Dye mixtures of fiber reactive azo dyes, production and use

Abstract

The invention relates to reactive dye mixtures containing one or several dyes of general formula (I), one or several dyes of general formula (II) and, optionally, one or several dyes or general formula (IIIa)-(IIIf), wherein D 1 -D 8 , R, R 1 —R 39 , Z, Z 1 -Z 3 and M have the meaning as cited in claim 1. The invention also relates to the production and the use thereof in order to dye and print fibrous material containing hydroxy and/or carbonamide groups.

1 . A reactive dye mixture comprising one or more dyes of the hereinbelow indicated and defined general formula (I),  
     
       
         
         
             
             
         
       
     
     one or more dyes of the hereinbelow indicated and defined general formula (II)  
     
       
         
         
             
             
         
       
     
     and, optionally, as further components for blending or shading, one or more dyes having, for example, the hereinbelow indicated and defined general formulae (IIIa)-(IIIf)  
     
       
         
         
             
             
         
       
     
     where: 
 D 1  and D 2  are each a group of the general formula (1)  
                     
 where 
 R 1  is hydrogen, (C 1 -C 4 )-alkyl, aryl or a substituted aryl radical;  
 R 2  and R 3  are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and  
 A is a phenylene group of the general formula (2)  
                     where    R 4  and R 5  are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or    
 a naphthylene group of the general formula (3)  
                     where    R 6  and R 7  are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; or    
 a polymethylene group of the general formula (4)  
   —(CR 8 R 9 ) k —  (4)  
 where  
 k is an integer greater than 1 and 
 R 8  and R 9  are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, cyano, amido, halogen or aryl; and  
 
 
 X 1  is hydrogen or a group of the formula —SO 2 -Z; or  
 are each a phenyl group of the general formula (5)  
                     where      10  and R 11  are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and    X 2  has one of the meanings of X 1 ;    
 or are each a naphthyl group of the general formula (6)  
                     where    R 12  and R 13  are independently hydrogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido or halogen; and    X 3  has one of the meanings of X 1 ;    
 Z is —CH═CH 2 , —CH 2 CH 2 Z 1  or hydroxyl, 
 where  
 Z 1  is hydroxyl or an alkali-eliminable group; and  
 
 M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal;  
 D 3  has one of the meanings of D 1  or D 2  or is a group of the general formula (7)  
                     where    R 21  and R 22  independently have one of the meanings of R 2  and R 3 ;    R 23  is hydrogen, (C 1 -C 4 )-alkyl, unsubstituted or (C 1 -C 4 )-alkyl-, (C 1 -C 4 )-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; and    Z 21  is a fiber-reactive heterocyclic group;    
 R is hydrogen, (C 1 -C 4 )-alkyl or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido; or 
 is a group of the formula (14)  
   CH 2 —SO 3 M   (14),  where M is as defined above; and    
 
 n is 1 or 2,  
 D 4 , D 5 , D 6 , D 7  and D 8  have one of the meanings of D 1 , D 2  or D 3 , and, if R 31  is not a group of the general formula (8) or (9), D 4 , and also D 5  or D 6  and D 8 , contain at least one fiber-reactive group of the formula —SO 2 Z or Z 21 ;  
 R 31  is hydrogen, acetyl, carbamoyl, sulfomethyl or a group of the general formula (8) or (9),  
 R 32  is hydrogen or sulfomethyl,  
 R 33  is methyl, carboxyl or carboxyalkyl, with C 1 -C 4 -alkyl,  
 R 34  is hydrogen or methyl,  
 R 35  is hydrogen, cyano, carbamoyl, carboxyl or sulfomethyl,  
 R 36  is methyl, ethyl or B3-sulfoethyl,  
 R 37  is methyl, carboxyl or carboxyalkyl, with C 1 -C 4 -alkyl,  
 R 38  is acetamido, ureido or methyl,  
 R 39  is hydrogen, methyl or methoxy,  
 m is 0 or 1,  
 p is 1, 2 or 3, and  
 Z 3  has one of the meanings of Z 21 , where  
 in the general formula (I) at least one of D 1  and D 2  is a group of the general formula (1); and when A is a group of the general formula (4), R 1  is aryl or substituted aryl; and the reactive dye of the general formula (I) contains at least one —SO 2 -Z group.  
 
   
   
       2 . The dye mixture as claimed in  claim 1 , wherein the heterocyclic reactive group Z 21  is a fiber-reactive group of the general formula (8) or (9) or (10)  
     
       
         
         
             
             
         
       
     
     where 
 V is fluorine or chlorine;  
 U 1 , U 2  are independently fluorine, chlorine or hydrogen; and  
 Q 1  , Q 2  are independently chlorine, fluorine, cyanamido, hydroxyl, (C 1 -C 6 )-alkoxy, phenoxy, sulfophenoxy, mercapto, (C 1 -C 6 )-alkylmercapto, pyridino, carboxypyridino, carbamoylpyridino or a group of the general formula (11) or (12)  
                     where    R 2′  is hydrogen or (C 1 -C 6 )-alkyl, sulfo-(C 1 -C 6 )-alkyl, or phenyl which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, sulfo, halogen, carboxyl, acetamido or ureido;    R 3′  and R 4′  independently have one of the meanings of R 2′ , or combine to form a cyclic ring system of the formula —(CH 2 ) j —, where j is 4 or 5, or alternatively —(CH 2 ) 2 -E-(CH 2 ) 2 —, where E is oxygen, sulfur, sulfo, —NR 5 —, where R 5′  is equal to (C 1 -C 6 )-alkyl, or they are a group of the general formula (13)                        where    R 24 , R 25  and R 26  are each (C 1 -C 4 )-alkyl or (C 1 -C 4 )-hydroxyalkyl; and    B −  is the equivalent of an anion, such as hydrogensulfate, sulfate, fluoride, chloride, bromide, dihydrogenphosphate, hydrogenphosphate, phosphate, hydroxide or acetate;    W is phenylene which is unsubstituted or substituted by 1 or 2 substituents, such as (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, carboxyl, sulfo, chlorine, bromine, or is (C 1 -C 4 )-alkylene-arylene or (C 2 -C 6 )-alkylene, which can be interrupted by oxygen, sulfur, sulfo, amino, carbonyl, carboxamido, or is phenylene-CONH-phenylene, which is unsubstituted or substituted by (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy, hydroxyl, sulfo, carboxyl, amido, ureido or halogen, or is naphthylene, which is unsubstituted or substituted by one or two sulfo groups; and    Z is as in  claim 1 .      
 
   
   
       3 . The reactive dye mixture as claimed in  claim 1 , wherein the substituents R 1  to R 5 , R 8  to R 11  and R 23  are each hydrogen, R 6 , R 7 , R 12 , R 13 , R 21  and R 22  are each hydrogen or sulfo and R 24 , R 25  and R 26  are each methyl.  
   
   
       4 . The reactive dye mixture as claimed in  claim 1 , wherein Z is vinyl, β-chloroethyl or β-sulfatoethyl.  
   
   
       5 . The reactive dye mixture as claimed in  claim 1 , wherein the groups Q 1  and Q 2  in the general formula (9) independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino, 4-(vinylsulfonyl)phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino or N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.  
   
   
       6 . The reactive dye mixture as claimed in  claim 1 , comprising at least one dye of the general formula (Ia)  
     
       
         
         
             
             
         
       
     
     and at least one dye of the general formula (IIa)  
     
       
         
         
             
             
         
       
     
     where M, A, R 1 , Z, D 3  and R are each as defined in  claim 1 .  
   
   
       7 . The reactive dye mixture as claimed in  claim 6 , wherein, in formula (Ia), A is phenylene and Z is vinyl or β-sulfatoethyl and, in formula (IIa), R is hydrogen or sulfomethyl and D 3  has one of the meanings of D 1  or D 2  or is a group of the general formula (7)  
     
       
         
         
             
             
         
       
     
     where 
 R 21  and R 22  independently have one of the meanings of R 2  and R 3 :  
 R 23  is hydrogen, (C 1 -C 4 )-alkyl, unsubstituted or (C 1 -C 4 )-alkyl-, (C 1 -C 4 )-alkoxy-, sulfo-, halogen- or carboxyl-substituted phenyl; and  
 Z 21  is a fiber-reactive heterocyclic group;  
 
   
   
       8 . The reactive dye mixture as claimed in  claim 1 , comprising a dye of the formula (I) in a fraction of 30 to 95% by weight and a dye of the formula (II) in a fraction of 5 to 70% by weight.  
   
   
       9 . The reactive dye mixture as claimed in  claim 8 , further comprising at least one dye of the formulae (IIIa) to (IIIf) in a fraction of 3 to 50% by weight.  
   
   
       10 . The reactive dye mixture as claimed in  claim 1 , comprising one or more monoazo dyes of the formula (15) and/or one or more monoazo dyes of the formula (16) each at 0.5 to 6% by weight  
     
       
         
         
             
             
         
       
     
     where D and M are each as defined in  claim 1 .  
   
   
       11 . The reactive dye mixture as claimed in  claim 1 , comprising more than one navy disazo dye of the general formula (I) in a fraction of up to 95% by weight.  
   
   
       12 . A process for producing dye mixtures as claimed in  claim 1 , which comprises mixing the individual dyes of the formulae (I) and (II) and, if used, (III) with each other either mechanically in solid form or in the form of the aqueous solutions.  
   
   
       13 . A process for producing dye mixtures as claimed in  claim 1 , where the diazo components with the groups D 2  and D 3  in the general formulae (I) and (II) are the same, which comprises diazotizing an amine of the general formula (17)  
       D 2 -NH 2    (17),  
     where D 2  is as defined in  claim 1 , and then reacting the resulting diazonium compound with a mixture of 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid or 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid and an optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid to give the monoazo dyes of the formulae (15) and (II)  
     
       
         
         
             
             
         
       
     
     where D 2  and M are each as defined in  claim 1 , and then diazotizing an amine of the general formula (18)  
       D 1 -NH 2    (18),  
     where D 1  is as defined in  claim 1 , and then coupling the resulting diazonium compound in a second stage with the mixture of the monoazo dyes of the general formulae (15) and (II) obtained in the first stage to give a mixture of the dyes of the general formulae (I) and (II).  
   
   
       14 . A process for producing dye mixtures as claimed in  claim 1 , where the diazo components with the groups D 1  and D 3  in the general formulae (I) and (II) are the same, which comprises diazotizing an amine of the general formula (18),  
       D 1 -NH 2    (18),  
     where D 1  is as defined in  claim 1 , and then reacting the resulting diazonium compound with a mixture of defined proportion of a red monoazo dye of the general formula (15)  
     
       
         
         
             
             
         
       
     
     where D 2  and M are each as defined in  claim 1 , and an optionally N-substituted 6-amino-4-hydroxynaphthalene-2-sulfonic acid or 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid in a first stage to give a mixture of monoazo dyes of the general formulae (15) and (II) and then carrying out the second coupling of the monoazo dye of the general formula (15) to give a mixture of the two dyes of the general formulae (I) and (II).  
   
   
       15 . An aqueous liquid preparation comprising a dye mixture as claimed in  claim 1  with a total dye content of 5-50% by weight.  
   
   
       16 . (canceled)  
   
   
       17 . The reactive dye mixture as claimed in  claim 2 , wherein the substituents R 1  to R 5 , R 8  to R 11  and R 23  are each hydrogen, R 6 , R 7 , R 12 , R 13 , R 21  and R 22  are each hydrogen or sulfo and R 24 , R 25  and R 26  are each methyl and Z is vinyl, β-chloroethyl or β-sulfatoethyl.  
   
   
       18 . The reactive dye mixture as claimed in  claim 17 , wherein the groups Q 1  and Q 2  in the general formula (9) independently of one another are fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino, 4-sulfophenylamino, 3-trimethylammoniumphenylamino, 4-trimethylammoniumphenylamino, 3-(2-sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl)phenylamino, 3-(vinylsulfonyl)phenylamino, 4-(vinylsulfonyl)phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino or N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)amino.  
   
   
       19 . The reactive dye mixture as claimed in  claim 18 , comprising a dye of the formula (I) in a fraction of 30 to 95% by weight and a dye of the formula (II) in a fraction of 5 to 70% by weight.  
   
   
       20 . The reactive dye mixture as claimed in  claim 19 , further comprising at least one dye of the formulae (IIIa) to (IIIf) in a fraction of 3 to 50% by weight.  
   
   
       21 . A process of dyeing and printing hydroxyl- and/or carboxamido-containing fiber material which comprises contacting said material with the reactive dye mixture of  claim 1.