁-C₆)-alkyl substituted by Q, hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q, or phenyl substituted by Q; R²⁷is hydrogen, R²⁸is (C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q; R²⁵is hydrogen and R²⁶is (C₁-C₆)-alkyl substituted by Q;
Q is a tris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group which is bonded to X; and
A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.
Examples of dyestuffs of this type are the dyestuffs of the formulae (Iz), (Iaa), (Ibb) and (Icc):
Still further especially preferred dye compositions of the present invention comprise one or more dyestuffs of the general formula (I) in which
R is hydrogen or (C₁-C₆)-alkyl;
Z is —NR⁵¹R⁵²wherein R⁵¹is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl;
Y is OR⁵³, wherein R⁵³is hydrogen;
X is hydrogen,

R¹is —NH₂or —NH-alkyl;

T is alkyl substituted by Q or aryl substituted by —OR²³⁰; wherein R²³⁰is (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, —C(O)R⁶⁰⁰or —SO₂R⁹⁰⁰wherein R⁶⁰⁰and R⁹⁰⁰are (C₁-C₆)-alkyl substituted by Q or hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q;
Q is a tris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and
A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.
Examples of dyestuffs of this type are the dyestuffs of the formulae (Ikk) to (Inn):
The dyestuffs of the formula (I) are partly known from for example U.S. Pat. No. 2,737,517, U.S. Pat. No. 2,888,467, CH 463666, FR 1,363,216 or DE 16 19 365.
Dyestuffs of the below defined formula (Ia), however, are still novel.
Accordingly, the present invention provides dyestuffs of the general formula (Ia)
wherein
R is hydrogen, alkyl, alkyl substituted by —OR², —SR³or —NR⁵R⁴, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷—SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸or —SO₂R⁹;
X is hydrogen, —OR²³⁵, —SO₂NR²⁷⁰R²⁸⁰or —SO₂OR³¹⁰;
Y is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷, —NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;
Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷, NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;
T is hydrogen or aryl substituted by —OR²³⁰;
R¹is hydrogen, —OH, —NH₂, —NHalkyl or NO₂;
R²³⁵is aryl substituted by —SO₂—NR¹⁸⁰R¹⁹⁰or —SO₂R²²⁰;
and Q, R²to R²², R⁵¹to R⁶¹, R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁴⁰, R¹⁵⁰, R¹⁶⁰, R¹⁷⁰, R¹⁸⁰, R¹⁹⁰, R²⁰⁰, R²¹⁰, R²²⁰, R²³⁰, R²⁷⁰, R²⁸⁰and R³¹⁰are defined as given above.
In preferred dyestuffs of the formula (Ia)
Z is hydrogen or amino;
R¹is hydrogen or hydroxy;
R is hydrogen;
Y is hydroxy or amino; and
X is —OR²³⁵, wherein R²³⁵is (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl group is substituted by Q; and
T is hydrogen or aryl substituted by —OR²³⁰, wherein R²³⁰is (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, —C(O)R⁶⁰⁰or —SO₂R⁹⁰⁰, wherein R⁶⁰⁰and R⁹⁰⁰are (C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q.
Especially preferred dyestuffs of the formula (Ia) are the dyestuffs (Ii), (Is) and (Ikk) to (Inn).
The dyestuffs of the general formula (I) can be obtained by generally known methods, for instance via Ullmann type substitutions of anthraquinone derivatives which contain exchangeable atoms or groups such as halogen, sulfonic acid group or nitro group by aliphatic amines, aromatic amines, alcohols, phenols, thiols, thiophenols and sulfur containing reagents. General procedures are described, for example, in “Ullmann's Encyclopedia of Industrial Chemistry”, VCH Verlagsgesellschaft, Weinheim 1985, volume A2, Anthraquinone Dyes and Intermediates, pages 357-412. The preparing reactions of the dyestuffs can be carried out in an organic solvent such as dimethylformamide, dimethylacetamide, halogenobenzenes etc., in water or preferably in surplus reagent. It is of advantage to carry out the reactions at elevated temperatures, preferably between 60° C. and 150° C. Acid-binding agents must be added or an excess of amine is used. Adding usual catalysts such as copper or copper salts or mixtures thereof can be advantageously.
The alkoxyanthraquinones of the general formula (I) can be obtained via the conversion of anthraquinonesulfonic acids by alcoholic alkali at 50-130° C. The direct replacement of halogen to alkoxy- or aryloxyanthraquinones can be advantageously carried out with e.g. alcoholate or phenolate generated in situ with alkali or advantageously with metallic sodium. It is advantageously to carry out these reactions under water free conditions with dried reagents.
Preferred hair dye compositions according to the present invention comprise dyestuff mixtures comprising one or more dyestuffs of the general formula (I) and one or more direct or oxidation dyestuff.
Examples of such direct dyes include dyes from the publicly available dyestuff list issued by The European Cosmetic, Toiletry and Perfumery Association (COLIPA) and especially Acid Yellow 1, Disperse Red 17, Basic Brown 17, Acid Black I, 4-Nitro-o-phenylenediamine, Picramic acid, HC Red 13, N,N-bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, HC Red 7, HC Blue 2, HC Yellow 4, HC Yellow 2, HC Orange 1, HC Red 1, HC Red 3,4-Amino-3-nitrophenol, 2-Hydroxyethylamino-5-nitroanisole, 3-Nitro-p-hydroxyethylaminophenol, 3-Methylamino-4-nitrophenoxytheanol, 2-nitro-5-glyceryl methylaniline, HC Violet 1, HC Orange 2, HC Yellow 9,4-Nitrophenylaminoethylurea, HC Red 10, HC Red 11, 2-Hydroxy-ethyl picramic acid, HC Blue 12, Hydroxyethyl-2-nitro-p-toluidine, HC Blue 11, HC Yellow 7, HC Yellow 10, 4-Amino-2-nitrophenylamine-2-carboxylic acid, 2-Chloro-6-ethylamino-4-nitrophenol, HC Violet 2,2-Amino-6-chloro-4-nitrophenol, 4-Hydroxpropylamino-3-nitrophenol, HC Yellow 13, 2,6-Diamino-3-((pyridin-3-yl)azo)pyridine, N-(2-nitro-4-aminophenyl)-allylamine, Basic Violet 2, Basic Red 51, Basic Yellow 87, Basic Orange 31, Basic Red 76, Basic Brown 16, Basic Yellow 57, Acid Orange 7, Acid Red 33, Acid Yellow 23, Acid Blue 9, Acid Red 92, Acid Yellow 3, Acid Violet 43, Disperse Violet 1, Acid Blue 62, Disperse Black 9, Hydroxyanthraquinoneaminopropylmethyl morpholinium methosulfate, Lawsone, HC Blue 14, Curry Red, Acid Red 18, Acid Red 52, Acid Green 25, Disperse Blue 377, Pigment Red 57, HC Blue 15, Tetrabromophenol Blue, Basic Blue 7, Basic Blue 26, Basic Blue 99, Basic Violet 10, Basic Violet 14; cationic dyes as described in Japanese Patent Laid-Open Nos. 2204/1983, 118832/1997 and Japanese Laid-Open Publications (PCT) Nos. 501322/1996 and 507545/1996 (please check numbers); and methine type cationic dyes having a cyanine structure.
Preferred inventive hair dye compositions containing mixtures usually contain one or more dyestuffs of the general formula (I) in an amount 90 to 10 wt. % and one or more direct or oxidation dyestuff in an amount of 10 to 90 wt. % based on the total weight of the dyestuff mixture.
Preferably, they contain one or more dyestuffs of the general formula (I) in an amount 80 to 20 wt. % and one or more direct or oxidation dyestuff in an amount of 20 to 80 wt. % based on the total weight of the dyestuff mixture.
Especially preferably, the they contain one or more dyestuffs of the general formula (I) in an amount 65 to 35 wt. % and one or more direct or oxidation dyestuff in an amount of 35 to 65 wt. % based on the total weight of the dyestuff mixture.
Further preferred hair dye compositions according to the present invention contain the dyestuff of the general formulae (I) in amounts of 0.0001 to 20 wt. %, preferably 0.001 to 20 wt. %, more preferably from 0.01 to 10 wt. % and especially preferably from 0.05 to 5 wt. %, based on the weight of the hair dye composition.
Hair dye compositions according to the present invention comprising a dyestuff mixture as described above usually have a dyestuff content between 0.001 to 20 wt. %, preferably from 0.01 to 20 wt. %, more preferably from 0.05 to 10 wt. % and especially preferably from 0.1 to 5 wt. %, based on the weight of the hair dye composition.
In the hair dye compositions according to the present invention, the inventive dyestuffs of the general formula (I) exhibit a high storage stability within a wide pH range from 2 to 11, which is a pH range ordinarily employed for hair dyes, so that the hair dye composition of the present invention can be used at any pH in the above-described pH range. Use in a pH range of from 2 or greater is however preferred from the viewpoint of dyeing property. Hair dye compositions of a pH range of 2 to 8 and hair dye compositions of a pH range of 8 to 12 are preferred.
The desired pH value is usually adjusted using an alkali agent. Examples of alkali agents include ammonia, alkanolamines such as monoethanolamine and isopropanolamine or salts thereof, guanidium salts such as guanidine carbonate and hydroxides such as sodium hydroxide. The inventive hair dye compositions contain an alkali agent preferably in an amount of from 0.01 to 20 wt. %, more preferably from 0.1 to 10 wt. %, especially preferably from 0.5 to 5 wt. % based on the total weight of the composition.
Since the dyestuffs of the formula (I) have high stability against oxidizing agents, the inventive hair dye composition may also be applied to hair together with an oxidizing agent. In other words, it can be provided as a two-part composition composed of a first part containing the dyestuff of the general formula (I) and a second part containing an oxidizing agent. In this case, hair dyeing and bleaching can be carried out simultaneously, which facilitates more vivid hair dyeing.
Examples of oxidizing agent include hydrogen peroxide, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, perborates such as sodium perborate, percarbonates such as sodium percarbonate and bromates such as sodium bromate and potassium bromate. Hydrogen peroxide is especially preferred from the viewpoints of hair bleaching property, stability and effectiveness of the inventive dyestuffs of the general formula (I). Hydrogen peroxide may be used in combination with another oxidizing agent. The oxidizing agent is preferably used in an amount of from 0.5 to 10 wt. %, especially preferably from 1 to 8 wt. %, based on the hair dye composition.
The first part containing the inventive dyestuff of the general formula (I) and the second part containing the oxidizing agent are mixed at a volume ratio preferably ranging from 2:1 to 1:3.
In the hair dye composition of the present invention, an oxidation dye can be used in combination with the inventive dyestuff of the general formula (I). Such combined use enables considerably vivid and intense dyeing which cannot be accomplished by the single use of the oxidation dye. For the oxidation dye, known developers and couplers ordinarily employed for an oxidation type hair dye can be used.
Examples of the developer include paraphenylenediamine, toluene-2,5-diamine, 2-chloro-paraphenylenediamine, N-methoxyethyl-paraphenylenediamine, N,N-bis(2-hydroxyethyl)-paraphenylenediamine, 2-(2-hydroxyethyl)-paraphenylenediamine, 2,6-dimethyl-para-phenylenediamine, 4,4′-diaminodiphenylamine, 1,3-bis(N-(2-hydroxyethyl)-N-(4-aminophenyl)amino)-2-propanol, PEG-3,2,2′-paraphenylenediamine, paraaminophenol, paramethylaminophenol, 3-methyl-4-aminophenol, 2-aminomethyl-4-aminophenol, 2-(2-hydroxyethylaminomethyl)-4-aminophenol, orthoaminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 2-amino-5-acetamidophenol, 3,4-diaminobenzoic acid, 5-aminosalicylic acid, 2,4,5,6-tetraaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine and 4,5-diamino-1-(4′-chlorobenzyl)pyrazole and salts thereof.
Examples of the coupler include metaphenylenediamine, 2,4-diaminophenoxyethanol, 2-amino-4-(2-hydroxyethylamino)anisole, 2,4-diamino-5-methylphenetole, 2,4-diamino-5-(2-hydroxyethoxy)toluene, 2,4-dimethoxy-1,3-diaminobenzene, 2,6-bis(2-hydroxyethylamino)toluene, 2,4-diamino-5-fluorotoluene, 1,3-bis(2,4-diaminophenoxy)propane, metaminophenol, 2-methyl-5-aminophenol, 2-methyl-5-(2-hydroxyethylamino)phenol, 2,4-dichloro-3-aminophenol, 2-chloro-3-amino-6-methylphenol, 2-methyl-4-chloro-5-aminophenol, N-cyclopentyl-metaaminophenol, 2-methyl-4-methoxy-5-(2-hydroxyethylamino)phenol, 2-methyl-4-fluoro-5-aminophenol, resorcin, 2-methylresorcin, 4-chlororesorcin, 1-naphthol, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2-isopropyl-5-methylphenol, 4-hydroxyindole, 5-hydroxyindole, 6-hydroxyindole, 7-hydroxyindole, 6-hydroxybenzomorpholine, 3,4-methylenedioxyphenol, 2-bromo-4,5-methylenedioxyphenol, 3,4-methylenedioxyaniline, 1-(2-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dimethoxy-3,5-diaminopyridine, 2,3-diamino-6-methoxypyridine, 2-methylamino-3-amino-6-methoxypyridine, 2-amino-3-hydroxypyridine, and 2,6-diaminopyridine and salts thereof.
As each of the developer and coupler, at least two of the above-described developers or couplers are usable. The content of each of them is preferably from 0.01 to 20 wt. %, especially preferably from 0.05 to 10 wt. % based on the hair dye composition.
To the hair dye composition of the present invention, an autoxidation dye typified by an indole or an indoline, or a known direct dye such as a nitro dye or a disperse dye can also be added.
Addition of a polyol, polyol alkyl ether, cationic or amphoteric polymer and/or silicone to the hair dye composition of the present invention is preferred, because the resulting composition can dye the hair uniformly and provides improved cosmetic effects of the hair.
In addition to the above-described components, those ordinarily employed as a raw material for cosmetics can be added to the hair dye composition of the present invention. Examples of such an optional component include hydrocarbons, animal or vegetable fats and oils, higher fatty acids, organic solvents, penetration promoters, cationic surfactants, natural or synthetic polymers, higher alcohols, ethers, amphoteric surfactants, nonionic surfactants, anionic surfactants, protein derivatives, amino acids, antiseptics, chelating agents, stabilizers, antioxidants, plant extracts, crude drug extracts, vitamins, colorants, perfumes and ultraviolet absorbers.
The hair dye composition of the present invention can be prepared in a conventional manner to form a one-part composition or a two-part composition having a first part containing an alkali agent and a second part containing an oxidizing agent. The inventive dyestuff of the general formula (I) may be incorporated in at least one of these parts of the two-part or three-part composition. When the hair dye composition of the present invention is of the one-part type, it is applied to the hair directly, while when it is of the two- or three-part type, these parts are mixed just before hair dyeing and the mixture is applied to the hair.
In the case of preparation of a two-part type hair dye composition, the first part is typically prepared by mixing the Inventive dyestuff of the general formula (I) and optionally an oxidation dye and adjusting the pH of the mixture to 8 to 12 with an alkali agent such as ammonia. The second part is prepared by incorporating about 2 to 6 wt. % of hydrogen peroxide, adjusting the mixture to weakly acidic with phosphoric.
The hair dye composition of the present invention can be provided in the form of powder, transparent liquid, emulsion, cream, gel, paste, aerosol, aerosol foam or the like. It preferably has a viscosity of 2000 to 100000 mPa·s upon its application to the hair (after mixing of all the parts when the composition is a two-part or three-part type). The above-described viscosity is measured at 20° C. by using a Brookfield rotary viscometer (No. 5 spindle, 5 rpm).
The present invention also refers to a process for colouring hair characterized in that a hair dye composition as described above is applied onto hair, left for 1 to 45 minutes and than rinsed off from hair.
In a preferred inventive process the hair dye composition is mixed with a composition comprising at least one oxidizing agent.
In the following, embodiments of the invention are described in detail for the purpose of illustrating only and not for the purpose of limiting the same.

Preparation of Dyestuffs

a) Preparation of ([2-(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydro-anthracen-2-ylsulfanyl)-ethyl]-trimethyl-ammonium methylsulfate)

5.0 parts of sulfur, 14.0 parts of sodium sulfide hydrate are dissolved in 80 parts of ethyl alcohol at 50-60° C. Thereafter 10 parts of 1-amino-2-bromo-4-hydroxy-anthraquinone were added and the reaction mixture was kept for 5 hours under reflux. After cooling off and acidification with 100 parts of 2N HCl, the precipitate was filtered off and washed with water. Upon drying 14.3 parts of a red powder were obtained. The isolated product was taken in 250 parts of 3% sodium hydroxide solution, stirred for 20 minutes and filtered off. The sulfur-free filtrate was treated further with 7.7 parts of 2-dimethylaminoethyl chloride hydrochloride and the solution was heated at reflux for 7 hours. After cooling off, the pH was adjusted to ca. 9.0 with conc. HCl and the precipitate was filtered off, washed and dried to give 10.1 parts of product. For the quaternisation the isolated dye was dispersed in 75 parts of chlorobenzene and treated with 3.3 parts of dimethylsulfate. The mixture was stirred at 30° C. for 1 hour and thereafter for another hour at 40° C. After cooling at room temperature the precipitate was filtered off and washed with acetone. Upon drying 11.7 parts of the dye of formula Ig were obtained. The reddish violet dye Ig is very good water-soluble. The analytic data are consistent with the assigned structure for dye Ig.
Melting point: >204° C.;
λ_max(H₂O)=535 nm (9100).

b) Preparation of ([2-(1,4-diamino-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-ethyl]-trimethyl-ammonium methylsulfate)

15 parts of 1,4-diamino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid, 100 parts of 2-dimethylamino-ethanol and 15 parts of solid KOH were heated together at 80° C. and kept at this temperature for 1 hour. After cooling off, mixture was poured into 500 parts of cold water. The precipitate was filtered off, washed with water and dried to yield a reddish violet powder. 2.5 parts of the dyestuff thus obtained were dispersed in 50 parts of chlorobenzene and treated with 1.0 part of dimethylsulfate. The reaction mixture was stirred at 40° C. for 3½ hours. The precipitate was filtered off at 30° C. and washed with acetone. Upon drying 3.3 parts of the dye of formula Ih were obtained. The reddish violet dye 1 h is very good water-soluble. The analytic data are consistent with the assigned structure for dye 1 h.
Melting point: >223° C.;
λ_max(H₂O)=533 nm (9200), 569 nm (9000).

c) Preparation of ({3-[4-(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-benzenesulfonylamino]-propyl}-trimethyl-ammonium methylsulfate)

30 parts of 4-(1-amino-4-hydroxy-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)benzenesulfonyl chloride were dispersed in 160 parts of acetonitrile. 20 parts of 3-dimethylaminopropylamine were added dropwise. After stirring 4 hours at room temperature, the reaction mixture was filtered off, washed with water and dried to yield 35.0 parts of a dark red powder. 10.0 parts of the dye thus obtained were dispersed in 100 parts of chlorobenzene and treated with 2.4 parts of dimethylsulfate. The reaction mixture was stirred at 40° C. for 3 hours. The precipitate was filtered off and washed with acetone. Upon drying 10.6 parts of the dye of the formula Ii were obtained. The red dye Ii is very good water-soluble. The analytic data are consistent with the assigned structure for dye Ii.
Melting point: >145° C.;
λ_max(H₂O)=521 nm (12200), 550 nm (shoulder, 9600).

d) Preparation of ([2-(1-amino-4-methanesulfonylamino-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-ethyl]-trimethyl-ammonium methylsulfate)

5.7 parts of N-[4-amino-3-(2-dimethylamino-ethoxy)-9,10-dioxo-9,10-dihydro-anthracen-1-yl]-methanesulfonamide, prepared from 1-amino-4-methanesulfonylamino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid, N,N-dimethylaminoethanolamine and potassium hydroxide at 60° C., were dispersed in 50 parts of chlorobenzene and treated with 1.7 parts of dimethylsulfate. The reaction mixture was stirred at room temperature for 5 hours. The precipitate was filtered off and washed with acetone. Upon drying 5.8 parts of the dye of the formula Idd were obtained. The red dye Idd is very good water-soluble. The analytic data are consistent with the assigned structure for dye Idd.
Melting point: >206° C.;
λ_max(H₂O)=515 nm (9000).

e) Preparation of ([2-(5-acetylamino-1-amino-9,10-dioxo-9,10-dihydro-anthracen-2-yloxy)-ethyl]-trimethyl-ammonium methylsulfate)

5.5 parts of N-[5-amino-6-(2-dimethylamino-ethoxy)-9,10-dioxo-9,10-dihydro-anthracen-1-yl]-acetamide, prepared from 5-acetylamino-1-amino-9,10-dioxo-9,10-dihydro-anthracene-2-sulfonic acid, N,N-dimethylaminoethanolamine and potassium hydroxide at 60° C., were dispersed in 75 parts of chlorobenzene and treated with 1.7 parts of dimethylsulfate. The reaction mixture was stirred at room temperature for 5 hours. The precipitate was filtered off and washed with acetone. Upon drying 4.8 parts of the dye of the formula Iz were obtained. The red dye Iz is very good water-soluble. The analytic data are consistent with the assigned structure for dye Iz.
Melting point: >280° C.;
λ_max(MeCN)=487 nm (18300).

Preparation of Hair Dye Compositions

EXAMPLE A

The dyes listed in Table 1 below were dissolved into Base Formulation 1 together with the compounds as follows:


Dyestuff of general formula (I)	0.5	g
iso-Propanol	5.0	g
Ammonium Hydroxide (25%)	5.0	g
Water	up to 100	g

	pH	10.2

EXAMPLE B

The dyes listed in Table 2 below were dissolved into Base Formulation 2 together with the compounds as follows:


Dyestuff of general formula (I)	0.5	g
iso-Propanol	5.0	g
Ammonium Hydroxide (25%)	5.0	g
Hydrogen Peroxide (50%)	6.0	g
Water	up to 100	g

	pH	10.2

Dyeing Performance

a) Approximately 1.5 g of the Base Formulation I was applied to 1 g of undamaged white goat hair at 30° C. for 30 mins. At the end of the processing time the tresses were rinsed with water, shampooed and then dried.
The color of the tresses was recorded by measuring L, a and b values of the tresses before and after the colouring using a hand held Datacolor Mercury colour-measuring instrument and the value of delta E, which is a known measure for the chroma, was calculated according to the well-known equation: ΔE=(ΔL²+Δa²+Δb²)^1/2for each example (this will apply equally to every example hereinafter).
The results are shown in Table 1

TABLE 1

Dyestuff	Color of Dyed Hair	L	a	b	Delta E

Formula Ii	Pure Magenta	53.9	30.3	−5.7	45.0
Formula Ig	Intense Violet	40.3	23.2	−13.9	54.7
Formula Ih	Brilliant Purple	42.5	23.8	−20.8	57.7
Formula Idd	Intense Blue-Red	54	28.9	−0.52	41.8
Formula Ic	Intense Purple	47.3	20.5	−16	50.9

b) Approximately 1.5 g of the Base Formulation 2 was applied to 1 g of undamaged white goat hair at 30° C. for 30 mins. At the end of the processing time the tresses were rinsed with water, shampooed and then dried. The color of the tresses was recorded as given in Example A above.
The results are shown in Table 2

TABLE 2

Dyestuff	Color of Dyed Hair	L	a	b	Delta E

Formula Ii	Pure Magenta	53.9	30.3	−5.7	45.0
Formula Ig	Intense Violet	40.3	23.2	−13.9	54.7
Formula Ih	Brilliant Purple	42.5	23.8	−20.8	57.7
Formula Idd	Intense Blue-Red	51.9	33.8	−0.63	46.6
Formula Ic	Intense Purple	57.9	20.1	−11.6	39.5

Claims

1: A dye composition comprising one or more dyestuffs of formula (I)

wherein

R is hydrogen, alkyl, alkyl substituted by —OR², —SR³or —NR⁵R⁴, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²², —C(O)R⁶, —SO₂NR⁷R⁸or —SO₂R⁹;

X is hydrogen, —OR²³⁰, —SR²⁴⁰, —NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰, —SO₂OR³¹⁰, —C(O)OR³²⁰, —C(O)R³³⁰, —SO₂R³⁴⁰, alkyl substituted by Q, —OR²⁰¹, —SR³⁰⁰or —NR⁵⁰⁰R⁴⁰⁰, aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰or —SO₂R²²⁰, —NHSO₂R³⁶⁰R³⁷⁰or CH═NR³⁵⁰;

T is hydrogen, alkyl substituted by Q or aryl substituted by —OR²³⁰;

Y is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂OR⁵⁷, —NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;

Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵⁵, —NHC(O)R⁵⁶, —SO₂R⁵⁷, NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;

R¹is hydrogen, —OH, —NH₂, —NHalkyl or NO₂;

each of R²to R⁸, R⁶⁰and R⁶¹, independently, is hydrogen, alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;

R⁹is alkyl, aryl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;

each of R¹⁰to R²¹, independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;

R²²is alkyl, hydroxyalkyl, polyhydroxyalkyl or cycloalkyl;

each of R⁵¹to R⁵⁴, independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl, cycloalkyl substituted by —C(O)R⁶, —SO₂R⁹, or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²²;

each of R⁵⁵to R⁵⁷, independently, is hydrogen, alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²²;

each R⁵⁸and R⁵⁹, independently, is alkyl, hydroxyalkyl, polyhydroxyalkyl, cycloalkyl or aryl substituted by R¹⁰, R¹¹O-alkyl, —OR¹², —SR¹³, —NR¹⁴R¹⁵, —CONR¹⁵R¹⁶, —C(O)OR¹⁷, —SO₂—NR¹⁸R¹⁹, —SO₂OR²⁰, —C(O)R²¹or —SO₂R²²;

each of R²³⁰, R²⁴⁰and R³⁵⁰, independently, is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q, —C(O)R⁶⁰⁰or —SO₂R⁹⁰⁰, or aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂—NR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R²¹⁰or —SO₂R²²⁰;

each of R²⁰¹, R²⁰⁰, R⁶⁰⁰, R⁹⁰⁰, independently, is alkyl substituted by Q, aryl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q,

each of R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁷⁰, R²⁰⁰, R²¹⁰, R²²⁰, independently, is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q,

each of R¹⁴⁰, R¹⁵⁰, R¹⁶⁰, R¹⁸⁰and R¹⁹⁰is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, with the proviso that each the groups —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰R¹⁶⁰and —SO₂—NR¹⁸⁰R¹⁹⁰must contain comprise one group Q;

each of R³¹⁰, R³²⁰, R³³⁰and R³⁴⁰, independently, is alkyl substituted by Q, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl substituted by Q or aryl substituted by R¹⁰⁰, R¹¹⁰O-alkyl, —OR¹²⁰, —SR¹³⁰, —NR¹⁴⁰R¹⁵⁰, —CONR¹⁵⁰OR¹⁶⁰, —C(O)OR¹⁷⁰, —SO₂OR¹⁸⁰R¹⁹⁰, —SO₂OR²⁰⁰, —C(O)R210 or —SO₂R²²⁰;

each of R³⁶⁰and R³⁷⁰is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q, with the proviso that the group —NHSO₂R³⁶⁰R³⁷⁰must comprise one group Q;

each of R²⁵⁰, R²⁶⁰, R²⁷⁰, R²⁸⁰, R²⁹⁰and R³⁰⁰independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q.—C(O)R⁶⁰¹, —SO₂R⁹⁰¹, or aryl substituted by R¹⁰¹, R¹¹¹O-alkyl, —OR¹²¹, —SR¹³¹, —NR¹⁴¹R¹⁵¹, —CONR¹⁵¹R¹⁶¹, —C(O)OR¹⁷¹, —SO₂—NR¹⁸¹R¹⁹¹, —SO₂OR²⁰², —C(O)R²¹¹or —SO₂R²²¹, with the proviso that each of the groups —NR²⁵⁰R²⁶⁰, —SO₂NR²⁷⁰R²⁸⁰and —CONR²⁹⁰R³⁰⁰must comprise one group Q;

each of R¹¹¹, R¹²¹, R¹³¹, R¹⁴¹, R¹⁵¹, R¹⁶¹, R¹⁷¹, R¹⁸¹, R¹⁹¹, R²⁰²and R²¹¹, independently, is hydrogen, alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q;

R is alkyl, alkyl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q;

R⁶⁰¹is hydrogen, alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; and

R⁹⁰¹is alkyl, alkyl substituted by Q, aryl, aryl substituted by Q, hydroxyalkyl, hydroxyalkyl substituted in the alkyl group by Q, polyhydroxyalkyl, polyhydroxyalkyl substituted in the alkyl group by Q, cycloalkyl or cycloalkyl substituted by Q; and

Q is a group of formula (II)

wherein each of R′, R″, and R′″, independently, is alkyl, aryl, arylalkyl, cycloalkyl, cycloalkylalkyl, heteroaryl, heteroarylalkyl, heterocycloalkyl, heterocycloalkyl-alkyl, either of which can be substituted by a heteroatom containing comprising groups or R′ and R″ form together with the nitrogen to which they are bonded a 5- or 6-membered heterocyclic ring; and

A⁻ is a cosmetically acceptable anion;

whereby the dyestuff of formula (I) comprises exactly one group Q; whereby at least one of the groups Y and Z are groups other than hydrogen; and whereby T and R¹are hydrogen if X is different from hydrogen.

2: The dye composition according to claim 1, wherein in the group of formula (II) R′, R″, and R′″ are (C-1-C₆)-alkyl or benzyl and A⁻ is chloride, bromide, iodide, hydroxide, hydrogenphosphate, phosphate, carbonate, hydrogencarbonate, hydrogensulfate, perchlorate, fluoroborate, chlorozincate, methylsulfate, ethylsulfate, acetate, propionate, lactate or citrate or a mixture thereof.

3: The dye composition according to claim 1, wherein in formula (I)

Z, T and R¹are hydrogen;

R is hydrogen or (C-₁-C₆)-alkyl;

Y is —NR⁵¹R⁵², —NHSO₂R⁵⁸or —OR⁵³, wherein R⁵¹is hydrogen and R⁵²is hydrogen,

(C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl; R⁵³is hydrogen, (C₁-C₆)-alkyl or phenyl; and R⁵⁸is (C₁-C₆)-alkyl or phenyl;

X is —OR²³⁰or —SR²⁴⁰, wherein R²³⁰and R²⁴⁰are (C₁-C₆)-alkyl substituted by Q, phenyl substituted by Q, (C₁-C₆)-alkyl-SO₂-phenyl wherein the alkyl group is substituted by Q or (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl group is substituted by Q;

Q is a tris-(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.

4: The dye composition according to claim 1, wherein in the general formula (I)

R is hydrogen or (C₁-C₆)-alkyl;

Z, T and R¹are hydrogen;

Y is —NR⁵¹R⁵²or OR⁵³, wherein R⁵¹and R⁵³are hydrogen, R⁵²is (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl;

X is —SO₂NR²⁷⁰R²⁸⁰, —CONR²⁹⁰R³⁰⁰, —SO₂OR³¹⁰, —C(O)OR³²⁰, wherein R²⁷⁰and R²⁹⁰are hydrogen or (C₁-C₆)-alkyl; R²⁸⁰, R³⁰⁰, R³¹⁰and R³²⁰are (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q or phenyl substituted by Q;

Q is a tris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group; and

A⁻ is chloride, sulfate, hydrogensulfate, methylsulfate, ethylsulfate, phosphate, formate, acetate or lactate.

5: The dye composition according to claim 1, wherein in formula (I)

R is hydrogen or (C₁-C₆)-alkyl; T and R¹are hydrogen; Z is —NR⁵¹R⁵²or —NHC(O)R⁵⁶, wherein R⁵¹is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl and R⁵⁶is (C₁-C₆)-alkyl or phenyl;

Y is —NR⁵¹R⁵², wherein R⁵¹is hydrogen, R⁵²is (C₁-C₆)-alkyl, hydroxy-(C₁-C₆)-alkyl or phenyl;

X is —OR²³⁰, —SO₂NR²⁷⁰OR²⁸⁰or —SO₂OR³¹⁰, wherein R²³⁰and R³¹⁰are (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, phenyl substituted by Q; R²⁷⁰is hydrogen, R²⁸⁰is (C₁-C₆)-alkyl substituted by Q or hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q;

6: The dye composition according to claim 1, wherein in the general formula (I)

Y, T and R¹are hydrogen;

R is hydrogen or (C₁-C₆)-alkyl;

Z is —NR⁵¹R⁵²or —NHC(O)R⁵⁶, wherein R⁵¹is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl and R⁵⁶is (C₁-C₆)-alkyl or phenyl;

X is —OR²³⁰, —SO₂NR²⁷⁰R²⁸⁰, —SO₂OR³¹⁰or —NR²⁵⁰R²⁶⁰, wherein R²³⁰and R³¹⁰are (C₁-C₆)-alkyl substituted by Q, hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by

Q, or phenyl substituted by Q; R²⁷is hydrogen, R²⁸is (C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q; R²⁵is hydrogen and R²⁶is (C₁-C₆)-alkyl substituted by Q;

Q is a tris(C₁-C₆)-alkyl-ammonium group, a bis(C₁-C₆)-alkyl-benzyl-ammonium group, a methyl-morpholinium group or a methyl-pyrrolidinium group which is bonded to X; and

7: The dye composition according to claim 1, wherein in formula (I)

R is hydrogen or (C₁-C₆)-alkyl;

Z is —NR⁵¹R⁵²wherein R⁵¹is hydrogen and R⁵²is hydrogen or (C₁-C₆)-alkyl;

Y is OR⁵³, wherein R⁵³is hydrogen;

X is hydrogen, R¹is —NH₂or —NH-alkyl;

T is alkyl substituted by Q or aryl substituted by —OR²³⁰; wherein R²³⁰is (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, —C(O)R⁶⁰⁰or —SO₂R⁹⁰⁰wherein R⁶⁰⁰and R⁹⁰⁰are (C₁-C₆)-alkyl substituted by Q or hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q;

8: The dye composition according to claim 1, which further comprises at least one oxidative dye precursor, at least one coupling compound, or a combination thereof.

9: The dye composition according to claim 1, which further comprises an oxidizing agent.

10: The dye composition according to claim 1, which has a pH value in the range of 2 to 11.

11: A process for colouring hair comprising: (1) applying the hair dye composition according to claim 1 onto hair for 1 to 45 minutes, and (2) rinsing off said hair dye composition from said hair.

12: A dyestuff of formula (Ia)

wherein

X is hydrogen, —OR²³⁵, —SO₂NR²⁷⁰R²⁸⁰or —SO₂OR³¹⁰;

Z is hydrogen, —NR⁵¹R⁵², —OR⁵³, —SR⁵⁴, —SO₂NHR⁵³, —NHC(O)R⁵⁶, —SO₂OR⁵⁷, NHSO₂R⁵⁸, —SO₂R⁵⁹, —NHSO₂NR⁶⁰R⁶¹, halogen or NO₂;

T is hydrogen or aryl substituted by —OR²³⁰;

R¹is hydrogen, —OH, —NH₂, —NHalkyl or NO₂;

R²³⁵is aryl substituted by —SO₂—NR¹⁸⁰R¹⁹⁰or —SO₂R²²⁰; and Q, R²to R²², R⁵¹to R⁶¹, R¹⁰⁰, R¹¹⁰, R¹²⁰, R¹³⁰, R¹⁴⁰, R¹⁵⁰, R¹⁶⁰, R¹⁷⁰, R¹⁸⁰, R¹⁹⁰, R²⁰⁰, R²¹⁰, R²²⁰, R²³⁰, R²⁷⁰, R²⁸⁰and R³¹⁰are defined as given in claim 1.

13: The dyestuff according to claim 12, where

Z is hydrogen or amino;

R¹is hydrogen or hydroxy;

R is hydrogen;

Y is hydroxy or amino; and

X is —OR²³⁵, wherein R²³⁵is (C₁-C₆)-alkyl-NH—SO₂-phenyl, wherein the alkyl group is substituted by Q; and

T is hydrogen or aryl substituted by —OR²³⁰, wherein R²³⁰is (C₁-C₆)-alkyl substituted by Q, hydroxy(C₁-C₆)-alkyl substituted in the alkyl group by Q, —C(O)R⁶⁰⁰or —SO₂R⁹⁰⁰, wherein R⁶⁰⁰and R⁹⁰⁰are (C₁-C₆)-alkyl substituted by Q or hydroxy-(C₁-C₆)-alkyl substituted in the alkyl group by Q.