Acid dyes, process for the production thereof and their use

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

Acid dyes with pyridine couplers are known from prior art and can be used as colorants in different applications, see for example US 3,959,250 A, US 5,468,848 A, EP 2 457 956 A and WO 2007/045825 A.

However, in the context of the dyeing and printing of hydroxyl- and/or carboxamido- containing material the known dyes have a number of technical disadvantages, which require improvement.

One such disadvantage is, that many of them are comprising heavy metals such as Cu, Cr or Ni. Such heavy metals are critical from a toxicological as well as an environmental point of view and shall thus be excluded.

Surprisingly, it has now been found that the dyes of formula (1 ) as described below show highly advantageous properties over the known dyes. These include high tinctorial strength with high brilliancy as well as high fastness properties such as wash, contact and light fastness on the materials mentioned above, on blends containing them as well as on microfibres. Most importantly, dyes of formula (1 ) are substantially heavy metal free and provide dyeings that are levelled. Metals may only be present as counter ions and are selected from the groups of alkali and earth alkali metals, which do not have such effects as heavy metals.

If heavy meatals are present at all in the dyes of the present invention they do not result from being integral part of the dye but are coursed by the production process in general. Reasons in general for these impurities can be impurities resulting from educts and catalysts being used in the respective reactions - the levels of such impurities can be managed and be kept well below those recommended e.g. by ETAD® and would thus be below 100 ppm for Cr, below 250 ppm for Cu and below 200 ppm for Ni just to mention the values for the metals mentioned above. This is a significant improvement as compared to dyes where such metals are present at molar levels. The present invention refers to dyes of formula (1 ) and mixtures thereof

(1 ) wherein

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,

R ⁹ , R ¹⁰ , R ^{1 1} , R ¹² independent of each other is hydrogen, alkyl, substituted alkyl, alkyl chain interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyi, heterocycloalkyi, cyano, acyloxy, alkylcarbonyl, acylamino, alkylsulfonylamino, amino, monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, carbamoyl, sulfamoyl, ureido,alkylureido or SO3M,

R ¹³ and R ¹⁸ independent of each other is cyano, carbamoyl, substituted carbamoyl, alkoxycarbonyl, trifluoromethyl, carbonyltrifluoromethyl or halogen,

R ¹⁴ and R ¹⁹ independent of each other is hydrogen, alkyl, cycloalkyi, trifluoromethyl, alkoxy, cyano, carbamoyl, alkoxycarbonyl, COOM, amino, hydroxyl, monocycloalkyl- amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino, diaryl- amino, monocycloalkylmonoarylamino, monoalkyl monoaryl amino, alkylthio, arylthio or

is alkyi substituted by one or more substituents selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, acyloxy, carbamoyl, nitro, amino, acylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkyl- ureido and phenylureido, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²⁰ , R ²¹ and R ²² independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl- thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocyclo- alkylalkyl

or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

alkyi 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-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, 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, N,N-di- aryl-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, N,N-diaryl- sulfamoyl, N-monocycloalkyl-N-monoarylsulfamoyl, N-monoalkyl-N-monoarylsulfamo- yl and SO ₃ M

or alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amino, N-monoalkyl-amino, Ν,Ν-dialkyl-amino, N-monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N- monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, 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, N- monoalkyl-N-monoarylsulfamoyl and SO3M,

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation, the dyes of formula (1 ) have two to six sulfonic acid groups

and

whereby the bonds with unfixed attachment points on the pyridine couplers mean that the amino rests bearing the substituents R ¹⁵ and R ¹⁶ , and -OR ¹⁷ , respectively can be positioned ortho or para to R ¹³ , meaning that when the amino rest bearing the substituents R ¹⁵ and R ¹⁶ is positioned ortho to R ¹³ , the -OR ¹⁷ is positioned para to R ¹³ , and vice versa;

and

the same applies to the amino rests bearing the substituents R ²⁰ and R ²¹ , and -OR ²² , respectively that can be positioned ortho or para to R ¹⁸ , meaning that when the amino rest bearing the substituents R ²⁰ and R ²¹ is positioned ortho to R ¹⁸ , the -OR ²² is positioned para to R ¹⁸ , and vice versa.

This invention refers to all tautomeric and geometric isomers of the dyes of formula (1 ) and mixtures thereof. Alkyl groups appearing in this invention may be straight-chain or branched and are (Ci- Ci2)-alkyl groups, preferably (Ci-C8)-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, tert- butyl and methylbutyl.

The same applies to alkoxy groups which accordingly are preferably (Ci-C8)-alkoxy, for example methoxy and ethoxy, to thioalkoxy groups, which are preferably (Ci-Cs)- thioalkoxy, for example -SCH3 or -SC2H5.

Cycloalkyl groups are preferably (C3-C8)-cycloalkyl and preferably cyclopentyl and cyclohexyl. The term cyloalkyl comprises for the purpose of the present invention substituted cycloalkyl groups and unsaturated cycloalkyl 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(hydroxy- alkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy. Alkenyl groups may be straight-chain or branched and are preferably (C2-C6)-g roups for example vinyl and allyl. The term alkenyl comprises for the purpose of the present invention alkynyl groups as well, for example ethynyl and propargyl.

Aryl groups appearing in this invention are preferably phenyl or naphthyl. The terms phenyl and naphthyl comprise unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxy, alkylthio, acyl, nitro, cyano, amino, monoalkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis(hydroxyalkyl)amino, monoalkyl-mono(hy- droxyalkyl)amino, carbamoyl, sulfamoyl, acylamino, ureido, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Heteroaryl groups 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, benz- oxazole and isoxazole. The term heteroayl 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, mono- alkylamino, dialkylamino, mono(hydroxyalkyl)amino, bis (hydroxyalkyl)amino, mono- alkyl-mono(hydroxyalkyl)amino, carbamoyl, sulfamoyi, acylamino, ureido, aminosul- fonylamino, alkoxycarbonyl and acyloxy.

Heterocycloalkyi groups are preferably pyrrolidine, piperidine, morpholine, tetra- hydrofuran or piperazine. The term heterocycloalkyi 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, monoalkyl- amino, dialkylamino, mono(hydroxyalkyl)amino, bis-(hydroxyalkyl)amino, monoalkyl- mono(hydroxyalkyl)amino, carbamoyl, sulfamoyi, acylamino, aminocarbonylamino, aminosulfonylamino, alkoxycarbonyl and acyloxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(Ci-C ₄ )- alkylammonium.

Particular preferred embodiments of the present invention are the dyes of formula (1 a) and mixtures thereof

(1 a) wherein R ^{1 a} , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,

R ^9a , R ^10a , R ^{1 1 a} and R ^12a independent of each other is hydrogen, (Ci -C )-alkyl, (C1 -C4)- alkoxy, halogen, trifluoromethyl, (Ci -C ₄ )-acylamino or SO3M,

R ^13a and R ^18a independent of each other is cyano, carbamoyl or alkoxycarbonyl,

R ^14a and R ^19a independent of each other is unsubstituted, linear or branched (Ci -C ₄ )- alkyl, unsubstituted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R ^15a , R ^16a R ^17a , R ^20a , R ^{21 a} and R ^22a independent of each other is hydrogen, alkyi, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl- thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, hetero- cycloalkylalkyl

or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur

or

alkyi substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, Ν,Ν-dialkyl-amino, N- monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono- cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SOsM

or

alkyi interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, 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-monocycloalkyl-amino, N,N-monoaryl- monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SOsM

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In especially preferred dyes of formula (1 a) R ^{1 a} , R ^3a , R ^4a , R ^5a , R ^6a and R ^8a independent of each other is SO ₃ M, hydrogen, alkyl, alkoxy or halogen, whereby at least two of them are SO3M,

R ^2a and R ^7a is hydrogen,

R ^9a , R ^10a , R ^{1 1 a} and R ^12a independent of each other is hydrogen, methyl, methoxy, ethoxy, halogen, -SO3M or acetylamino,

R ^13a and R ^18a independent of each other is cyano or carbamoyl,

R ^14a and R ^19a is methyl,

R ^15a , R ^16a , R ^20a and R ^{21 a} independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3- methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1 -ethyl propyl, 1 ,2- dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxy propyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 2-(2- hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2- hydroxyethoxy)propyl, 2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 2-(2- hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3- ethoxy-propyl or 3-ethoxybutyl

or

(C ₂ -C ₆ )-alkyl substituted by COOM or by SO ₃ M,

R ^17a and R ^22a independent from each other is hydrogen, (C1-C6) alkyl or (C1-C6) alkyl interrupted by -O- or -S- and

M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of formula (1 a) are the compounds of formulae (1 a ¹ to 1 a ⁴⁰⁴ ) and mixtures thereof (Table 1 ): hereby R ^{1 a} and R ^8a are hydrogen DYS 2013/00

Table 1

Further particular preferred embodiments of the present invention are the dyes of formula 1 b) and mixtures thereof

(1 b) wherein

R ^{1 b} , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b and R ^8b independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, and wherein at least two of them are SO3M, R ^9b , R ^10b , R ^{11 b} and R ^12b independent of each other is hydrogen, (Ci -C )-alkyl, (C1 -C4)- alkoxy, halogen, trifluoromethyl(Ci -C ₄ )-acylamino or SO3M,

R ^13b and R ^18b independent of each other is cyano, carbamoyl or alkoxycarbonyl, R ^14b and R ^19b independent of each other is unsubstituted, linear or branched (Ci -C ₄ )- alkyl, unsubstituted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R ^15b , R ^16b , R ^20b and R ^{21 b} independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkyl- thioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, hetero- cycloalkylalkyl

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur

or

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, Ν,Ν-dialkyl-amino, N- monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono- cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SOsM

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, 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-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M

or

joined together to form five or six membered ring being unsubstituted or substituted by one or more (Ci-C ₄ )-alkyl-groups and the ring being uninterrupted or interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur, R ^17b and R ^22b , independent from each other is hydrogen, (C1-C6) alkyl, (C1-C6) alkoxy,

(C1-C6) alkyl terminated by halogen, hydroxyl

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In especially preferred dyes of formula (1 b)

R ^{1 b} , R ^3b , R ^4b , R ^5b , R ^6b and R ^8b independent of each other is SO ₃ M, hydrogen, alkyl, alkoxy or halogen, whereby at least two of them are SO3M,

R ^2b and R ^7b is hydrogen,

R ^9b , R ^10b , R ^{11 b} and R ^12b independent of each other is hydrogen, methyl, methoxy, ethoxy, halogen, -SO3M or acetylamino,

R ^13b and R ^18b independent of each other is cyano or carbamoyl,

R ^14b and R ^19b is methyl,

R ^15b , R ^16b , R ^20b and R ^{21 b} independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3- methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1 -ethyl propyl, 1 ,2- dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxy propyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 2-(2- hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2- hydroxyethoxy)propyl, 2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 2-(2- hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3- ethoxy-propyl, 3-ethoxybutyl

or

(C2-C6) alkyl substituted by COOM or by SO3M

or joined together to form five or six membered ring being unsubstituted or substituted by one or more (Ci-C ₄ )-alkyl-groups and the ring being uninterrupted or interrupted by one or more heteroatoms selected from the group consting of oxygen and sulphur, R ^17b and R ^22b independent from each other is hydrogen or (C1-C6) alkyl

and

M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of formula (1 b) are the compounds of formulae (1 b ¹ to 1 b ²⁴ ) and mixtures thereof, (Table 2) whereby R ^{1 b} and R ^8b are hydrogen

DYS 2013/00

Table 2

^* refers to the point of attachment to the nitrogen atom

Further preferred embodiments of the present invention are the dyes of formula (1 c) and mixtures thereof

(1 c) wherein

R ^1c , R ^2c , R ^3c , R ^4c , R ^5c , R ^6c , R ^7c and R ^8c independent of each other is hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO3M, whereby at least two of them are SO3M,

R ^9c , R ^10c , R ^{1 1c} and R ^12c independent of each other is hydrogen, (Ci -C )-alkyl, (C1 -C4)- alkoxy, halogen, trifluoromethyl, (Ci -C ₄ )-acylamino or SO3M,

R ^13c and R ^18c independent of each other is cyano, carbamoyl or alkoxycarbonyl,

R ^14c and R ^19c independent of each other is unsubstituted, linear or branched (Ci -C ₄ )- alkyl, unsubstituted (Cs-CzJ-cycloalkyl or substituted (Cs-CzJ-cycloalkyl with one or more substituents preferably selected from the group consisting of methyl, ethyl, isobutyl, sec-butyl, tert-butyl and methylbutyl, R ^15c , R ^16c R ^17c , R ^20c , R ^21c and R ^22c independent of each other is hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, carbamoyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkyloxyalkyl, aminoalkylthioxyalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioxyalkyl, heteroarylalkyl, heterocycloalkylalkyl

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur

or

alkyl substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, amino, N-monoalkyl-amino, Ν,Ν-dialkyl-amino, N- monoaryl-amino, Ν,Ν-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, Ν,Ν-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-mono- cycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfa-

or

alkyl interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulphur and substituted by one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, 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-monocycloalkyl-amino, Ν,Ν-monoaryl-monocycloalkyl-amino, N-acylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, acyl, alkylsulfonyl, aryloyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, acyloxy, aryloyloxy, carbamoyl, sulfamoyl and SO3M

and

M is hydrogen, an alkali metal, ammonium, one equivalent of an alkali earth metal or a monovalent organic cation.

In especially preferred dyes of formula (1 c) R ^1c , R ^3c , R ^4c , R ^5c , R ^6c and R ^8c independent of each other is SO ₃ M, hydrogen, alkyl, alkoxy or halogen, whereby at least two of them are SO3M,

R ^2c and R ^7c is hydrogen,

R ^9c , R ^10c , R ^11c and R ^12c independent of each other is hydrogen, methyl, methoxy, ethoxy, halogen, -SO3M or acetylamino,

R ^13c and R ^18c independent of each other is cyano or carbamoyl,

R ^14c and R ^19c is methyl, pi5 _Cj pi 6c pi 7 _Cj p2o _Cj p2ic _{a nc} | p22c independent of each other is hydrogen, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2- methylcyclohexyl, 3-methylcyclohexyl, isopropyl, sec-butyl, 2-methylbutyl, 1 - ethylpropyl, 1 ,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, allyl, 2-methoxyethyl, 3-methoxy- propyl, 2-cyanoethyl, 2-(methylthio)ethyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 2-(2-tertbutylsulfanylethanesulfonyl)-ethyl, 2-(2- hydroxyethoxy)propyl, 2-(2-hydroxy ethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 2-(2- hydroxyethanesulfonyl)-ethyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3- ethoxy-propyl, 3-ethoxybutyl

or

(C2-C6) alkyl substituted by COOM or by SO ₃ M

and

M is hydrogen, sodium, potassium, lithium or ammonium.

Examples of preferred dyes of formula (1 c) are the compounds of formulae (1 c ¹ to 1 c ¹⁸⁴ ) and mixtures thereof (Table 3):

Hereby R ^1c and R ^8c are hydrogen DYS 2013/00

Table 3

1c ²⁵ SOsH H H SOsH

6-SOsH H CN H Sec-butyl

1c ²⁶ H SOsH SOsH H

1c ²⁷ SOsH H H SOsH 2-Methyl

6-SOsH H CN H

1c ²⁸ H SOsH SOsH H butyl H

1c ²⁹ SOsH H H SOsH

_{1 c} 30 6-SOsH H CN H 1 -Ethyl propyl H

H SOsH SOsH H

1c ³¹ SOsH H H SOsH 1 ,2-Dimethyl

6-SOsH H CN H H propyl

1c ³² H SOsH SOsH H

_{1 c} 33 SOsH H H SOsH

6-SOsH H CN H Tert-butyl H

1c ³⁴ H SOsH SOsH H

_{1 c} 35 SOsH H H SOsH

_{1 c} 36 6-SOsH H CN H 3-Methyl butyl H

H SOsH SOsH H

1c ³⁷ SOsH H H SOsH

_{1 c} 38 6-SOsH H CN H Pentan-2-yl H

H SOsH SOsH H

_{1 c} 39 SOsH H H SOsH

6-SOsH H CN H 2-Ethylhexyl H

1c ⁴⁰ H SOsH SOsH H

1c ⁴¹ SOsH H H SOsH 2,2-Dimethyl

6-SOsH H CN H H propyl

1c ⁴² H SOsH SOsH H

1c ⁴³ SOsH H H SOsH

6-SOsH H CN H Phenyl H

1c ⁴⁴ H SOsH SOsH H

1c ⁴⁵ SOsH H H SOsH

6-SOsH H CN H Benzyl H

1c ⁴⁶ H SOsH SOsH H

1c ⁴⁷ SOsH H H SOsH

7-SOsH H CN H Methyl

1c ⁴⁸ H SOsH SOsH H H

1c ⁴⁹ SOsH H H SOsH

_{1 c} 50 7-SOsH H CN H Ethyl H

H SOsH SOsH H

1c ⁵¹ SOsH H H SOsH

7-SOsH H CN H Propyl H

1c ⁵² H SOsH SOsH H

_{1 c} 53 SOsH H H SOsH

7-SOsH H CN H Butyl H

1c ⁵⁴ H SOsH SOsH H

_{1 c} 55 SOsH H H SOsH

_{1 c} 56 7-SOsH H CN H Pentyl H

H SOsH SOsH H

1c ⁵⁷ SOsH H H SOsH

_{1 c} 58 7-SOsH H CN H Hexyl H

H SOsH SOsH H

_{1 c} 59 SOsH H H SOsH

_{1 c} 60 7-SOsH H CN H Cyclobutyl H

H SOsH SOsH H

1c ⁶¹ SOsH H H SOsH

7-SOsH H CN H Cyclopentyl H

1c ⁶² H SOsH SOsH H

_{1 c} 63 SOsH H H SOsH

7-SOsH H CN H Cyclohexyl H

1c ⁶⁴ H SOsH SOsH H

_{1 c} 65 SOsH H H SOsH 2-Methyl

_{1 c} 66 7-SOsH H CN H H

H SOsH SOsH H cyclohexyl

1c ⁶⁷ SOsH H H SOsH 3-Methyl

_{1 c} 68 7-SOsH H CN H H

H SOsH SOsH H cyclohexyl

_{1 c} 69 SOsH H H SOsH

7-SOsH H CN H Isopropyl H

1c ⁷⁰ H SOsH SOsH H

1c ⁷¹ SOsH H H SOsH

7-SOsH H CN H Sec-butyl H

1c ⁷² H SOsH SOsH H

1c ⁷³ SOsH H H SOsH 2-Methyl

7-SOsH H CN H H

1c ⁷⁴ H SOsH SOsH H butyl

1c ⁷⁵ SOsH H H SOsH

7-SOsH H CN H 1 -Ethyl propyl H

1c ⁷⁶ H SOsH SOsH H

1c ⁷⁷ SOsH H H SOsH 1 ,2-Dimethyl

7-SOsH H CN H H propyl

1c ⁷⁸ H SOsH SOsH H

1c ⁷⁹ SOsH H H SOsH

_{1 c} 80 7-SOsH H CN H Tert-butyl H

H SOsH SOsH H

1c ⁸¹ SOsH H H SOsH

7-SOsH H CN H 3-Methyl butyl H

1c ⁸² H SOsH SOsH H

_{1 c} 83 SOsH H H SOsH

7-SOsH H CN H Pentan-2-yl H

1c ⁸⁴ H SOsH SOsH H

_{1 c} 85 SOsH H H SOsH

7-SOsH H CN H 2-Ethylhexyl H

_{1 c} 86 H SOsH SOsH H

1c ⁸⁷ SOsH H H SOsH 2,2-Dimethyl

7-SOsH H CN H H

_{1 c} 88 propyl

H SOsH SOsH H

_{1 c} 89 SOsH H H SOsH

_{1 c} 90 7-SOsH H CN H Phenyl H

H SOsH SOsH H

1c ⁹¹ SOsH H H SOsH

7-SOsH H CN H Benzyl H

1c ⁹² H SOsH SOsH H

_{1 c} 93 SOsH H H SOsH

6-SOsH H CONH ₂ H Methyl H

1c ⁹⁴ H SOsH SOsH H

_{1 c} 95 SOsH H H SOsH

_{1 c} 96 6-SOsH H CONH2 H Ethyl H

H SOsH SOsH H

1c ⁹⁷ SOsH H H SOsH

_{1 c} 98 6-SOsH H CONH2 H Propyl

H SOsH SOsH H H

1c ¹⁴⁷ SOsH H H SOsH

_{1 c} 148 7-SOsH H CONH2 H Pentyl H

H SOsH SOsH H

_{1 c} 149 SOsH H H SOsH

_{1 c} 150 7-SOsH H CONH2 H Hexyl H

H SOsH SOsH H

_{1 c} 151 SOsH H H SOsH

_{1 c} 152 7-SOsH H CONH2 H Cyclobutyl H

H SOsH SOsH H

_{1 c} 153 SOsH H H SOsH

_{1 c} 154 7-SOsH H CONH2 H Cyclopentyl H

H SOsH SOsH H

_{1 c} 155 SOsH H H SOsH

_{1 c} 156 7-SOsH H CONH2 H Cyclohexyl H

H SOsH SOsH H

_{1 c} 157 SOsH H H SOsH 2-Methyl

_{1 c} 158 7-SOsH H CONH2 H H

H SOsH SOsH H cyclohexyl

_{1 c} 159 SOsH H H SOsH 3-Methyl

_{1 c} 160 7-SOsH H CONH2 H H

H SOsH SOsH H cyclohexyl

_{1 c} 161 SOsH H H SOsH

_{1 c} 162 7-SOsH H CONH2 H Isopropyl H

H SOsH SOsH H

_{1 c} 163 SOsH H H SOsH

_{1 c} 164 7-SOsH H CONH2 H Sec-butyl H

H SOsH SOsH H

_{1 c} 165 SOsH H H SOsH

_{1 c} 166 7-SOsH H CONH2 H 2-Methyl butyl H

H SOsH SOsH H

_{1 c} 167 SOsH H H SOsH

_{1 c} 168 7-SOsH H CONH2 H 1 -Ethyl propyl H

H SOsH SOsH H

_{1 c} 169 SOsH H H SOsH 1 ,2-Dimethyl

7-SOsH H CONH2 H H

_{1 c} 170 propyl

H SOsH SOsH H

1c ¹⁷¹ SOsH H H SOsH 7-SOsH H CONH2 H Tert-butyl H

1c ¹⁷² H SOsH SOsH H

_{1 c} 173 SOsH H H SOsH

7-SOsH H CONH2 H 3-Methyl butyl H

1c ¹⁷⁴ H SOsH SOsH H

_{1 c} 175 SOsH H H SOsH

7-SOsH H

76 CONH2 H Pentan-2-yl H

_{1 c} 1 H SOsH SOsH H

1c ¹⁷⁷ SOsH H H SOsH

7-SOsH H CONH2 H 2-Ethylhexyl H

_{1 c} 178 H SOsH SOsH H

_{1 c} 179 SOsH H H SOsH 2,2-Dimethyl

7-SOsH H CONH2 H H

_{1 c} 180 propyl

H SOsH SOsH H

_{1 c} 181 SOsH H H SOsH

7-SOsH H CONH2 H Phenyl H

_{1 c} 182 H SOsH SOsH H

_{1 c} 183 SOsH H H SOsH

7-SOsH H CONH2 H Benzyl H

_{1 c} 184 H SOsH SOsH H

The present invention also provides a process for the preparation of the dyes of formula (1 ) and mixtures thereof, comprising the steps

a) diazotization of a compound of formula (2)

(2)

wherein R ¹ to R ⁸ are defined as given above,

b) reacting diazonium salt obtained in step a) with the compounds of formula (3) and (4) in stoichiometric amoun

wherein R ⁹ to R ¹² are defined as given above, to yield an intermediate of formula (5)

c) diazotization of the compound of formula (5),

d) reacting the diazonium salts obtained in step c) with the compounds of the formula (6), (7), (8) and (9) or mixtures thereof

wherein R ¹³ to R ²² are defined as given above.

The diazotization of the compound of formula (2) and (5), respectively 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 reaction of the diazonium salts obtained by diazotization of the compound of the formula (2) onto the compounds of formulae (3) and (4) as well as the coupling reaction of the the diazonium salts obtained by diazotization of the compound of the formula (5) onto the compounds of formulae (6), (7), (8) and (9) can likewise be performed by known methods.

The compounds of formula (2) are known and commercially available and can also be synthesised by means of common chemical reactions known to a person skilled in the art such as the methods disclosed in US5728874 or DE172106.

The pyridines of formula (6), (7), (8) and (9) in which R ¹³ and R ¹⁸ denote cyano are commercially available or can be synthesized via methods disclosed in the literature such as DE2230392. Through analogy, all the pyridine derivatives that are used in this invention can be synthesized with the protocol. The obtained pyridines can be further derivatized by reactions known to persons skilled in the art, such as hydrolysis to form pyridines of formula (6), (7), (8) and (9) in which R ¹³ and R ¹⁸ are carbonamide or by hydrolysis and further esterification to form pyridine derivatives in which R ¹³ and R ¹⁸ are alkoxycarbonyl.

The above-mentioned derivatization reactions can be carried out in alkaline or acidic media, preferably in acidic media using strong inorganic acids such as sulfuric acid or hydrochloric acid gaseous or solution, acidic resins or chlorotrimethylsilane or other suitable acid catalyst in the presence of the corresponding alcohol. The reactions are advantageously carried out under inert atmosphere at temperatures in the range from 40 to 150 °C. Alternatively, the above mentioned derivatization reactions can be undertaken as a final step after the synthesis of the corresponding dyes with pyridine nitriles.

The dyes of the present invention can be used alone or as a mixture with other dyes according to the present invention and/or other substances.

Thus a chemical composition comprising one or more dye(s) as described above is also an aspect of the present invention. A chemical composition consisting of two or more dyes as described above forms another preferred aspect of the present invention.

Also an aqueous solution for dyeing comprising one or more dye(s) as described above forms an aspect of the present invention.

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 acid dyes. Therefore, the present invention also provides 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.

The use of a dye as described above, a chemical composition as described above or of an aqueous solution as described above for dyeing fibers, as well as blends of such fibres selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers and Lyocell fibers forms another aspect of the present invention.

Still another aspect of the present invention is/are: Fiber and blends containing such fiber selected from the group consisting of: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aramid fibres, vegetable fibres, seed fibres, cotton, organic cotton, kapok, coir from coconut husk; bast fibers, flax, hemp, jute, kenaf, ramie, rattan; leaf fibres, sisal, henequen, banana; stalk fibres, bamboo; fibres from animals, wool, organic wool, silk, cashmere wool, alpaca fiber, mohair, Angora fibre as well as fur and leather materials; manufactured, regenerated and recycled fibres, cellulosic fibres; paper fibres, cellulosic regenerated fibres, viscose rayon fibres, acetate and triacetate fibers, and Lyocell fibers comprising one or more dye(s) of the present invention either in chemically and/or physically bound form.

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. For instance in the form of sheetlike structures, such as paper and leather, in the form of films, such as nylon films, or in the form of a bulk mass, for example composed of polyamide and polyurethane, in particular in the form of fibers, for example cellulose fibers. The fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of hanks or wound packages. The dyes of the present invention and their salts and/or mixtures can be used as a single dyeing colorant in dyeing or printing processes or can be part of a di-, tri- or multi-component combination colorant in dyeing or in printing compositions. The di-, tri- or multi-component shade dyeings show similar fastness level as compared to dyeing performed with a single colorant component.

Dyes of the present invention and their salts or mixtures are highly compatible with other known and/or commercially available acid dyes and they can be used together with such dyes of related chromophores and similar technical performance to obtain specific hues. Similar technical performance includes: comparable build-up, comparable fastness properties and comparable exhaustion rates during dyeings.

The dyes according to the invention can be applied to the materials mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes. This applies to both, dyeing and printing processes.

It applies in particular to the production of dyeings on fiber materials composed of wool or other natural polyamides or of synthetic polyamides and their mixtures with other fiber material. In general, the material to be dyed is introduced into the bath at a temperature of about 40 °C, agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98 °C. However, the dyeings can also be carried out at the boil or in a sealed dyeing apparatus at temperatures of up to 106 °C.

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. For this the dyes of the present invention need to be formulated in aqueous inks. An Ink for digital textile printing, comprising a dye of the present invention is another aspect 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 to 50 % by weight, more preferably from 0.5 to 30 % by weight and most preferably from 1 to 15 % by weight, based on the total weight of the ink.

If desired the inks may contain further dyes used in digital printing in addition to the one or more dyes of the present invention.

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 to 50 % by weight and preferably 5 to 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-cyclohexylpyrrolidone, 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 present 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, 1 ,2- hexanediol.

The inks of the present invention may further comprise 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 invention are particularly useful in inkjet printing processes for printing a wide variety of pretreated materials, such as silk, leather, wool, polyamide fibers and polyurethanes, and cellulosic fiber materials of any kind. Blend fabrics, for example blends of cotton, silk, wool with polyester fibers or polyamide fibers can similarly be printed.

In contrast to conventional textile printing, where the printing ink already contains all necessary chemicals, in digital or inkjet printing the auxiliaries have to be applied to the textile substrate in a separate pretreatment step. The pretreatment of the textile substrate, for example cellulose and regenerated cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor prior to printing. In addition there is a need for thickeners to prevent flowing of the motives when the printing ink is applied, for example sodium alginates, modified polyacrylates or highly etherified galactomannans.

These pretreatment reagents are uniformly applied to the textile substrate in a defined amount using suitable applicators, for example using a 2- or 3-roll pad, contactless spraying technologies, by means of foam application or using appropriately adapted inkjet technologies, and subsequently dried.

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

8.62 g of 4,4'-Diamino-biphenyl-2,2'-disulfonic acid was first dissolved in water at slightly acidic pH to give a complete solution. Ice was added to the solution and when temperature reached 10 to 15 °C, 10.6 ml of 5 N sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into 12.38 g of concentrated HCI with 12 g of ice. Yellow suspension was formed and reaction mixture was completed within an hour. 6.30 g of 2,5-Dimethyl-phenylamine were added directly into the diazo suspension and stirred. A violet precipitate was observed upon addition. The obtained intermediate precipitate, 4,4'-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2'-disu lfonic acid, was filtered off with suction and washed with organic solvent and dried. 15.22 g of the dried intermediate, 4,4'-Bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl- 2,2'-disulfonic acid, was then dissolved in water at slightly acidic pH to give a complete reddish orange solution. Ice was added to the solution and when the temperature reached 10 to 15 °C, 10.1 ml of 5 N sodium nitrite solution were added dropwise. The reaction mixture was further cooled down to 0 to 8 °C when the mixture was added dropwise into concentrated HCI with ice. Violet suspension was formed and reaction mixture was completed in 90 mins.

The obtained reaction mixture was used in the next step as described below:

1 1 .63 g of 6-Hydroxy-2-(3-methoxy-propylamino)-4-methyl-nicotinonitrile were stirred in methanol and adjusted to slightly acidic. The reaction mixture was added dropwise into the methanol solution and stirred. Brilliant orange precipitate was observed upon addition. Precipitate obtained was filtered off with suction and washed with brine giving product of the formula 1 a ¹⁹⁰ . The analytic data are consistent with the assigned structure for product 1 a ¹⁹⁰ . The product dyes the targeted fibre materials in brilliant scarlet to red shades.

Through analogy, all the dyes of formulae (1 a ¹ -1 a ⁴⁰⁴ ), (1 b ¹ -1 b ²⁴ ) and (1 c ¹ -1 c ¹⁸⁴ ) can be synthesized according to the method described above. Dyeing example 1

1 part of the dye 1 a ¹⁹⁰ of this invention was 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 were added. The pH was then adjusted to 5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6 fabric. The temperature was raised to 98 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing example 2

1 part of the dye 1 a ¹⁹⁰ of this invention was 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 were added. The pH was then adjusted to 5.5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven polyamide-6, 6 fabric. The temperature was raised to 120 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 60 °C and removal of the dyed material. The polyamide-6, 6 fabric was washed with hot and cold water, soaped and then spun and dried. The dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing example 3

100 parts of polyamide-6 material were padded with a 1000 parts 50 °C liquor solution that consisted of 40 parts of the dye 1 a ¹⁹⁰ , 100 parts of urea, 20 parts of a non ionic solubilizer based on butyldiglycol, 20 parts of acetic acid to adjust the pH to 4.0, 10 parts of levelling assistant (based on ethoxylated aminopropyl fatty acid amide) and 815 parts of water. The material was rolled up and placed into a steaming chamber at 85 to 98 °C for 3 to 6 hours. After fixation, the fabric was washed with hot and cold water, soaped and then spun and dried. The dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing example 4

1 part of the dye 1 a ¹⁹⁰ of this invention was dissolved in 2000 parts of water and 5 parts of sodium sulphate, and 1 part of levelling assistant (based on condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate are added. The pH was then adjusted to 4.5 using acetic acid (80 %). The dyebath was heated to 50 °C for 10 minutes and then entered with 100 parts of a woven wool fabric. The temperature was raised to 100 °C over the course of 50 minutes and then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling to 90 °C and removal of the dyed material. The wool fabric was washed with hot and cold water, soaped and then spun and dried. The dyeing obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

Dyeing example 5

1 part of the dye 1 a ¹⁹⁰ of this invention was dissolved in 1000 parts of soft water and 7.5 parts of sodium sulphate and 1 part of a wetting agent (anionic) were added. 100 parts of bleached cotton knitted fabric were added to this solution. The dye bath was then heated up to 98 °C with a gradient of 2 °C/min, then dyeing was carried out at this temperature for 60 minutes. This was followed by cooling down to 80 °C. At 80 °C the dyeing was continued for another 20 minutes. The dyed material was then removed and was washed with hot and cold water, soaped and then spun and dried. The dyeings obtained gave red shade and has very good light and wet fastness and also good levelness in the fibre.

Example 6 - Preparation of an Ink

3 parts of the dye 1 a ¹⁹⁰ of this invention dissolved in 82 parts of deionized water was added into the dyebath with 15 parts of diethylene glycol at 60 °C. On cooling, a red printing ink was obtained. The red printing ink can be used for ink jet printing on paper, polyamide or wool textiles. Dyeing example 7

4 parts of chemically bleached (pine wood) sulphite pulp was mixed up with 100 parts of 55 °C water. 1 part of the dye 1 a ¹⁹⁰ of this invention was dissolved in 100 parts of hot water. 80 parts of this solution were given to the mixed-up pulp and mixed for 2 minutes. After that the mixture was sized with resin size in a conventional manner and mixed for another 2 minutes. 55 parts of this solution were then diluted with 2000 parts of cold water and the paper was produced out of this solution. The red paper produced from the mixture has good wet fastnesses.