The present invention relates to the technical field of reactive dyestuffs for dyeing and printing of hydroxyl-, amino-, and/or carboxamido-containing material.

Metal free reactive dyes are known from prior art and can be used as colorants in different applications, see for example US 20030172476. However, in the context of the dyeing and printing of hydroxyl-, amino- and/or carboxamido-containing material the known dyes that are metal free have a number of technical disadvantages such as unsatisfactory light fastness and especially limitations in achieving darker shades such as dark violet, dark brown, navy and black shades of very good overall fastness level.

Surprisingly, it has now been found that the dyes of the formula (I) as described below show highly advantageous properties over the known dyes. These include high build-up to darker shades with high fastness properties such as light fastness, wash and contact fastness on the materials mentioned above and on blends containing them. Most importantly, dyes of formula (I) are metal free and thus superior in ecological performance and provide dyeings that are of very good levelness.

The present invention refers to dyes of the formula (I) and mixtures thereof

wherein, A is a radical of diazo component as described below; and

B is a radical of middle component as described below; and

K is a radical of coupling component as described below; and

a is an integer of 0 or 1 ; and

with the general proviso that dyes of general formula (I) contain at least one reactive anchor; and

this invention refers to all kinds of tautomeric and geometric isomers of the dyes of the formula (I), A is a radical of general formula (1 a)

wherein,

each of R ¹ to R ³ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammo- nium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c)

wherein,

each of R ⁴ and R ⁷ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO ₃ M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R ⁵ , R ⁶ , R ⁸ and R ¹² , independent of each other is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R ⁹ to R ¹¹ , independent of each other is hydrogen, halogen, alkyl, alkoxy or b is an integer of 0 to 6; and c is an integer of 1 to 6; and when each of b and c, independent of each other is > 2, R ⁴ and R ⁷ can have different meanings within the same rest as per meaning defined above; and d is 0 or 1 ; and

RG is a reactive anchor of general formula (3a), (3b) or (3c);

wherein, each of R ¹⁴ to R ¹⁹ , independent of each other is halogen; and R ¹⁴ can additionally be a rest of formula (8a)

(8a) wherein,

R ⁹⁶ is hydrogen, halogen, alkyl, alkoxy, thioalkoxy, hydroxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and

R ¹³ is one of the groups selected from general formula (4a) or (4b);

(4a) (4b) wherein, each of R ²⁰ , R ²³ and R ⁹⁴ , independent of each other is hydrogen, alkyl, cycloalkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and each of R , R and R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, sulfamoyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and

R ⁹⁴ can additionally be -CH ₂ CH ₂ -SO ₂ -X, where X is vinyl or a radical -CH ₂ CH ₂ -Y where Y is a group removable under alkaline conditions such as OSO3M, SSO3M, OCOCH3, OPO3M or halogen; and

R ⁹⁵ can additionally be -SO ₂ -X where X is the same as defined above.

B is a radical of general formula (5a)

(5a) wherein, each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO ₃ M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium N,N-dialkyl-N-monoarylammonium N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula 2a) or (2b)

(2a)

where R ⁴ to R ⁸ , b, c and RG are the same as defined above

K is a radical of general formula (6a) or (6b)

(6a) (6b) wherein, D is a radical of general formula (1 a) as defined above; and each of R ²⁷ to R ²⁹ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, ureido, alkylureido, phenylureido, sulfamoyl, acyl, thioacyl, aryloyi, trifluoromethyl, acyloxy, aryloyloxy, carbamoyl, cycloalkyi, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylamnnoniunn, Ν,Ν,Ν- triarylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N-monoalkyl- ammoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; and each of R ³⁰ , R ³¹ , R ⁷³ and R ⁷⁴ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkyl- ammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a)

(7a) wherein,

RG is the same as defined above; and R ³² is hydrogen, halogen, alkyl, N-acylamino, alkoxy, thioalkoxy, hydroxy, cyano, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and

R ³³ is hydrogen, alkyl or aryl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, N-acylamino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy or aryloyloxy; and e is an integer of 1 to 6; and when e is > 2, R ³² can have different meanings within the same rest, as per meaning defined above.

Alkyl groups appearing in this application may be straight-chain or branched and are (Ci-Ci2)-alkyl groups, preferably (Ci-Cs)-alkyl groups, for example n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert-butyl and methylbutyl. The same logic applies to alkoxy groups which accordingly are preferably (Ci-Cs)- alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (d-CsHhioalkoxy, for example -SCH ₃ or -SC2H ₅ .

Cycloalkyi groups are preferably (C3-C8)-cycloalkyl and especially preferably cyclopentyl and cyclohexyl. The term cycloalkyi comprises for the purpose of the present application substituted cycloalklyl groups and unsatured cycloalkyi groups as well. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, acyl, cyano, nitro, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy. Aryl groups appearing in this application are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyi, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl or acyloxy.

Heteroaryl groups appearing in this application are preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzoisothiazole, 1 ,3,4- thiadiazole, furane, oxazole, benzoxazole or isoxazole. The term heteroaryl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heterocycloalkyl groups are preferably pyrrolidine, piperidine, morpholine, tetrahydrofuran or piperazine. The terms heterocycloalkyl comprises the above groups in unsubstituted as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyi, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, monoalkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, amino- carbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium, ammonium or mono-, di-, tri- or tetra-(Ci-C ₄ )-alkylammonium, one equivalent of an alkali earth metal, or a monovalent organic cation.

Particular preferred embodiments of the present invention are dyes of the formula (la) and mixtures thereof

(la)

wherein, each of R ³⁴ to R ³⁶ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO ₃ M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R ³⁷ and R ³⁸ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.

In especially preferred dyes of general formual (la), each of R ³⁴ to R ³⁶ , independent of each other is hydrogen, (Ci-C ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO ₃ M; or is SO ₂ -X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ ) _f -NH-RG, where f is an integer of 1 to 3 and RG is the same as defined above; and each of R ³⁷ and R ³⁸ , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ ) _g -NH-RG, where g is an integer of 1 to 3 and RG is the same as defined above.

Further preferred embodiments of this invention are dyes of general formula (lb) and mixtures thereof

wherein, each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO ₃ M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R ³⁹ to R ⁴¹ , independent of each other can additionally be a group of general formula (2c) as defined above; and each of R ⁴⁵ and R ⁴⁶ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.

In especially preferred dyes of general formual (lb), each of R ³⁹ to R ⁴⁴ , independent of each other is hydrogen, (Ci-C ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ )h-NH-RG, where h is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁴⁵ and R ⁴⁶ , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ )i-NH-RG, where i is an integer of 1 to 3 and RG is the same as defined above.

Further preferred embodiments of this invention are dyes of general formula (Ic) and mixtures thereof

wherein, j is 0 or 1 ; and each of R to R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, Ν,Ν-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylannnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R ⁵⁰ and R ⁵¹ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-annino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-nnonocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-annino, Ν,Ν,Ν-thalkylannnnoniunn, Ν,Ν,Ν- tharylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylammoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. In especially preferred dyes of general formual (lc), each of R ⁴⁷ to R ⁴⁹ , independent of each other is hydrogen, (Ci-C ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO ₃ M; or is SO ₂ -X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ ) _k -NH-RG, where k is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁵⁰ and R ⁵¹ , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyi; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ ) _m -NH-RG, where m is an integer of 1 to 3 and RG is the same as defined above.

Further preferred embodiments of this invention are dyes of general formula (Id) and mixtures thereof:

wherein, n is 0 or 1 ; and each of R ⁵² to R ⁵⁷ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined above; and each of R ⁵² to R ⁵⁴ , independent of each other can additionally be a group of general formula (2c) as defined above; and each of R ⁵⁸ and R ⁵⁹ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.

In especially preferred dyes of general formual (Id), each of R to R , independent of each other is hydrogen, (Ci-C ₄ )alky, (Ci- C ₄ )alkoxyl, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ ) _P -NH-RG, where p is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁵⁸ and R ⁵⁹ , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ ) _q -NH-RG, where q is an integer of 1 to 3 and RG is the same as defined above.

Further preferred embodiments of this invention are dyes of general formula (le) and mixtures thereof:

wherein, each of R , R and R , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO ₃ M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R ⁶³ and R ⁶⁴ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.

In especially preferred dyes of general formual (le), each of R ⁶⁰ to R ⁶² , independent of each other is hydrogen, (CrC ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ ) _r -NH-RG, where r is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁶³ and R ⁶⁴ , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ )s-NH-RG, where s is an integer of 1 to 3 and RG is the same as defined above.

Further preferred embodiments of this invention are dyes of general formula (If) and mixtures thereof:

(if) wherein, each of R ⁶⁵ to R ⁷⁰ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO ₃ M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R ⁶⁵ to R ⁶⁷ , independent of each other can additionally be a group of general formula (2c) as defined above; and each of R ⁷¹ and R ⁷² , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-annino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-nnonocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-annino, Ν,Ν,Ν-thalkylannnnoniunn, Ν,Ν,Ν- tharylamnnoniunn, N,N-dialkyl-N-monoarylannnnoniunn, N,N-diaryl-N- monoalkylamnnoniunn, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above. In especially preferred dyes of general formual (If), each of R ⁶⁵ to R ⁷⁰ , independent of each other is hydrogen, (Ci-C ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO ₃ M; or is SO ₂ -X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ )t-NH-RG, where t is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁷¹ and R ⁷² , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyi; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ )u-NH-RG, where u is an integer of 1 to 3 and RG is the same as defined above.

Further preferred embodiments of this invention are dyes of general formula (Ig) and mixtures thereof:

wherein, each of R to R independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyi, aryl, heteroaryl, heterocycloalkyi, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyi, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO3M or halogen; or is a group of general formula (2a), (2b) or (2c) as defined above; and each of R ⁸¹ and R ⁸² , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyi, cycloalkyl, aryl, heteroaryl, heterocycloalkyi or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfannoyl, Ν,Ν-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfannoyl or N- monoalkyl-N-monoarylsulfannoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyi, trifluoromethyl, heteroaryl, heterocycloalkyi, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.

In especially preferred dyes of general formual (Ig), each of R ⁷⁵ to R ⁸⁰ , independent of each other is hydrogen, (Ci-C ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO ₃ M; or is SO ₂ -X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ )v-NH-RG, where v is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁸¹ and R ⁸² , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ )w-NH-RG, where w is an integer of 1 to 3 and RG is the same as defined above. Further preferred embodiments of this invention are dyes of general formula (Ih) and mixtures thereof:

wherein, each of R ⁸³ to R ⁹¹ , independent of each other is hydrogen, halogen, alkyl, N- acylamino, alkoxy, thioalkoxy, hydroxy, cyano, nitro, alkoxycarbonyl, alkoxythiocarbonyl, acyl, thioacyl, aryloyl, trifluoromethyl, acyloxy, aryloyloxy, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, N-cinnamoylamino, SO3M or COOM; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO ₃ M, SSO ₃ M, OCOCH ₃ , OPO ₃ M or halogen; or is a group of general formula (2a) or (2b) as defined above;and each of R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁹ , R ⁹⁰ and R ⁹¹ , independent of each other can additionally be a group of general formula (2c) as defined above; and each of R ⁹² and R ⁹³ , independent of each other is hydrogen, alkyl, acyl, thioacyl, aryloyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl or cinnamoyl; or is alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl- amino, N-monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν- triarylammonium, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N- monoalkylammonium, N-acylamino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N- monoalkyl-carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N- monoaryl-carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N-monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is alkyl interrupted by one or more heteroatoms such as oxygen or sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, N,N-dialkyl- amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo- alkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-N-monocycloalkyl-amino, N- monoaryl-N-monocycloalkyl-amino, Ν,Ν,Ν-trialkylammonium, Ν,Ν,Ν-triarylammoni- um, N,N-dialkyl-N-monoarylammonium, N,N-diaryl-N-monoalkylammonium, N-acyl- amino, N-cinnamoylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, SO3M, COOM, nitro, acyl, thioacyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, acyloxy, aryloyloxy, carbamoyl, N-monocycloalkyl-carbamoyl, N-monoalkyl- carbamoyl, N,N-dicycloalkyl-carbamoyl, Ν,Ν-dialkyl-carbamoyl, N-monoaryl- carbamoyl, Ν,Ν-diaryl-carbamoyl, N-monocycloalkyl-N-monoarylcarbamoyl, N- monoalkyl-N-monoaryl-carbamoyl, sulfamoyl, N-monocycloalkyl-sulfamoyl, N- monoalkyl-sulfamoyl, N,N-dicycloalkyl-sulfamoyl, Ν,Ν-dialkyl-sulfamoyl, N-monoaryl- sulfamoyl, Ν,Ν-diaryl-sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl or N- monoalkyl-N-monoarylsulfamoyl; or is a reactive anchor RG, where RG is the same as defined above; or is a rest of the general formula (7a) as defined above.

In especially preferred dyes of general formual (Ih), each of R ⁸³ to R ⁹¹ , independent of each other is hydrogen, (CrC ₄ )alkyl, (Ci- C ₄ )alkoxy, halogen, acyl or SO3M; or is SO2-X, where X is vinyl or a radical -CH ₂ CH ₂ -Y and Y is a group removable under alkaline conditions such as OSO3M; or is -NH-RG, where RG is the same as defined above; or is -(CH ₂ )x-NH-RG, where x is an integer of 1 to 3 and RG is the same as defined above; and each of R ⁹² and R ⁹³ , independent of each other is hydrogen, alkyl, aryl, sulfomethyl, acyl or aryloyl; or is a reactive anchor RG, where RG is the same as defined above; or is -(CH ₂ ) _y -NH-RG, where y is an integer of 1 to 3 and RG is the same as defined above.

Examples of preferred dyes of the formulae (la) to (Ih) are the compounds I ¹ to I ¹⁴⁰ listed in the table 1 below and having the general formula (Γ). 41

Table 1

43







55



60

61

62

64

65

66



72

73

80

81

85

86

^* refers to the attachment point of A and of K;

^* also refers to the attachment point of B with A when a is 1 ;

refers to the other attachment point of B when a is 1 . Further examples of preferred dyes of the formulae (la) to (Ih) are th compounds I ¹⁴¹ to I ²⁸⁰ listed in the table 2 below ' aarnd having the general formula (I").

Table 2

91

92

93

103

104

106

107

109

111

112

114

117

118

120

ı32

^* refers to the attachment point of A and of K;

^* also refers to the attachment point of B with A when a is 1 ^** refers to the other attachment point of B when a is 1 .

The present invention also provides a process for the preparation of the dyes of the formula (I). This process comprises diazotization of the compounds of the formula (II) and reacting the correspondingly obtained diazonium salts with a compound of the formula K to obtain the intermediate of general formula (III).

In a further step the diazo component (A-NH ₂ ) is diazotised and coupled onto the intermediate III to obtain the bisazo dye product of general formula (IV).

(III) (IV)

Alternatively, the diazo component (A-NH ₂ ) can be diazotised and coupled onto the compound (B-NH ₂ ) to obtain intermediate (V). Further, the intermediate (V) is diazotised and coupled onto compound (III) to obtain the trisazo dye product of general formula (VI). _A .NH _{2 + B} .NH ₂

A ^' ^N^NH.

(V)

The diazotization reactions, in general, can be performed by means of diazotization methods that are known to a person skilled in the art, preferably by using sodium nitrite or nitrosylsulfuric acid in acidic medium using inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid or mixtures thereof or organic acids such as acetic acid or propionic acid or mixtures thereof. Also mixtures of inorganic acid with organic acids can be advantageously used.

The coupling reactions in general can be performed by known methods.

The compounds of the formula A-NH ₂ , B-NH ₂ , K are known and commercially available or can be synthesised by means of common chemical reactions known to a person skilled in the art.

The end product can optionally also be subjected to a vinylization reaction. For example, a vinylizable reaction group such as the β-sulfatoethylsulfonyl is converted into its vinyl form. Such reactions are known to a person skilled in the art. They are generally performed in a neutral to alkaline medium at a temperature, for example, from 20 to 80°C, at a pH of, for example, from 7 to 14.

The dyes of formula (I) are fiber-reactive containing fiber-reactive functional rests. Fiber-reactive functional rests refer to rests capable of reacting with the hydroxyl groups of cellulosic materials, the amino, carboxyl, hydroxyl and thiol groups in the case of wool and silk, or with the amino and possibly carboxyl groups of synthetic polyamides to form covalent chemical bonds. The dyes of the present invention are suitable for dyeing and printing of natural, manufactured regenerated, modified or synthetic hydroxyl-, amino-, and/or carboxamido-containing fiber materials and their blends by the application methods numerously described in the art for reactive dyes. Therefore, the present invention also provides for a process for dyeing and printing of the above-mentioned fiber materials and their blends in which a dye or a dye mixture according to the present invention is used.

Examples of natural fibre materials as described above are vegetable fibres such as seed fibres i.e. cotton, kapok, coir from coconut husk; bast fibers i.e. cotton, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres i.e. sisal, henequen, banana; stalk fibres i.e. bamboo; and fibres from animals such as wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials.

Examples of manufactured and manufactured regenerated fibres are cellulosic fibres such as paper and cellulosic regenerated fibres such as viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers.

Examples of synthetic fiber materials as described above are nylon materials, like nylon-6, nylon-6.6 and aramid fibres.

The above-mentioned substrates to be dyed can be present in various forms such as but not limited to yarn, woven fabric, loop-formingly knitted fabric or carpet.

The dyes of the present invention and their salts or mixtures can be used as a single dyeing product in dyeing or printing processes or it can be part of a di/tri or multi- component combination product in dyeing or in printing compositions.

Dyes of this invention and their salts or mixtures are highly compatible with other known and/or commercially available dyes and they can be used together with such dyes to obtain specific hues of similarly good technical performance. Technical performance includes build-up, fastness properties and levelness.

Since the water solubility of the dyes according to the invention is very good, they can also be used with advantage in customary continuous dyeing processes.

The dyes of the present invention can also be used in digital printing processes, in particular in digital textile printing. Aqueous inks for digital printing which comprise a dye of the present invention likewise form part of the subject matter of the present invention.

The inks of the present invention comprise the dye of the present invention in amounts which preferably range from 0.1 % by weight to 50% by weight, more preferably from 1 % by weight to 30% by weight and most preferably from 1 % by weight to 15% by weight, based on the total weight of the ink.

The inks, as well as the dyes of the present invention may, if desired, contain further dyes used in digital printing.

For the inks of the present invention to be used in the continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include for example lithium nitrate and potassium nitrate. The inks of the present invention may include organic solvents at a total level of 1 -50% and preferably 5-30% by weight. Suitable organic solvents are for example alcohols, for example methanol, ethanol, 1 -propanol, isopropanol, 1 -butanol, tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1 ,2-ethanediol, 1 ,2,3-propanetriol, butanediol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,2-propanediol, 2,3-propanediol, pentanediol, 1 ,4-pentanediol, 1 ,5-pentanediol, hexanediol, D,L-1 ,2-hexanediol, 1 ,6- hexanediol, 1 ,2,6-hexanetriol, 1 ,2-octanediol, polyalkylene glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols having 1 to 8 alkylene groups, for example: monoethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amines, such as for example: methylamine, ethylamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine, N-acetylethanolamine, N-formylethanolamine, ethylenediamine, urea derivatives, such as for example: urea, thiourea, N-methylurea, Ν,Ν'-epsilon dimethylurea, ethyleneurea, 1 ,1 ,3,3-tetramethylurea, amides, such as for example: dimethylformamide, dimethylacetamide, acetamide, ketones or keto alcohols, such as for example: acetone, diacetone alcohol, cyclic ethers, such as for example: tetrahydrofuran, trimethylolethane, trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma butyrolactone, epsilon-caprolactam, further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide, N-cyclohexyl pyrrol idone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone,

1 - (2-hydroxyethyl)-2-pyrrolidone, 1 -(3-hydroxypropyl)-2-pyrrolidone, 1 ,3-dimethyl-

2- imidazolidinone, 1 ,3-dimethyl-2-imidazolinone, 1 ,3-bismethoxymethylimidazolidine, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane, 1 ,2-dimethoxypropane, dioxane ethyl acetate, ethylenediaminetetraacetate ethyl pentyl ether, 1 ,2-dimethoxypropane and trimethylpropane.

The inks of the invention may further include customary additives, for example viscosity moderators to set viscosities in the range from 1 .5 to 40.0 mPas in a temperature range from 20 to 50°C. Preferred inks have a viscosity of 1 .5 to 20 mPas and particularly preferred inks have a viscosity of 1 .5 to 15 mPas.

Useful viscosity moderators include rheological additives, for example: polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol, associative thickeners, polyurea, polyurethane, sodium alginates, modified galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.

As further additives the inks of the invention may include surface-active substances to set surface tensions of 20 to 65 mlM/m, which are adapted if necessary as a function of the process used (thermal or piezo technology). Useful surface-active substances include for example all surfactants, preferably nonionic surfactants, butyldiglycol and 1 ,2-hexanediol. The inks of the present invention may further include customary additives, for example substances to inhibit fungal and bacterial growth in amounts from 0.01 to 1 % by weight based on the total weight of the ink.

The inks may be prepared in a conventional manner by mixing the components in water.

The inks of the present invention are particularly useful in inkjet printing processes for printing a wide variety of materials, in particular of wool and polyamide fibers. The examples below serve to illustrate the invention. Parts and percentages are by weigh unless noted otherwise. The relationship between parts by weight and parts by volume is that of the kilogram to the liter.

Example 1 : i) 6.2 parts of sulfuric acid mono-[2-(2-phenylamino-ethanesulfonyl)-ethyl] ester was suspended in 70 parts of water. 14 parts of sodium bicarbonate was added. The reaction vessel was cooled to 0~5°C using ice. 3.8 parts of cyanuric chloride was added. The reaction was stirred at temperature of 0~5°C and pH of 4-4.5 for 3 hours. Thereafter, 4.8 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was added and the pH was adjusted to 6-6.5 using 15% soda solution. The reaction was stirred at ambient temperature and pH of 6-6.5 for 2 hours. The product (a) obtained was used in next ste without isolation.

ii) 6.7 parts of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid was added into 70 parts of water. The pH was adjusted to 5-6 using 15% soda solution. The reaction vessel was cooled to 0~5°C using ice. 4.3 milliliters of 5M sodium nitrite solution was added into the reaction mixture. After stirring for 10 min, 20.7 parts of 37% hydrochloric acid was added. The reaction was stirred at 0~5°C for 0.5 h and then 0.2 parts of sulfamic acid was added.

The solution of product (a) obtained above was cooled to 0~5°C using ice. The diazonium salt was added into this coupler solution slowly while maintaining the pH to 5-6.5. The reaction was stirred until completion to yield the intermediate (b).

iii) 5.9 parts of {2-[(4-aminobenzene)sulfonyl]ethoxy}sulfonic acid was suspended in 50 parts of water. The reaction vessel was cooled to 0~5°C using ice. 6.2 parts of 37% hydrochloric acid was added into the reaction mixture. After stirring for 10 min, 4.3 milliliters of 5M sodium nitrite solution was added. The reaction was stirred at 0~5°C for 1 h and then 0.2 parts of sulfamic acid was added.

The diazonium salt was added slowly into the solution of (b) synthesized above while maintaining the pH to 5-6.5. The reaction was stirred until completion. The product was precipitated out, collected by filtration and dried to give 21 .8 parts of dye I ⁵⁶ as black solid.

Through analogy, all the dyes of fornnulae (l ¹ -1 ²⁸⁰ ) can be synthesized according to the method described above in the example 1 . Dyeing example 1

3 parts of the dye I ⁵⁶ of this invention is dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) is added. The pH is then adjusted to 3.8-4.2 using acetic acid (60%). The dyebath is entered with 100 parts of a woven wool fabric. The temperature is raised to 40°C over the course of 30 minutes, maintained at this temperature for 15 minutes and then increased to 98°C over the course of 58 minutes and dyeing is carried out at this temperature for 90 minutes. This is followed by cooling to 90°C and removal of the dyed material. The wool fabric is washed with hot and cold water, alkaline-treated and then spun and dried.

Dyeing example 2

2 parts of the dye I ⁵⁶ of this invention and 60 parts of sodium chloride are dissolved in 1000 parts of water, and 12 parts of sodium carbonate and 0.5 part of a wetting agent are added. This dyebath is entered with 100 parts of bleached cotton knitted fabric. The temperature of the dye bath is raised to 30°C at a gradient of 0.5°C/minute and held at this temperature for 30 minutes, and then increased to 60°C over 30 minutes, this temperature being maintained for a further 60 minutes. Thereafter the dyed goods are initially rinsed with tapwater for 5 minutes. The dyed goods are neutralized at 50°C using 60% strength acetic acid for 30-40 minutes. The goods are rinsed with tapwater at boil for 30-40 minutes followed by a final rinse at 40~50°C for 20 minutes and dried.

Dyeing example 3

1 part of the dye I ⁵⁶ of this invention is dissolved in 2000 parts of water and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 6 parts of sodium acetate are added. The pH is then adjusted to 4.5 using acetic acid (80%). The dyebath is heated to 50°C for 10 minutes and then entered with 100 parts of a woven polyamide fabric. The temperature is raised to 1 10°C over the course of 50 minutes and then dyeing is carried out at this temperature for 60 minutes. This is followed by cooling to 60°C and removal of the dyed material. The polyamide fabric is washed with hot and cold water, soaped and then spun and dried. Dyeing example 4

A textile fabric consisting of mercerized cotton is padded with liquor containing 35 g/l of calcium sodium carbonate, 100 g/l of urea and 150 g/l of a low-viscosity sodium alginate solution (6%), and then dried. The liquor pickup is 70%. The textile thus pretreated is printed with an aqueous ink containing 2% of the dye I ⁵⁶ of this invention, 20% of sulfolane, 0.01 % of Mergal K9N and 77.99% of water using a drop- on-demand (bubblejet) ink-jet printing head. The print is fully dried. It is fixed by means of saturated steam at 102°C for 8 minutes. The print is then rinsed warm, subject to a fastness wash with hot water at 95°C, rinsed warm and then dried.