TW201522523A - Acid dyes, methods for the production thereof and their use - Google Patents

Abstract

Dyes according to formula (1): the production and use thereof.

Description

Acid dye, its production method and use thereof

The present invention relates to the technical field of pigments for dyeing and printing materials containing hydroxyl groups and/or carboguanamine groups.

Acid dyes having an aminopyrazolone coupling agent are known from the prior art and can be used as colorants in various applications, see for example US 5,543,259, JP 60215082 A and WO 2005/018931 A1.

However, known dyes have many technical disadvantages that require improvement in the context of dyeing and printing of materials containing hydroxyl, amine and/or carboxamide groups. One such drawback is that many of them contain heavy metals such as Cu, Cr or Ni. Such heavy metals are dangerous from a toxicological and environmental point of view and should therefore be excluded.

Surprisingly, it has now been found that dyes of formula (1) as described below show highly advantageous properties over known dyes. These characteristics include high tint strength and high color fastness as well as high color fastness characteristics such as the materials mentioned above, blends containing the same, and the washing, contact and light fastness of the microfibers. Most importantly, have a chemical formula The dye of (1) is substantially free of heavy metals and provides levelled dyeing. The metal may exist only as a counter ion and is selected from the group of alkali metals and alkaline earth metals, which do not function like heavy metals.

The present invention relates to a dye of formula (1):

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, by At least two of them are SO ₃ M; X is oxygen or sulfur; and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ are each independently hydrogen, alkyl, Substituted alkyl, alkyl interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, Alkylcarbonyl, mercaptoamine, alkylsulfonylamino, amine, monoalkyl-amine, monocycloalkyl-amino, dialkyl-amine, di(cyclo)alkyl-amine Alkyl, alkylthio, alkylsulfonyl, alkoxycarbonyl, aminemethanyl, sulfonyl, ureido, alkylureido or -SO ₃ M; R ¹³ and R ²⁰ are hydroxy or amine ; R ¹⁴ and R ²¹ are, independently of each other, hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, aminecaraki, alkoxycarbonyl, COOM, amine, hydroxy, monocyclic Alkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino Diaryl-amino, monocycloalkylmonoarylamine, monoalkylmonoarylamine, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl; or as one or more a substituent-substituted alkyl group, the one or more substituents being selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy , alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, aminecarbamyl, nitro, amine, decylamino, arylcarbonylamino, alkyl sulfonate a mercaptoamine group, an arylsulfonylamino group, a ureido group, an alkylureido group, and a phenylureido group; R ¹⁵ and R ²² are each independently hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl , cycloalkyl, aryl, heteroaryl, heterocycloalkyl, amine mercapto, alkyl ureido, phenyl-ureido, hydroxyalkyl sulfonylalkyl, aminoalkyl, amine - Hydroxy-alkyl, alkoxyalkyl-aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkoxyalkyl, amino-alkylthioalkyl, cycloalkylane Base, aryloxyalkyl, arylthioalkyl, heteroaryl An alkyl group, a heterocycloalkylalkyl group; or an alkyl group interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur; or by one or more a substituent-substituted alkyl group, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl -Amino, N,N-dialkyl-amino, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N- Monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl Sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N- Monocycloalkyl-amine, mercapto, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N- Single Fang -Aminomethyl sulfhydryl, N,N-diaryl-aminocarbamimidyl, N-monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl-amine A Sulfhydryl, sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-bicycloalkyl-amine sulfonyl, N,N- Alkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N a monoalkyl-N-monoarylamine sulfonyl group and SO ₃ M; or an alkyl group interrupted by one or more heteroatoms and substituted by one or more substituents selected from a group consisting of oxygen and sulfur, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amino, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl- Amino, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkane Amino-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkane Urea, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkylsulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkane Oxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-aminecarbamyl, N, N-bicycloalkyl-aminecarbamyl, N,N-dialkyl-aminecarbamyl, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl, N -monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl-aminecarbamyl, aminesulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N , N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; An aryl group substituted with one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amino, N,N-dialkyl-amine, N-single Aryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amine , N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, Urea group, alkyl urea group, phenyl urea group, halogen, cyano group, COOM, nitro group, sulfhydryl group, thiol group, alkyl sulfonyl group, aryl fluorenyl group, trifluoromethyl group, heteroaryl group, hetero Cycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, aminecarboxamido, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-amine A Mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, mercapto, N,N-diaryl-amine Mercapto, N-monocycloalkyl-N-monoarylamine, mercapto, N-monoalkyl-N-monoaryl-amine, mercapto, aminesulfonyl, N-monocycloalkyl- Aminesulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine Sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl And SO ₃ M; M is hydrogen, alkali metal, ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation; such dye of formula (1) having two to six sulfonic acid groups.

The present invention relates to all tautomers and geometric isomers of the dye of formula (1), as well as mixtures thereof.

The alkyl group which is present in the present invention may be linear or branched and is a (C ₁ -C ₁₂ )-alkyl group, preferably a (C ₁ -C ₈ )-alkyl group. For example, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, secondary butyl, tert-butyl and methylbutyl.

The same applies for alkoxy groups, which are therefore preferred (C ₁ -C ₈₎ - alkoxy, such as methoxy and ethoxy; for sulfur alkoxy groups, they are preferably (C ₁ -C ₈ )-thioalkoxy, for example -SCH ₃ and -SC ₂ H ₅ .

The cycloalkyl group is preferably a (C ₃ -C ₈ )-cycloalkyl group and particularly preferably a cyclopentyl group or a cyclohexyl group. For the purposes of the present invention, the term cycloalkyl includes substituted cycloalkyl groups as well as unsaturated cycloalkyl groups. A preferred group of this type is cyclopentenyl. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxy, alkoxy, decyl, cyano, nitro, amine, monoalkylamino, dialkylamino, mono(hydroxyalkyl) Amino, bis-(hydroxyalkyl)amino, monoalkyl-mono(hydroxy-alkyl)amine, aminemethanyl, aminesulfonyl, decylamino, ureido, amine sulfonium Alkyl-amino, alkoxycarbonyl and anthracenyloxy.

The alkenyl group may be straight-chain or branched, and is preferably a (C ₂ -C ₆ ) group such as a vinyl group and an allyl group. For the purposes of the present invention, the term alkenyl also includes alkynyl groups such as ethynyl and propynyl.

The aryl group which is present in the present invention is preferably a phenyl group or a naphthyl group. The terms phenyl and naphthyl include unsubstituted as well as substituted phenyl and naphthyl. Preferred substituents are alkyl, cycloalkyl, heterocycloalkyl, hydroxyalkyl, halogen, hydroxy, alkoxy, alkylthio, decyl, nitro, cyano, amine, monoalkylamine Base, dialkylamino group, mono(hydroxyalkyl)amino group, bis-(hydroxyalkyl)amino group, monoalkyl-mono(hydroxyalkyl)amino group, amine methyl group, amine sulfonyl group, Mercaptoamine, ureido, aminosulfonylamino, alkoxycarbonyl and decyloxy.

Preferred heteroaryl groups are pyridine, pyrimidine, pyrene Pyr , pyrrole, imidazole, pyrazole, 1,2,4-thiadiazole, 1,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, benzothiazole, benzisothiazole, 1,3, 4-thiadiazole, furan, Azole, benzo Oxazole or different Oxazole. The term heteroaryl includes the above-mentioned groups in unsubstituted form as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxy, alkoxy, alkylthio, decyl, nitro, cyano, amine, monoalkylamino, dialkylamino, single (Hydroxyalkyl)amine, bis-(hydroxyalkyl)amine, monoalkyl-mono(hydroxyalkyl)amine, aminecarbamyl, amine sulfonyl, decylamino, ureido, amine A sulfonylamino group, an alkoxycarbonyl group, and a decyloxy group.

Preferred heterocycloalkyl groups are pyrrolidine, piperidine, Porphyrin, tetrahydrofuran or piper . The term heterocycloalkyl includes the above-mentioned groups in unsubstituted form as well as in substituted form. Preferred substituents are alkyl, hydroxyalkyl, halogen, hydroxy, alkoxy, alkylthio, decyl, nitro, cyano, amine, monoalkylamino, dialkylamino, single (Hydroxyalkyl)amine, bis(hydroxyalkyl)amine, monoalkyl-mono(hydroxyalkyl)amine, aminecarbamyl, aminesulfonyl, decylamino, amino-carbonyl- Amino, aminosulfonylamino, alkoxycarbonyl and alkoxy.

Halogen is preferably chlorine, bromine or fluorine.

M is preferably hydrogen, lithium, sodium, potassium or mono-, di-, tri- or tetra-(C ₁ -C ₄ )-alkyl ammonium.

There are different sets of preferred embodiments. In a preferred embodiment, one of R ¹³ and R ²⁰ is a hydroxyl group and the other is an amine group. In another preferred embodiment, both R ¹³ and R ²⁰ are amine groups, and in yet another embodiment, both R ¹³ and R ²⁰ are hydrogen. The latter two are described in further detail below.

The present invention relates to a dye of the formula (1): wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, alkyl, alkoxy a group, a halogen, a trifluoromethyl group or a SO ₃ M, whereby at least two of them are SO ₃ M; X is oxygen or sulfur; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ And R ¹⁸ and R ¹⁹ are each independently hydrogen, alkyl, substituted alkyl, alkyl interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, ring Alkyl, heterocycloalkyl, cyano, decyloxy, alkylcarbonyl, decylamino, alkylsulfonylamino, amine, monoalkyl-amine, monocycloalkyl-amine, Dialkyl-amino, di(cyclo)alkyl-amine, alkylthio, alkylsulfonyl, alkoxycarbonyl, aminemethanyl, sulfonyl, ureido, alkylureido or -SO ₃ M; R ¹³ and R ²⁰ are a hydroxyl group; R ¹⁴ and R ²¹ are independently of each other hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, aminecaraki, alkoxy Carbonyl group, COOM, amine group, hydroxyl group, monocycloalkyl-amino group, monoalkyl-amino group, di(cyclo) Amino-amino, dialkyl-amino, monoaryl-amino, diaryl-amine, monocycloalkylmonoarylamine, monoalkylmonoarylamine, alkylthio, aryl a thio group, an alkylcarbonyl group, an alkylsulfonyl group; or an alkyl group substituted by one or more substituents selected from the group consisting of a hydroxyl group, a cycloalkyl group, Heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, aminecarbamyl, nitrate Alkyl, amine, mercaptoamine, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, ureido, alkylureido and phenylureido; R ¹⁵ and R ²² Independent of each other, hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, aminemethanyl, alkylureido, phenyl-urea , hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkyl-aminoalkyl, thioalkoxyalkyl-aminoalkyl, amin Oxyalkyl, amino-alkylthioalkyl, cycloalkylalkyl An aryloxyalkyl group, an aryl thiooxyalkyl group, a heteroarylalkyl group, a heterocycloalkylalkyl group; or an alkyl group interrupted by one or more heteroatoms selected from the group consisting of a group of components: oxygen and sulfur; or an alkyl group substituted with one or more substituents selected from the group consisting of hydroxyl, aryl, cycloalkyl, Alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl-amine , N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino , N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, Cyano, COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, Oxyloxy, arylhydrazinooxy, carbamoyl, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-aminecarbamyl, N,N-dicycloalkyl-amine Mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, mercapto, N,N-diaryl-amine, mercapto, N-monocycloalkyl-N- Monoarylamine, mercapto, N-monoalkyl-N-monoaryl-amine, mercapto, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonate Mercapto, N,N-bicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine Sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or interrupted by one or more heteroatoms And an alkyl group substituted with one or more substituents selected from the group consisting of oxygen and sulfur, the one or more substituents being selected from the group consisting of : hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amino, N,N-dialkyl-amino, N-monoaryl-amino , N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-single Alkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-fluorenyl Amine, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, Aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N-monocycloalkyl -Aminomethyl sulfhydryl, N-monoalkyl-amine carbhydryl, N,N-bicycloalkyl-amine, fluorenyl, N,N-dialkyl-amine, fluorenyl, N-monoaryl Aminomethyl, N,N-diaryl-amine, mercapto, N-monocycloalkyl-N-monoarylamine, N-monoalkyl-N-monoaryl-amine formazan Amine, sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dioxane -Aminosulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N- a monoalkyl-N-monoarylamine sulfonyl group and SO ₃ M; or an aryl group substituted by one or more substituents selected from the group consisting of hydroxyl groups, Aryl, cycloalkyl, alkoxy, thioalkoxy, amine N-monoalkyl-amino, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl- Amino, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkane Amino-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, sulfhydryl, sulfur Sulfhydryl, alkylsulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine Indenyl, N-monocycloalkyl-amine, mercapto, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine Mercapto, N-monoaryl-aminecarboxylidene, N,N-diaryl-aminecarbamyl, N-monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl- N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-bicycloalkyl-amine sulfonate Mercapto, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-single Aryl Sulfo acyl, N- monoalkyl monoaryl amine -N- sulfo acyl and SO ₃ M; M is hydrogen, alkali metal, ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation; having the chemical formula (1) The dye has two to six sulfonic acid groups.

A particularly preferred embodiment of the invention is a dye of formula (1a):

Wherein R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a are each independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, by At least two of them are SO ₃ M; R ^9a , R ^10a , R ^16a and R ^17a are each independently hydrogen, alkyl, substituted alkyl, alkyl interrupted by one or two heteroatoms, alkane Oxyl, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, alkylcarbonyl, decylamino, alkylsulfonylamino, amine , monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amine, alkylthio, alkylsulfonyl, alkoxycarbonyl, amine Mercapto, sulfonyl, ureido, alkylureido or -SO ₃ M; R ^13a and R ^20a are hydroxy; R ^14a and R ^21a are independently of each other hydrogen, alkyl, cycloalkyl, trifluoro Methyl, alkoxy, cyano, amine, mercapto, alkoxycarbonyl, COOM, amine, hydroxy, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amine Base, dialkyl-amino group, monoaryl-amine group, diaryl-amino group, monocycloalkyl group Alkylamino, monoalkylmonoarylamine, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl; or alkyl substituted by one or more substituents, one or more The substituent is selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano , COOM, alkoxycarbonyl, decyloxy, aminecarbamyl, nitro, amine, decylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, Ureido, alkylureido and phenylurea; R ^15a and R ^22a are, independently of each other, hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, hetero Cycloalkyl, aminemethanyl, alkylureido, phenyl-ureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylaminoalkane Base, thioalkoxyalkyl-aminoalkyl, aminoalkoxyalkyl, aminoalkylthioalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioalkyl , heteroarylalkyl, heterocycloalkylalkyl; or One or more heteroatoms interrupted alkyl groups, the one or more heteroatoms being selected from the group consisting of: oxygen and sulfur; or an alkyl group substituted with one or more substituents, one or more The substituent is selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl- Amino, N-monoaryl-amino, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N-monocycloalkyl-amine, N,N- Dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkyl sulfonate Mercapto-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, sulfhydryl, thiol, alkylsulfonyl, aryl fluorenyl, trifluoromethyl , heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N-monocycloalkyl-aminecarbamyl, N- Monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, mercapto, N, N -diaryl-amine A , N-monocycloalkyl-N-monoarylamine, mercapto, N-monoalkyl-N-monoaryl-amine, mercapto, amine sulfonyl, N-monocycloalkyl-amine sulfonate Mercapto, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonate , N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ Or an alkyl group interrupted by one or more heteroatoms and substituted with one or more substituents selected from the group consisting of oxygen and sulfur, the one or more The substituent is selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl- Amino, N-monoaryl-amino, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N-monocycloalkyl-amine, N,N- Dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkyl sulfonate Mercapto-amino, ureido, alkylureido, phenylureido, halogen, cyanide , COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, oxime , aryl fluorenyloxy, amine carbhydryl, N-monocycloalkyl-amine carbhydryl, N-monoalkyl-amine, fluorenyl, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-aminecarboxylidene, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl, N-monocycloalkyl-N-monoarylamine Mercapto, N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N , N-bicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or an aryl substituted by one or more substituents, The one or more substituents are selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N, N -dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N , N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano , COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, oxime , aryl fluorenyloxy, amine carbhydryl, N-monocycloalkyl-amine carbhydryl, N-monoalkyl-amine, fluorenyl, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-aminecarboxylidene, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl, N-monocycloalkyl-N-monoarylamine Mercapto, N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N , N-bicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N- monocyclic aromatic mono-alkyl -N- acyl amine sulfonamide, N- monoalkyl monoaryl amine -N- sulfo acyl and SO ₃ M; and M is hydrogen, an alkali metal , Ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation; In a particularly preferred dyes of formula (1a) of: R ^1a and R ^6a is SO ₃ M, and ^{R 2a, R 3a, R 4a} , R 5a, R ^7a and R ^8a is hydrogen; or R ^2a and R ^5a is SO ₃ M; and ^{R 1a, R 3a, R 4a} , R 6a, R 7a and R ^8a is ^{hydrogen; R 9a, R 10a, R} 16a and R ^17a independently of each other is hydrogen, (C ₁ -C ₄ )-alkyl, (C ₁ -C ₄ )-alkoxy, halogen, trifluoromethyl, (C ₁ -C ₄ )-decylamino or -SO ₃ M; R ^13a and R ^20a are hydroxy; R ^14a and R ^21a are, independently of each other, alkyl, cycloalkyl, trifluoromethyl, cyano, aminecarbenyl, alkoxycarbonyl, COOM, alkane a carbonyl group; or an alkyl group substituted by one or more substituents selected from the group consisting of hydroxy, alkoxy, halogen, cyano, COOM, alkoxy a carbonyl group, a decyloxy group and an amine carbaryl group; R ^15a and R ^22a are each independently methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, or Hexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl , secondary butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pent-2-yl, 2- Ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2- Chloroethyl, 3-chloropropyl, 2-ethylhexyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 4-(2-hydroxyethanesulfonyl)phenyl, 2-(2 -hydroxyethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3 -ethoxy-propyl, 3-ethoxybutyl, phenyl, 3-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methyl Oxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl , 4-fluorophenyl or 3-phenylsulfonamide; and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation.

Examples of particularly preferred dyes of the formula (1a) are compounds of the formula (1a ¹ to 1a ³¹² ), mixtures and/or tautomers thereof, wherein R ³ , R ⁴ , R ⁷ and R ⁸ are hydrogen, R ¹³ and R ²⁰ are hydroxyl groups, and the other R ^{x are} as given in Table 1:

As summarized above, another preferred embodiment of the present invention is a dye of the formula (1) as shown above, wherein: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ And R ⁸ are independently of each other hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, whereby at least two of them are SO ₃ M; X is oxygen or sulfur; R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently hydrogen, alkyl, substituted alkyl, alkyl interrupted by one or two heteroatoms, alkoxy, Substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, alkylcarbonyl, decylamino, alkylsulfonylamino, amine, single Alkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, aminecarbamyl Aminesulfonyl, ureido, -SO ₃ M or alkylurea; R ¹³ and R ²⁰ are each independently an amine group; R ¹⁴ and R ²¹ are each independently hydrogen, alkyl, cycloalkyl, tri Fluoromethyl, alkoxy, cyano, aminemethanyl, alkoxycarbonyl, COOM, amine Base, hydroxy, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, mono-aryl-amino, diaryl-amino Monocyclic alkyl monoarylamine, monoalkylmonoarylamine, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl; or alkyl substituted by one or more substituents The one or more substituents are selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, aryl Thio group, halogen, cyano group, COOM, alkoxycarbonyl group, mercaptooxy group, amine mercapto group, nitro group, amine group, mercaptoamine group, arylcarbonylamino group, alkylsulfonylamino group, Arylsulfonylamino, ureido, alkyl-ureido and phenylurea; R ¹⁵ and R ²² are each independently hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl , aryl, heteroaryl, heterocycloalkyl, amidyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, Alkoxyalkyl-amino-alkyl, thioalkoxyalkyl-aminoalkyl Aminoalkoxyalkyl, aminoalkylthioalkyl, cycloalkylalkyl, aryloxyalkyl, arylthioalkyl, heteroaryl-alkyl, heterocycloalkylalkyl Or an alkyl group interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur; or an alkyl group substituted with one or more substituents, the one Or a plurality of substituents selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-di Alkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclic-alkyl-amino, N,N-Dicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N -alkylsulfonyl-amino, ureido, alkyl-ureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl , trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N- Cycloalkyl-aminecarbamyl, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-single Aryl-amine-methyl indenyl, N,N-diaryl-amine, mercapto, N-monocycloalkyl-N-monoarylamine, N-monoalkyl-N-monoaryl Aminomethyl sulfhydryl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N, N -dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl , N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or an alkyl group interrupted by one or more heteroatoms and substituted by one or more substituents, the one or more heteroatoms Selected from the group consisting of oxygen and sulfur, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine , N-monoalkyl-amino, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl Amino-amino, N-monocyclic-alkyl-amino, N,N-bicycloalkyl-amino, N- Alkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-decylamino, N-alkyl-sulfonyl-amino, ureido, Alkyl urea group, phenyl urea group, halogen, cyano group, COOM, nitro group, mercapto group, thiol group, alkyl sulfonyl group, aryl fluorenyl group, trifluoromethyl group, heteroaryl group, heterocycloalkyl group , alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl methoxyoxy, amine carbaryl, N-monocycloalkyl-amine carbhydryl, N-monoalkyl-amine carbhydryl, N,N-bicycloalkyl-aminecarbamyl, N,N-dialkyl-aminecarbamyl, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl , N-monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl-aminecarbamyl, aminesulfonyl, N-monocyclic-alkyl-amine sulfonate Mercapto, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonate , N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ Or an aryl group substituted by one or more substituents selected from the group consisting of Groups: hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl-amine, N-mono Amino-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amine, N-monocyclic-alkyl-amino, N,N-dicycloalkyl-amine , N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino , urea group, alkyl urea group, phenyl urea group, halogen, cyano group, COOM, nitro group, mercapto group, thiol group, alkyl sulfonyl group, aryl fluorenyl group, trifluoromethyl group, heteroaryl group, Heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, aminecarboxamido, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-amine Mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, mercapto, N,N-diaryl Aminomethyl, N-monocycloalkyl-N-monoarylamine, N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl - aminoxime, N-monoalkyl-amine sulfonyl, N,N-bicyclo-alkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-single An aryl-amine sulfonyl group and SO ₃ M; M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation; and the dye of the formula (1) has two to six sulfonic acid groups .

Preferred are dyes of formula (1b):

Wherein R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b and R ^8b are each independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, by At least two of them are SO ₃ M; X is oxygen; R ^9b , R ^10b , R ^16b and R ^17b are each independently hydrogen, alkyl, substituted alkyl, interrupted by one or two heteroatoms Alkyl, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, alkylcarbonyl, decylamino, alkylsulfonyl Amino, amine, monoalkyl-amine, monocyclo-alkyl-amino, dialkyl-amino, di(cyclo)alkyl-amine, alkylthio, alkylsulfonyl, alkane An oxycarbonyl group, an amine carbaryl group, an amine sulfonyl group, a ureido group, a -SO ₃ M or an alkyl urea group; R ^13b and R ^20b are each independently an amine group; and R ^14b and R ^21b are each independently hydrogen, Alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, aminemethanyl, alkoxycarbonyl, COOM, amine, hydroxy, monocycloalkyl-amino, monoalkyl-amino , di(cyclo)alkyl-amino, dialkyl-amino, mono-aryl-amino, diaryl- Amino, monocycloalkylmonoarylamine, monoalkylmonoarylamine, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl; or substituted by one or more substituents The alkyl group, the one or more substituents being selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio , arylthio, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, aminecarbamyl, nitro, amine, decylamino, arylcarbonylamino, alkylsulfonylamino , arylsulfonylamino, ureido, alkylureido, and phenylurea; R ^15b and R ^22b are, independently of each other, hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl , aryl, heteroaryl, heterocycloalkyl, amidyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, Alkoxyalkyl-amino-alkyl, thioalkoxyalkyl-aminoalkyl, aminoalkoxyalkyl, aminoalkylthioalkyl, cycloalkylalkyl, aryloxy Alkyl, arylthioalkyl, heteroaryl-alkyl a heterocycloalkylalkyl group; or an alkyl group interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur; or substituted by one or more substituents The alkyl group, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amino , N,N-dialkyl-amino, N-monoaryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclic- Alkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N - mercaptoamine, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, sulfhydryl, thiol, alkyl sulfonate Mercapto, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N-single Cycloalkyl-aminecarbamyl, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-single Aryl-amine Mercapto, N,N-diaryl-aminecarbamyl, N-monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl-aminecarbamyl, Aminesulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-bicycloalkyl-amine sulfonyl, N,N-dialkyl- Aminesulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkane a base-N-monoarylamine sulfonyl group and SO ₃ M; or an alkyl group interrupted by one or more heteroatoms and substituted by one or more substituents selected from the group consisting of a group consisting of oxygen and sulfur, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-single Alkyl-amino, N,N-dialkyl-amino, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amine Base, N-decylamino group, N-alkylsulfonyl-amino group, urea group, alkylureido group Phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkylsulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl , alkoxythiocarbonyl, decyloxy, aryl fluorenyloxy, amine carbaryl, N-monocycloalkyl-amine carbhydryl, N-monoalkyl-amine carbaryl, N,N-di Cycloalkyl-amine-methyl fluorenyl, N,N-dialkyl-amine, fluorenyl, N-monoaryl-amine, fluorenyl, N,N-diaryl-amine, fluorenyl, N-monocyclic -alkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N- Monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N -diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or by a Or a plurality of substituent-substituted aryl groups, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N- Monoalkyl-amino, N,N-dialkyl-amine, N-mono -Amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclo-alkyl-amino, N,N-bicycloalkyl-amino , N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, Urea group, alkyl urea group, phenyl urea group, halogen, cyano group, COOM, nitro group, sulfhydryl group, thiol group, alkyl sulfonyl group, aryl fluorenyl group, trifluoromethyl group, heteroaryl group, hetero Cycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, aminecarboxamido, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-amine A Mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, mercapto, N,N-diaryl-amine Mercapto, N-monocycloalkyl-N-monoarylamine, mercapto, N-monoalkyl-N-monoaryl-amine, mercapto, aminesulfonyl, N-monocycloalkyl- Aminesulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine Sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl SO ₃ M; and M is hydrogen, alkali metal, ammonium, one equivalent of an alkaline earth metal cation or a monovalent organic.

Preferred are dyes of the formula (1b) wherein: R ^1b and R ^6b are SO ₃ M, and R ^2b and R ^5b are hydrogen; or R ^1b and R ^6b are hydrogen, and R ^2b and R ^5b are SO ₃ M; R ^3b , R ^4b , R ^7b and R ^8b are hydrogen; R ^9b , R ^10b , R ^16b and R ^17b are each independently hydrogen, (C ₁ -C ₄ )-alkyl, (C ₁ -C) ₄ )-alkoxy, halogen, trifluoromethyl, -SO ₃ M or (C ₁ -C ₄ )-fluorenylamino; R ^13b and R ^20b are each independently an amine group; R ^14b and R ^21b are each other Independently an alkyl group, a cycloalkyl group, a trifluoromethyl group, a cyano group, an amine carbaryl group, an alkoxycarbonyl group, a COOM group, an alkylcarbonyl group; or an alkyl group substituted with one or more substituents, the one Or a plurality of substituents selected from the group consisting of a hydroxyl group, an alkoxy group, a halogen, a cyano group, a COOM, an alkoxycarbonyl group, a decyloxy group, and an amine mercapto group; and R ^15b and R ^22b are independently of each other Is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, isopropyl , secondary butyl, 2-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, three Butyl, 3-methylbutyl, pent-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl, 2-hydroxyethyl, 2-methoxy Ethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 2-ethylhexyl, 2-(2-hydroxyethylsulfanyl)-ethyl , 4-(2-hydroxyethanesulfonyl)phenyl, 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxybutoxy)propyl, 3-(2-phenoxy- Ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, phenyl, 3-methylphenyl, 2-methylbenzene , 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorobenzene a group, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl or 3-phenylsulfonamide; and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or Monovalent organic cation.

Examples of particularly preferred dyes of the formula (1b) are compounds of the formula (1b ¹ to 1b ³¹² ), mixtures and/or tautomers thereof, wherein R ³ , R ⁴ , R ⁷ and R ⁸ are hydrogen, R ¹³ and R ²⁰ are amine groups, and the other R ^{x are} as given in Table 2:

The invention also provides a process for the production of a dye of formula (1) and mixtures thereof, which process comprises: a) diazotization of a compound of formula (2):

Wherein R ¹ to R ^{8 are} as defined above; b) reacting the diazonium salt obtained in a) with a compound of the formula (3) and the formula (4):

Wherein R ⁹ to R ¹² and R ¹⁶ to R ^{19 are} as defined above to give an intermediate of the formula (5):

c) diazotizing the intermediate of formula (5); and d) subjecting the diazonium salt obtained in c) to the compound of formula (6) and formula (7) or a mixture thereof reaction:

Wherein R ¹³ to R ¹⁵ and R ²⁰ to R ^{22 are} as defined above.

The diazotization of the compounds of the formulae (2) and (5) can be carried out by a diazotization method known to those skilled in the art, preferably by using an acidic medium such as hydrochloric acid. Sodium nitrite or sodium nitrosylsulfate is used in sulfuric acid, or phosphoric acid or a mixture thereof, or an organic acid such as acetic acid or propionic acid or a mixture thereof. It is also advantageous to use a mixture of a mineral acid and an organic acid.

a coupling reaction of a diazonium salt obtained by diazotization of a compound of the formula (2) to a compound of the formulae (3) and (4), and a diazonium by a compound of the formula (5) The coupling reaction of the diazonium salt obtained by the catalysis to the compound of the formulae (6) and (7) can be carried out in the same manner by a known method. These reactions can be carried out using stoichiometric amounts of diazonium compounds, but can also be advantageously carried out using 5 to 10% excess diazonium compound.

Compounds of formula (2) are known and commercially available, or can be synthesized by conventional chemical reactions known to those skilled in the art, such as those disclosed in DE 140613C.

Pyrazoles of the formulae (6) and (7) (wherein R ¹³ and R ¹⁶ represent a hydroxyl group) are commercially available or such pyrazolone can be synthesized by the method disclosed in the literature, for example, in WO 2010/076553. Pyrazoles of the formulae (6) and (7) wherein R ¹³ and R ¹⁶ are amine groups are commercially available or such aminopyrazoles can be synthesized by the methods disclosed in the literature, for example, in US 6,338,741.

By analogy, all pyrazoles used in the present invention can be synthesized as described.

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

Thus, a chemical composition comprising one or more dyes as described above is also an aspect of the invention.

Another preferred aspect of the invention is formed from a chemical composition consisting of two or more dyes as described above.

An aqueous solution comprising one or more dyes as described above for dyeing also forms an aspect of the invention.

The dyes of the present invention are suitable for natural, manufactured, regenerated, modified or synthetic hydroxyl-containing amino- and/or carboguanamine groups by various methods of application for acid dyes described in the art. The fiber material and its blends are dyed and printed.

Accordingly, the present invention also relates to a method of dyeing or printing a material containing a carboxyguanamine group and/or a hydroxyl group, the method comprising contacting the carboxyguanamine group- and/or hydroxyl group-containing material with a dye as described above .

a dye as described above, a chemical composition as described above or as The use of the aqueous solution described above for dyeing fibers and blends of such fibers forms another aspect of the invention, such fibers being from the group consisting of synthetic fiber materials, nylon materials , nylon-6, nylon-6.6 and aromatic polyamide fibers, plant fibers, seed fibers, cotton, organic cotton, wood wool, coconut fiber from coconut shells; bast fiber, flax, hemp, jute, Hemp fiber, ramie, vine; leaf fiber, Qiongma, henequen, banana; stem fiber, bamboo; fiber from animal, wool, organic wool, silk, cashmere, alpaca fiber, mohair, Angola fiber and fur and leather materials; manufactured, regenerated and reused fibers, cellulose fibers; paper fibers, cellulose regenerated fibers, mucus crepe fibers, acetate and triacetate fibers, and lyocell ( Lyocell) fiber.

Yet another aspect of the invention is a fiber and a blend comprising such fibers, the fiber and a blend comprising such fibers or comprising one or more dyes of the invention in a chemically and/or physically bonded form The fibers are selected from the group consisting of synthetic fiber materials, nylon materials, nylon-6, nylon-6.6, and aromatic polyamide fibers, vegetable fibers, seed fibers, cotton, organic cotton, and wood wool. , coconut fiber from coconut shell; bast fiber, flax, hemp, jute, kenaf, ramie, vine; leaf fiber, Qiongma, Henaucun fiber, banana; stem fiber, bamboo; fiber from animal, Wool, organic wool, silk, cashmere, alpaca, mohair, Angora and fur and leather materials; manufactured, regenerated and recycled fibres, cellulose fibres; paper fibres, cellulose regenerated fibres, mucilage Fiber, acetate and triacetate fibers, and lyocell fiber dimension.

The substrate to be dyed described above may be present in various forms such as, but not limited to, yarns, woven fabrics, loop-woven fabrics or carpets. For example, in the form of a sheet-like structure, such as paper and leather; in the form of a film, such as a nylon film; or in the form of a bulk block, for example composed of polyamine and polyurethane; in particular in the form of fibers, such as cellulose fibers. The fibers are preferably textile fibers, for example in the form of woven fabrics or yarns or in the form of skeins or wound packages.

The dyes of the present invention, as well as salts and/or mixtures thereof, can be used as a single dye colorant during dyeing or printing, or can be part of a two, three, or multi-component combination colorant in a dyeing or printing composition. Two, three, or multi-component chroma staining shows similar levels of color fastness compared to dyeing with a single colorant component.

The dyes of the present invention, as well as salts or mixtures thereof, are highly compatible with other known and/or commercially available acid dyes, and they can be used with such dyes having associated chromophores and similar technical properties to achieve a particular hue. . Similar technical properties include comparable accumulation during dyeing, comparable color fastness characteristics, and comparable exhaustion rate.

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

In particular it is used to produce a dyeing effect on fibrous materials composed of wool or other natural polyamines or from synthetic polyamines and mixtures thereof with other fibrous materials. In general, the material to be dyed Introduced into a bath at a temperature of about 40 ° C, stirred therein for a period of time, and then the dye bath is adjusted to the desired weakly acidic (preferably weakly acetic acid) pH, and the actual dyeing is at 60 ° C. It is carried out at a temperature between 98 °C. However, the dyeing process can also be carried out at boiling points or in sealed dyeing units at temperatures up to 106 °C.

Since the dyes according to the invention are very water soluble, they can also be advantageously used in conventional continuous dyeing processes.

The dyes of the present invention can also be used in digital printing processes, particularly in digital textile printing. To this end, the dyes of the invention need to be formulated into aqueous inks.

An ink comprising the dye of the present invention for use in textile digital printing is another aspect of the invention.

The amount of the dye of the present invention contained in the ink of the present invention is preferably from 0.1% to 50% by weight, more preferably from 0.5% to 30% by weight, based on the total weight of the ink, and most preferably It ranges from 1% to 15% by weight.

Desirably, in addition to the one or more dyes of the present invention, the ink may contain additional dyes used in the digital printing process.

For the ink of the present invention to be used in the continuous flow method, the electrical conductivity of 0.5 mS/m to 25 mS/m can be set by adding an electrolyte. Useful electrolytes include, for example, lithium nitrate and potassium nitrate. The ink of the present invention may comprise an organic solvent having a total level of from 1% to 50% by weight and preferably from 5% to 30% by weight. Suitable organic solvents are, for example, alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, tertiary butanol, pentanol; polyols such as 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 glycol, for example: polyethylene glycol, polypropylene glycol; alkylene glycol having 1 to 8 alkylene groups, such as: monoethylene glycol, diethylene glycol, triethylene glycol Alcohol, tetraethylene glycol, thioethylene glycol, thiodiethylene glycol, butyl triethylene glycol, hexanediol, propylene glycol, dipropylene glycol, tripropylene glycol; lower alkyl ether of polyol, 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, diethyl Glycol monohexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol Butyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether; polyalkyl glycol ether, such as: polyethylene Alcohol monomethyl ether, polypropylene glycol glyceryl 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-methylethanolamine, ethylenediamine; urea derivatives such as, for example, urea, thiourea, N- Methylurea, N,N'-ε-dimethylurea, ethanediurea, 1,1,3,3-tetramethylurea; guanamines, such as, for example, dimethylformamide, dimethylamine Amidoxime or 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, γ-butyrolactone, ε-caprolactam; additional cyclobutyl hydrazine, dimethylcyclobutyl hydrazine, methylcyclobutyl hydrazine, 2,4-dimethyl Cyclobutane; dimethyl hydrazine, butadiene bismuth, dimethyl Azulene, dibutyl fluorene, N-cyclohexyl pyrrolidone, 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-imidazoline Ketone, 1,3-bismethoxymethyl-imidazolidinium, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butyl) Oxy-ethoxy)-ethanol, 2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, tri-methyl-propane, 1,2-dimethoxypropane, two Ethyl acetate, ethylenediaminetetraacetic acid ethylpentyl ether, 1,2-dimethoxypropane, and trimethylpropane.

The ink of the present invention may further comprise a conventional additive such as a viscosity modifier to set the viscosity in a range from 1.5 mPas to 40.0 mPas in a temperature range from 20 ° C to 50 ° C. Preferred inks have a viscosity of from 1.5 mPas to 20 mPas and particularly preferred inks have a viscosity of from 1.5 mPas to 15 mPas.

Useful viscosity modifiers include rheological additives such as polyethylene caprolactam, polyvinylpyrrolidone and copolymers thereof polyether polyols, associative thickeners, polyureas, polyurethanes, alginic acids Sodium, modified galactomannan, polyether urea, polyurethane, nonionic cellulose ether.

As a further additive, the ink of the invention may comprise a surface active substance to set a surface tension of 20 to 65 mN/m, which surface tension can be adapted, if necessary, depending on the method used (hot or pressure technology). . Useful surface active materials include, for example, all surfactants, preferably nonionic surfactants, butyl diethylene glycol, 1,2-hexanediol.

The inks of the present invention may further comprise conventional additives such as substances which inhibit the growth of fungi and bacteria in an amount of from 0.01% to 1% by weight based on the total weight of the ink.

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

The inks of the present invention are particularly useful in ink jet printing processes for printing a wide variety of pretreated materials such as silk, leather, wool, polyamide fibers, and polyurethanes, as well as any kind of fibers. Plain fiber material. Blend fibers, such as blends of cotton, silk, wool and polyester fibers or polyamide fibers, can be similarly printed.

Unlike conventional textile printing, which already contains all the necessary chemicals, the auxiliaries must be applied to the textile substrate in a single pretreatment step in digital or inkjet printing.

Pretreatment of the textile substrate, such as cellulose and regenerated cellulose fibers, as well as silk and wool, is accomplished by using an aqueous alkaline liquid prior to printing. Furthermore, there is a need for a thickener that prevents the flow of the flow when applying the ink, such as sodium alginate, modified polyacrylate or highly etherified galactomannan.

The pretreatment reagents are applied using a suitable coater, for example using a 2- or 3-roll pad, contactless spray technique, by application of foam or using appropriately adapted inkjet technology. A defined amount is applied uniformly to the textile substrate and subsequently dried.

The examples below are used to illustrate the invention. Parts and percentages are by weight unless otherwise indicated. The relationship between parts by weight and parts by volume is in kilograms versus liter.

Example 1

First, 10.06 g of 5,5'-diamino-2,2'-subureido-bis-benzenesulfonic acid was dissolved in water at a slightly acidic pH to obtain a complete solution. Ice was added to the solution, and when the temperature reached 10 to 15 ° C, 10.6 ml of a 5 N sodium nitrite solution was added dropwise. When the mixture was added dropwise to 12.38 g of concentrated HCl and 12 g of ice, the reaction mixture was further cooled to 0 to 8 °C. A yellow suspension formed and the reaction mixture was complete within one hour.

6.30 g of 2,5-dimethyl-phenylamine was added directly to the diazo suspension and stirred. After the addition, a purple precipitate was observed. The intermediate precipitate obtained by aspiration was 4,4'-bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2'-di The sulfonic acid was filtered off, washed with an organic solvent, and dried.

Then 15.22 g of the dried intermediate 5,5'-bis-(4-amino-2,5-dimethyl-phenylazo)-2,2'-subureido-dibenzenesulfonic acid Dissolved in water at a slightly acidic pH to give a complete red-orange solution. Ice was added to the solution, and when the temperature reached 10 to 15 ° C, 10.1 ml of a 5 N sodium nitrite solution was added dropwise. When the mixture was added dropwise to concentrated HCl and ice, the reaction mixture was further cooled to 0 to 8 °C. Purple suspension The reaction mixture was completed in 90 min.

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

The 5-methyl-2-phenyl-2H-pyrazol-3-ol was stirred in methanol and adjusted to slightly acidic. The obtained purple suspension was added dropwise to a methanol solution and stirred. After the addition, a bright orange precipitate was observed. The suction by the obtained precipitate was filtered off, and washed with brine to give a product of the formula 1a ^41. 1a ⁴¹ consistent with the assigned structure and the product analysis data.

The product obtained dyes the target fiber material to a bright orange shade.

By analogy, all dyes having the chemical formula (1a ¹ -1a ³¹² ) can be synthesized according to the methods described above.

Dyeing example 1-1

One part of the dye 1a ⁴¹ of the present invention was dissolved in 2000 parts of water, and 1 part of a leveling aid (based on a 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 100 parts of the woven polyamide-6 fabric was introduced. The temperature was raised to 98 ° C during the course of 50 minutes, and then dyeing was carried out at this temperature for 60 minutes. This is followed by cooling to 60 ° C and removing the dyed material. The polyamide-6 fabric was washed with hot and cold water, scrubbed with soap and then spun and dried.

The orange dye obtained has excellent light and wet color fastness in the fiber, and also has good levelness.

Dyeing example 1-2

One part of the dye 1a ⁴¹ of the present invention was dissolved in 2000 parts of water, and 1 part of a leveling aid (based on a 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 100 parts of the woven polyamide-6,6 fabric was introduced. The temperature was raised to 120 ° C during the course of 50 minutes, and then dyeing was carried out at this temperature for 60 minutes. This is followed by cooling to 60 ° C and removing the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, scrubbed with soap and then spun and dried.

The orange dye obtained has excellent light and wet color fastness in the fiber, and also has good levelness.

Dyeing examples 1-3

100 parts of polyamine-6 material was filled with 1000 parts of a 50 ° C liquid solution consisting of 40 parts of dye 1a ⁴¹ , 100 parts of urea, 20 parts of butyl diethylene glycol-based non-ion Solubilizer, 20 parts acetic acid (to adjust the pH to 4.0), 10 parts of leveling aid (based on ethoxylated aminopropyl fatty acid decylamine) and 810 parts of water. The material was rolled up and placed in a steam chamber at 85 to 98 ° C for 3 to 6 hours. After fixing, the fabric was washed with hot and cold water, scrubbed with soap and then spun and dried.

The orange dye obtained has excellent light and wet color fastness in the fiber, and also has good levelness.

Dyeing examples 1-4

One part of the dye 1a ⁴¹ of the present invention was dissolved in 2000 parts of water, and 5 parts of sodium sulfate and 1 part of a leveling aid (based on a condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were 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 100 parts of the woven wool fabric entered. The temperature was raised to 100 ° C during the course of 50 minutes, and then dyeing was carried out at this temperature for 60 minutes. This is followed by cooling to 90 ° C and removing the dyed material. The wool fabric was washed with hot and cold water, scrubbed with soap and then spun and dried.

The orange dye obtained has excellent light and wet color fastness in the fiber, and also has good levelness.

Dyeing examples 1-5

One part of the dye 1a ⁴¹ of the present invention was dissolved in 1000 parts of soft water, and 7.5 parts of sodium sulfate and 1 part of a wetting agent (anionic type) were added. 100 parts of bleached cotton woven fabric was added to this solution. Then, the dyebath was heated to 98 ° C in a gradient of 2 ° C / min, and then dyed at this temperature for 60 minutes. This is followed by cooling to 80 °C. Dyeing was continued for an additional 20 minutes at 80 °C. The dyed material is then removed and washed with hot and cold water, scrubbed with soap and then spun and dried.

The orange dye obtained has excellent light and wet color fastness in the fiber, and also has good levelness.

Dyeing examples 1-6

Three parts of the dye 1a ⁴¹ of the present invention dissolved in 82 parts of deionized water were added to the dyebath at 60 ° C together with 15 parts of diethylene glycol. When cooled, a yellow ink is obtained.

The orange printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

Dyeing examples 1-7

Four parts of chemically bleached (pine) sulfite pulp were mixed with 100 parts of water at 55 °C. One part of the dye 1a ⁴¹ of the present invention was dissolved in 100 parts of hot water. 80 parts of this solution was supplied to the mixed pulp and mixed for 2 minutes. Thereafter, the mixture was sized by a resin size in a conventional manner and mixed for an additional 2 minutes. Then, 55 parts of this solution was diluted with 2000 parts of cold water, and paper was produced using this solution.

The orange paper produced from this mixture has good wet color fastness.

Example 2

First, 10.06 g of 5,5'-diamino-2,2'-subureido-bis-benzenesulfonic acid was dissolved in water at a slightly acidic pH to obtain a complete solution. Ice was added to the solution, and when the temperature reached 10 to 15 ° C, 10.6 ml of a 5 N sodium nitrite solution was added dropwise. When the mixture was added dropwise to 12.38 g of concentrated HCl and 12 g of ice, the reaction mixture was further cooled to 0 to 8 °C. A yellow suspension formed and the reaction mixture was complete within one hour.

6.30 g of 2,5-dimethyl-phenylamine was added directly to the diazo suspension and stirred. After the addition, a purple precipitate was observed. The intermediate precipitate obtained by aspiration was 4,4'-bis-(4-amino-2,5-dimethyl-phenylazo)-biphenyl-2,2'-di The sulfonic acid was filtered off, washed with an organic solvent, and dried.

Then 15.22 g of the dried intermediate 5,5'-bis-(4-amino-2,5-dimethyl-phenylazo)-2,2'-subureido-bis-benzenesulfonic acid Dissolved in water at a slightly acidic pH to give a complete red-orange solution. Ice was added to the solution, and when the temperature reached 10 to 15 ° C, 10.1 ml of a 5 N sodium nitrite solution was added dropwise. When the mixture was added dropwise to concentrated HCl and ice, the reaction mixture was further cooled to 0 to 8 °C. A purple suspension formed and the reaction mixture was complete within 90 min.

The 5-methyl-2-o-tolyl-3,4-dihydro-2H-pyrazol-3-ylamine was stirred in methanol and adjusted to slightly acidic. The diazonium compound was added dropwise to the methanol solution and stirred. After the addition, a bright orange precipitate was observed. The obtained precipitate was filtered off by suction and washed with brine to give a product of formula 1b ¹⁶¹ . The analytical data is consistent with the specified structure of product 1b ¹⁶¹ . The product dyes the target fiber material to a bright orange shade.

By analogy, all dyes having the formula (1b ¹ -1b ³¹² ) can be synthesized according to the methods described above.

Dyeing example 2-1

One part of the dye 1b ¹⁶¹ of the present invention was dissolved in 2000 parts of water, and 1 part of a leveling aid (based on a 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 100 parts of the woven polyamide-6 fabric was introduced. The temperature was raised to 98 ° C during the course of 50 minutes, and then dyeing was carried out at this temperature for 60 minutes. This is followed by cooling to 60 ° C and removing the dyed material. The polyamide-6 fabric was washed with hot and cold water, scrubbed with soap and then spun and dried. The orange dye obtained has excellent light and wet fastness in the fiber and good levelness.

Dyeing example 2-2

One part of the dye 1b ¹⁶¹ of the present invention was dissolved in 2000 parts of water, and 1 part of a leveling aid (based on a 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 100 parts of the woven polyamide-6,6 fabric was introduced. The temperature was raised to 120 ° C during the course of 50 minutes, and then dyeing was carried out at this temperature for 60 minutes. This is followed by cooling to 60 ° C and removing the dyed material. The polyamide-6,6 fabric was washed with hot and cold water, scrubbed with soap and then spun and dried. The orange dye obtained has excellent light and wet fastness in the fiber and good levelness.

Dyeing example 2-3

100 parts of polyamine-6 material was filled with 1000 parts of a 50 ° C liquid solution consisting of 40 parts of dye 1b ¹⁶¹ , 100 parts of urea, 20 parts of butyl diethylene glycol-based non-ion Solubilizer, 20 parts acetic acid (to adjust the pH to 4.0), 10 parts of leveling aid (based on ethoxylated aminopropyl fatty acid decylamine) and 815 parts of water. The material was rolled up and placed in a steam chamber at 85 to 98 ° C for 3 to 6 hours. After fixing, the fabric was washed with hot and cold water, scrubbed with soap and then spun and dried. The orange dye obtained has excellent light and wet fastness in the fiber and good levelness.

Dyeing examples 2-4

One part of the dye 1b ¹⁶¹ of the present invention was dissolved in 2000 parts of water, and 5 parts of sodium sulfate and 1 part of leveling aid (based on a condensation product of a higher aliphatic amine and ethylene oxide) and 5 parts of sodium acetate were 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 100 parts of the woven wool fabric entered. The temperature was raised to 100 ° C during the course of 50 minutes, and then dyeing was carried out at this temperature for 60 minutes. This is followed by cooling to 90 ° C and removing the dyed material. The wool fabric was washed with hot and cold water, scrubbed with soap and then spun and dried. The orange dye obtained has excellent light and wet fastness in the fiber and good levelness.

Dyeing example 2-5

One part of the dye 1b ¹⁶¹ of the present invention was dissolved in 1000 parts of soft water, and 7.5 parts of sodium sulfate and 1 part of a wetting agent (anionic type) were added. 100 parts of bleached cotton woven fabric was added to this solution. Then, the dyebath was heated to 98 ° C in a gradient of 2 ° C / min, and then dyed at this temperature for 60 minutes. This is followed by cooling to 80 °C. Dyeing was continued for an additional 20 minutes at 80 °C. The dyed material is then removed and washed with hot and cold water, scrubbed with soap and then spun and dried. The orange dye obtained has excellent light and wet fastness in the fiber and good levelness.

Dyeing examples 2-6

Three parts of the dye 1b ¹⁶¹ of the present invention dissolved in 82 parts of deionized water were added to the dyebath at 60 ° C together with 15 parts of diethylene glycol. When cooled, an orange printing ink is obtained. The orange printing ink can be used for ink jet printing on paper, polyamide or wool textiles.

Dyeing examples 2-7

Four parts of chemically bleached (pine) sulfite pulp were mixed with 100 parts of water at 55 °C. One part of the dye 1b ¹⁶¹ of the present invention was dissolved in 100 parts of hot water. 80 parts of this solution was supplied to the mixed pulp and mixed for 2 minutes. Thereafter, the mixture was sized by a resin size in a conventional manner and mixed for an additional 2 minutes. Then, 55 parts of this solution was diluted with 2000 parts of cold water, and paper was produced using this solution. The orange paper produced from this mixture has good wet color fastness.

Claims (15)

Dye of formula (1): Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, by At least two of them are SO ₃ M; X is oxygen or sulfur; and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ are each independently hydrogen, alkyl, Substituted alkyl, alkyl interrupted by one or two heteroatoms, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, Alkylcarbonyl, mercaptoamine, alkylsulfonylamino, amine, monoalkyl-amine, monocycloalkyl-amino, dialkyl-amine, di(cyclo)alkyl-amine Alkyl, alkylthio, alkylsulfonyl, alkoxycarbonyl, aminemethanyl, sulfonyl, ureido, alkylureido or -SO ₃ M; R ¹³ and R ²⁰ are hydroxy or amine ; R ¹⁴ and R ²¹ are, independently of each other, hydrogen, alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, aminecaraki, alkoxycarbonyl, COOM, amine, hydroxy, monocyclic Alkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amino, dialkyl-amino, monoaryl-amino Diaryl-amino, monocycloalkylmonoarylamine, monoalkylmonoarylamine, alkylthio, arylthio, alkylcarbonyl, alkylsulfonyl; or as one or more a substituent-substituted alkyl group, the one or more substituents being selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy , alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, aminecarbamyl, nitro, amine, decylamino, arylcarbonylamino, alkyl sulfonate a mercaptoamine group, an arylsulfonylamino group, a ureido group, an alkylureido group, and a phenylureido group; R ¹⁵ and R ²² are each independently hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl , cycloalkyl, aryl, heteroaryl, heterocycloalkyl, amine mercapto, alkyl ureido, phenyl-ureido, hydroxyalkyl sulfonylalkyl, aminoalkyl, amine - Hydroxy-alkyl, alkoxy-alkyl-aminoalkyl, thioalkoxyalkyl-aminoalkyl, aminoalkoxyalkyl, amino-alkylthioalkyl, cycloalkyl Alkyl, aryloxyalkyl, arylthioalkyl, heteroaryl An alkyl group, a heterocycloalkylalkyl group; or an alkyl group interrupted by one or more heteroatoms; or an alkyl group substituted with one or more substituents selected from the group consisting of Group: hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl-amine, N-monoaryl- Amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N -monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, Alkyl urea group, phenyl urea group, halogen, cyano group, COOM, nitro group, mercapto group, thiol group, alkyl sulfonyl group, aryl fluorenyl group, trifluoromethyl group, heteroaryl group, heterocycloalkyl group , alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl methoxyoxy, amine carbaryl, N-monocycloalkyl-amine carbhydryl, N-monoalkyl-amine carbhydryl, N,N-bicycloalkyl-aminecarbamyl, N,N-dialkyl-aminecarbamyl, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl , N-monocycloalkyl-N-monoarylamine Mercapto, N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N, N-bicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N - monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or interrupted by one or more heteroatoms and one or more a substituent-substituted alkyl group, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkane Amino-amino, N,N-dialkyl-amino, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N -monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino , N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkane Sulfosyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkane Oxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-aminecarbamyl, N, N-bicycloalkyl-aminecarbamyl, N,N-dialkyl-aminecarbamyl, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl, N -monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl-aminecarbamyl, aminesulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N , N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; An aryl group substituted with one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amino, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl- Amino, N-monocycloalkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N -monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM , nitro, mercapto, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, Aryloxy, carbamoyl, N-monocycloalkyl-amine, mercapto, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N, N-Dialkyl-amine-mercapto, N-monoaryl-amine, mercapto, N,N-diaryl-amine, mercapto, N-monocycloalkyl-N-monoarylamine , N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N, N -bicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N- Monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; M is hydrogen, alkali metal, ammonium, one equivalent of alkaline earth metal or Monovalent organic cation; and the dyes of formula (1) have from two to six sulphur Acid group. The dye of claim 1, wherein R ¹³ and R ²⁰ are a hydroxyl group. The dye according to claim 1 or 2, which has the chemical formula (1a): Wherein R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a and R ^8a are each independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, by At least two of them are SO ₃ M; R ^9a , R ^10a , R ^16a and R ^17a are each independently hydrogen, alkyl, substituted alkyl, alkyl interrupted by one or two heteroatoms, alkane Oxyl, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, alkylcarbonyl, decylamino, alkylsulfonylamino, amine , monoalkyl-amino, monocycloalkyl-amino, dialkyl-amino, di(cyclo)alkyl-amino, alkylthio, alkylsulfonyl, alkoxycarbonyl, amine Mercapto, sulfonyl, ureido, alkylureido or -SO ₃ M; R ^13a and R ^20a are hydroxy; R ^14a and R ^21a are independently of each other hydrogen, alkyl, cycloalkyl, trifluoro Methyl, alkoxy, cyano, amine, mercapto, alkoxycarbonyl, COOM, amine, hydroxy, monocycloalkyl-amino, monoalkyl-amino, di(cyclo)alkyl-amine Base, dialkyl-amino group, monoaryl-amine group, diaryl-amino group, monocycloalkyl group An amine group, a monoalkyl monoarylamine group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an alkylsulfonyl group; or an alkyl group substituted with one or more substituents, the one or more substitutions The group is selected from the group consisting of hydroxy, cycloalkyl, heteroaryl, heterocycloalkyl, aryl, aryloxy, alkoxy, alkylthio, arylthio, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, aminemethanyl, nitro, amine, decylamino, arylcarbonylamino, alkylsulfonylamino, arylsulfonylamino, urea a group, an alkylureido group and a phenylurea group; R ^15a and R ^22a are each independently hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, aryl, heteroaryl, heterocyclic Alkyl, aminemethanyl, alkylureido, phenyl-ureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkoxyalkylamino-alkane Base, thioalkoxyalkyl-aminoalkyl, aminoalkoxyalkyl, aminoalkylthioalkyl, cyclo-alkyl-alkyl, aryloxyalkyl, arylthio An alkyl group, a heteroarylalkyl group, a heterocycloalkylalkyl group; or An alkyl group interrupted by one or more heteroatoms; or an alkyl group substituted with one or more substituents selected from the group consisting of hydroxy, aryl, cycloalkyl , alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl- Amino, N-alkyl-N-aryl-amino, N-mono-cyclo-alkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl -Amino, N,N-mono-aryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylurea Base, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxy Thiocarbonyl, decyloxy, aryl fluorenyloxy, carbamoyl, N-monocycloalkyl-amine, fluorenyl, N-monoalkyl-amine, fluorenyl, N,N-dicycloalkyl -Aminomethyl hydrazino, N,N-dialkyl-amine carbhydryl, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl, N-monocycloalkyl- N-monoarylamine-methyl, N-monoalkyl-N-monoaryl- Aminomethyl sulfhydryl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N, N -dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl , N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or an alkyl group interrupted by one or more heteroatoms and substituted by one or more substituents, the one or more substituents Selected from the group consisting of: hydroxy, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine, N,N-dialkyl-amino , N-monoaryl-amino, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N-monocycloalkyl-amine, N,N-bicyclic Alkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl -Amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, hetero Aryl, heterocycloalkyl, alkoxy-carbonyl, alkoxythiocarbonyl Alkoxy, aryl methoxy, amine carbyl, N-mono-cycloalkyl-amine, fluorenyl, N-monoalkyl-amine, fluorenyl, N,N-dicycloalkyl-amine Mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, mercapto, N,N-diaryl-amine, mercapto, N-monocyclic-alkyl-N- Monoarylamine, mercapto, N-monoalkyl-N-monoaryl-amine, mercapto, amine sulfonyl, N-mono-cycloalkyl-amine sulfonyl, N-monoalkyl-amine Sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl- Aminesulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M; or by one or more substituents a substituted aryl group, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine , N,N-dialkyl-amino, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N-monocyclic Alkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocycloalkyl-amino N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl Sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N- Monocycloalkyl-amine, mercapto, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N- Monoaryl-aminecarboxylidene, N,N-diaryl-aminecarbamyl, N-monocycloalkyl-N-monoarylaminecarbamyl, N-monoalkyl-N-monoaryl -Aminomethyl sulfhydryl, amine sulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N, N-Dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonate a group, N-monoalkyl-N-monoarylamine sulfonate and SO ₃ M; and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation. The dye according to any one of claims 1 to 3, wherein: R ^1a and R ^6a are SO ₃ M, and R ^2a , R ^3a , R ^4a , R ⁵ , R ⁷ and R ^8a are hydrogen Or R ^2a and R ^5a are SO ₃ M, and R ^1a , R ^3a , R ^4a , R ⁶ , R ⁷ and R ^8a are hydrogen; R ^9a , R ^10a , R ^16a and R ^17a are each independently hydrogen, (C ₁ -C ₄ )-alkyl, (C ₁ -C ₄ )-alkoxy, halogen, trifluoromethyl, (C ₁ -C ₄ )-fluorenylamino or -SO ₃ M; R ^13a And R ^20a are a hydroxyl group; R ^14a and R ^21a are, independently of each other, an alkyl group, a cycloalkyl group, a trifluoromethyl group, a cyano group, an amine formazan group, an alkoxycarbonyl group, a COOM group, an alkylcarbonyl group; or Or a plurality of substituent-substituted alkyl groups selected from the group consisting of hydroxyl, alkoxy, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, and amine Mercapto; R ^15a and R ^22a are, independently of each other, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylcyclo Hexyl, 3-methylcyclohexyl, isopropyl, secondary butyl, 2-methylbutyl, 1-ethyl 1,1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pent-2-yl, 2-ethylhexyl, 2,2-dimethylpropyl, phenyl, benzyl Base, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 2-ethylhexyl, 2- (2-hydroxyethylsulfanyl)-ethyl, 4-(2-hydroxyethanesulfonyl)phenyl, 2-(2-hydroxyethoxy)ethyl, 3-(4-hydroxybutoxy , propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-ethoxybutyl, phenyl , 3-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxy Phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl or 3-phenylsulfonamide; and M is Hydrogen, alkali metal, ammonium, one equivalent of alkaline earth metal or monovalent organic cation. The dye of claim 1, wherein R ¹³ and R ²⁰ are an amine group. The dye according to claim 1 or 5, which has the chemical formula (1b): Wherein R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b and R ^8b are each independently hydrogen, alkyl, alkoxy, halogen, trifluoromethyl or SO ₃ M, by At least two of them are SO ₃ M; X is oxygen; R ^9b , R ^10b , R ^16b and R ^17b are each independently hydrogen, alkyl, substituted alkyl, interrupted by one or two heteroatoms Alkyl, alkoxy, substituted alkoxy, halogen, trifluoromethyl, cycloalkyl, heterocycloalkyl, cyano, decyloxy, alkylcarbonyl, decylamino, alkylsulfonyl Amine, amine, monoalkyl-amine, monocyclo-alkyl-amino, dialkyl-amine, di(cyclo)alkyl-amine, alkylthio, alkylsulfonyl, alkane An oxycarbonyl group, an amine carbaryl group, an amine sulfonyl group, a ureido group, a -SO ₃ M or an alkyl urea group; R ^13b and R ^20b are each independently an amine group; and R ^14b and R ^21b are each independently hydrogen, Alkyl, cycloalkyl, trifluoromethyl, alkoxy, cyano, aminemethanyl, alkoxycarbonyl, COOM, amine, hydroxy, monocycloalkyl-amino, monoalkyl-amino , di(cyclo)alkyl-amino, dialkyl-amino, mono-aryl-amino, diaryl- a monocyclic alkyl monoarylamine group, a monoalkyl monoarylamine group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an alkylsulfonyl group; or substituted by one or more substituents An alkyl group, the one or more substituents being selected from the group consisting of a hydroxyl group, a cycloalkyl group, a heteroaryl group, a heterocycloalkyl group, an aryl group, an aryloxy group, an alkoxy group, an alkylthio group, Arylthio, halogen, cyano, COOM, alkoxycarbonyl, decyloxy, aminecarboxamidine, nitro, amine, decylamino, arylcarbonylamino, alkylsulfonylamino, An arylsulfonylamino group, a ureido group, an alkylureido group, and a phenylureido group; R ^15b and R ^22b are each independently hydrogen, alkyl, hydroxyalkyl, alkoxy, alkenyl, cycloalkyl, Aryl, heteroaryl, heterocycloalkyl, aminemethanyl, alkylureido, phenylureido, hydroxyalkylsulfonylalkyl, aminoalkyl, amino-hydroxy-alkyl, alkane Oxyalkyl-amino-alkyl, thioalkoxyalkyl-aminoalkyl, amino-alkoxy-alkyl, aminoalkylthioalkyl, cycloalkylalkyl, aryloxy Alkyl, arylthiooxy-alkyl, heteroaryl-alkyl a heterocycloalkylalkyl group; or an alkyl group interrupted by one or more heteroatoms selected from the group consisting of oxygen and sulfur; or by one or more substituents a substituted alkyl group, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N-monoalkyl-amine , N,N-dialkyl-amino, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl-amine, N-monocyclic -alkyl-amino, N,N-bicycloalkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl Sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N- Monocycloalkyl-amine, mercapto, N-monoalkyl-amine, mercapto, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N- Monoaryl-amine Mercapto, N,N-diaryl-amine, mercapto, N-monocycloalkyl-N-monoarylamine, N-monoalkyl-N-monoaryl-amine, mercapto Aminesulfonyl, N-monocycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-bicycloalkyl-amine sulfonyl, N,N-dialkyl - aminoxime, N-monoaryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-single An alkyl-N-monoarylamine sulfonyl group and SO ₃ M; or an alkyl group interrupted by one or more heteroatoms and substituted by one or more substituents selected from the group consisting of Group of constituents: oxygen and sulfur, the one or more substituents being selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine, N- Monoalkyl-amino, N,N-dialkyl-amine, N-monoaryl-amine, N,N-diaryl-amine, N-alkyl-N-aryl-amine , N-monocycloalkyl-amino, N,N-bicyclo-alkyl-amino, N-monoalkyl-monocycloalkyl-amino, N,N-monoaryl-monocyclo-alkane Amino-amino, N-decylamino, N-alkylsulfonyl-amino, ureido, alkyl urea Base, phenyl-ureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkylsulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl, heterocycloalkyl, alkane Oxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl decyloxy, amine carbaryl, N-monocycloalkyl-aminecarbamyl, N-monoalkyl-aminecarbamyl, N, N-bicycloalkyl-aminecarbamyl, N,N-dialkyl-aminecarbamyl, N-monoaryl-aminecarbamyl, N,N-diaryl-aminecarbamyl, N -monocyclic-alkyl-N-monoaryl-aminecarbamyl, N-monoalkyl-N-monoaryl-aminecarbamyl, amine sulfonyl, N-monocycloalkyl-amine sulfonium , N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-monoaryl-amine sulfonyl , N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine sulfonyl and SO ₃ M Or an aryl group substituted by one or more substituents selected from the group consisting of hydroxyl, aryl, cycloalkyl, alkoxy, thioalkoxy, amine , N-monoalkyl-amino, N,N-dialkyl-amine, N- Aryl-amino, N,N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocyclic-alkyl-amino, N,N-bicycloalkyl- Amino, N-monoalkyl-monocyclic-alkyl-amino, N,N-mono-aryl-monocycloalkyl-amino, N-decylamino, N-alkylsulfonyl- Amine, ureido, alkylureido, phenylureido, halogen, cyano, COOM, nitro, fluorenyl, thiol, alkyl sulfonyl, aryl fluorenyl, trifluoromethyl, heteroaryl , heterocyclo-alkyl, alkoxycarbonyl, alkoxythiocarbonyl, decyloxy, aryl methoxyoxy, amine methyl sulfhydryl, N-monocycloalkyl-amine methyl sulfhydryl, N-monoalkane -Amino-N-methyl-indenyl, N,N-dicycloalkyl-amine, mercapto, N,N-dialkyl-amine, mercapto, N-monoaryl-amine, N,N- Aryl-amine-methyl indenyl, N-monocycloalkyl-N-monoarylamine, fluorenyl, N-monoalkyl-N-monoaryl-amine, mercapto, N-mono Cycloalkyl-amine sulfonyl, N-monoalkyl-amine sulfonyl, N,N-dicycloalkyl-amine sulfonyl, N,N-dialkyl-amine sulfonyl, N-single Aryl-amine sulfonyl, N,N-diaryl-amine sulfonyl, N-monocycloalkyl-N-monoarylamine sulfonyl, N-monoalkyl-N-monoarylamine Sulfur And a group SO ₃ M; and M is hydrogen, alkali metal, ammonium, one equivalent of an alkaline earth metal cation or a monovalent organic. The dye according to any one of claims 1, 5 or 6, which has the formula (1b), wherein: R ^1b and R ^6b are SO ₃ M, and R ^2b and R ^5b are hydrogen; or R ^1b And R ^6b are hydrogen, and R ^2b and R ^5b are SO ₃ M; R ^3b , R ^4b , R ^7b and R ^8b are hydrogen; R ^9b , R ^10b , R ^16b and R ^17b are each independently hydrogen, (C ₁ -C ₄ )-alkyl, (C ₁ -C ₄ )-alkoxy, halogen, trifluoromethyl, -SO ₃ M or (C ₁ -C ₄ )-fluorenylamino; R ^13b and R ^20b are each independently an amine group; R ^14b and R ^21b are, independently of each other, alkyl, cycloalkyl, trifluoromethyl, cyano, aminecarbenyl, alkoxycarbonyl, COOM, alkylcarbonyl; An alkyl group substituted with one or more substituents selected from the group consisting of hydroxy, alkoxy, halogen, cyano, COOM, alkoxycarbonyl, decyloxy And an amine carbenyl group; R ^15b and R ^22b are each independently methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methyl Cyclohexyl, 3-methylcyclohexyl, isopropyl, secondary butyl, 2-methylbutyl , 1-ethylpropyl, 1,2-dimethylpropyl, tert-butyl, 3-methylbutyl, pentan-2-yl, 2-ethylhexyl, 2,2-dimethylpropane Base, phenyl, benzyl, 2-hydroxyethyl, 2-methoxyethyl, 3-methoxypropyl, 2-fluoroethyl, 2-chloroethyl, 3-chloropropyl, 2- Ethylhexyl, 2-(2-hydroxyethylsulfanyl)-ethyl, 4-(2-hydroxyethanesulfonyl)phenyl, 2-(2-hydroxy-ethoxy)ethyl, 3- (4-hydroxybutoxy)propyl, 3-(2-phenoxy-ethoxy)-propyl, 3-isopropoxy-propyl, 3-ethoxy-propyl, 3-B Oxybutyl, phenyl, 3-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methoxyphenyl, 3-methoxybenzene Base, 4-methoxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl or 3-phenyl Sulfonamide; and M is hydrogen, an alkali metal, ammonium, one equivalent of an alkaline earth metal or a monovalent organic cation. A method for producing a dye of the formula (1) and a mixture thereof, comprising: a) diazotization of a compound of the formula (2): Wherein R ¹ to R ^{8 are} as defined in claim 1; b) reacting the diazonium salt obtained in a) with a compound of formula (3) and formula (4): Wherein R ⁹ to R ¹² and R ¹⁶ to R ^{19 are} as defined in the first item of the patent application to obtain an intermediate of the formula (5): c) diazotizing the intermediate of formula (5); and d) subjecting the diazonium salt obtained in c) to the compound of formula (6) and formula (7) or a mixture thereof reaction: Wherein R ¹³ to R ¹⁵ and R ²⁰ to R ^{22 are} as defined in the first item of the patent application. A chemical composition comprising one or more dyes as described in any one of claims 1 to 7. A chemical composition consisting of two or more dyes as described in any one of claims 1 to 7. An aqueous solution for dyeing, which comprises a chemical compound as described in any one of claims 1 to 7. A method for dyeing or printing a material containing a carboxy guanamine group and/or a hydroxyl group, the method comprising the step of bringing the carbamoylamine group and/or hydroxy group-containing material to any one of claims 1 to 7 The dyes described are in contact with each other. An ink for use in textile digital printing, which comprises the dye of any one of claims 1 to 7. A dye according to any one of claims 1 to 7 or a chemical composition according to claim 5 or 6 or an aqueous solution according to claim 7 of the patent application. The use of fibers and blends of such fibers for dyeing, the fibers consisting of the following: synthetic fiber materials, nylon materials, nylon-6, nylon-6.6, and aromatic polyamide fibers , plant fiber, seed fiber, cotton, organic cotton, wood wool, coconut fiber from coconut shell; bast fiber, Asia Hemp, hemp, jute, kenaf fiber, ramie, vine; leaf fiber, Qiongma, henequen, banana; stem fiber, bamboo; fiber from animal, wool, organic wool, silk, cashmere , alpaca fiber, mohair, Angolan fiber and fur and leather materials; manufactured, regenerated and reused fiber, cellulose fiber; paper fiber, cellulose regenerated fiber, mucus fiber, acetate and triacetic acid Ester fiber and Lyocell fiber. a fiber and a blend comprising the fiber, the fiber and a blend comprising the fiber, or a chemically and/or physically combined form, according to any one of claims 1 to 7 Or a plurality of dyes selected from the group consisting of synthetic fiber materials, nylon materials, nylon-6, nylon-6.6 and aromatic polyamide fibers, vegetable fibers, seed fibers, cotton, organic cotton, Wood silk cotton, coconut fiber from coconut shell; bast fiber, flax, hemp, jute, kenaf, ramie, vine; leaf fiber, qiong hemp, henaquin fiber, banana; stem fiber, bamboo; from animal Fiber, wool, organic wool, silk, cashmere, alpaca fiber, mohair, angora fiber and fur and leather materials; manufactured, recycled and recycled fiber, cellulose fiber; paper fiber, cellulose recycled fiber, Mucoid fibers, acetate and triacetate fibers, and lyocell fibers.