Trichromatic dyeing process

Abstract

The present invention relates to a process for the trichromatic dyeing or printing of natural or synthetic polyamide fibres or such fibres as contain polyamide with dye mixtures and also to such dye mixtures and polyamide fibres dyed or printed therewith.

1 . Trichromatic dyeing process for dyeing or printing natural or synthetic polyamide fibres or such fibres as contain polyamide, characterized in that it comprises using a dye mixture consisting of at least one blue-dyeing compound of the formula (I)  
       
         
           
           
               
               
           
         
       
       where 
 A is a hydrogen atom or a discretionary substituent and  
 R is a discretionarily substituted alkyl, cycloalkyl or aryl radical,  
 and of at least one yellow-dyeing compound of the formula (II)  
                     
 where  
 B is hydrogen; alkyl; hydroxyl-, alkoxy-, alkanoyloxy- or phenoxy-substituted alkyl, aralkyl, cycloalkyl or unsubstituted or alkyl-, halogen-, alkoxy-, nitro-, cyano-, alkoxycarbonyl-, carbamoyl- or sulphamoyl-substituted phenyl,  
 R 4  is hydrogen; alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be substituted by hydroxyl, acyloxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy; unsubstituted or hydroxyl-, chlorine-, hydroxyalkyl-, chloroalkyl- or alkyl-substituted cycloalkyl or polycycloalkyl radicals of 5 to 15 carbon atoms, aralkyl radicals of 7 to 15 carbon atoms or unsubstituted or chlorine-, hydroxyl-, alkoxy-, alkyl-, hydroxyalkyl- or hydroxyalkoxy-substituted phenyl radicals and also alkenyl, pyrrolidonylalkyl and carbonylalkyl radicals,  
 R 1  is hydrogen; alkyl of 1-8 carbon atoms or hydroxyalkyl of 2 to 9 carbon atoms, and  
 R 4  and R 1  combine with the nitrogen to form the radical of pyrrolidine, of piperidine or of morpholine and independently  
 R 2  has the same meanings as R 4 ,  
 R 3  has the same meanings as R 1  and  
 R 2  and R 3  together have the same meanings as R 4  and R 1  together,  
 Y is hydrogen; cyano; chlorine; bromine; methyl sulphone; ethyl sulphone; phenyl sulphone; carbalkoxy or —SO 3 H,  
 Y 1  is hydrogen; chlorine; bromine or —SO 3 H  
 Y 2  is hydrogen; clorine; bromine; methyl; cabolkoxy; 2-benzothiazolyl or —SO 3 H,  
 and where B, R 1  to R 4  and Y to Y 2  contain sulphonic acid groups,  
 and of at least one red-dyeing compound of the formula (III)  
                     
 R 5  is hydrogen; C 1-4 alkyl or C 2-4 -hydroxyalkyl,  
 R 6  is hydrogen; C 1-4 alkyl; C 1-4 alkoxy; —NHCOC 1-4 alkyl; —-NHCOOC 1-4 alkyl or —NHCONH 2 ,  
 R 7  is hydrogen; halogen; C 1-4 alkyl or C 1-4 alkoxy and  
 R 8  is hydrogen; C 1-4 alkyl; C 1-4 alkoxy or halogen;  
                     
 where  
 R 9  is chlorine; hydroxyl or NHCN,  
 R 10  is hydrogen; chlorine or cyano,  
 R 11  is hydrogen; C 1-12 alkyl; hydroxyl-monosubstituted or -disubstituted C 2-8 alkyl, phenyl, phenyl(C 1-4 alkyl) or cyclohexyl and  
 R 12  is unsubstituted or halogen-substituted, hydroxyl-monosubstituted or -di-substituted. phenyl-substituted, carboxyl-substituted or C 1-2 alkoxy-substituted C 4-20 alkyl; —G—O—C 1-12 alkyl, where G is C 2-3 alkylene; phenyl or phenyl(C 1-3 alkyl), whose phenyl ring is unsubstituted or substituted by one to three substituents selected from the group consisting of halogen, C 1-16 alkyl, C 2-6 hydroxyalkyl, C 1-6 alkoxy, phenoxy and —NHCOCH 3 ; or is cyclohexyl which is unsubstituted or substituted by one to three C 1-4 alkyl groups,  
 with the proviso that the total number of carbon atoms in R 11  and R 12  together is at least 8, or  
                     
 and/or of at least one red-dyeing compound of the formula (IV)  
                     
 where  
 each R 13  is independently hydrogen, C 1-4 alkyl, halogen,  
 R 14  is hydrogen or substituted or unsubstituted C 1-4 alkyl,  
 R 15  independently has the same meanings as R 1-4 , or  
 R 14  and R 15  combine to form a cycloaliphatic ring of 5-8 carbon atoms,  
 R 16  is hydrogen or hydroxyl and  
 R 17  independently has the same meanings as R 16 ,  
 and/or at least one red-dyeing compound of the formula (V)  
                     
 where  
 E represents an aromatic, araliphatic, hydroaromatic radical or two aromatic radicals,  
 Z represents hydrogen or a discretionary substituent except sulphonic acid and carboxylic acid groups,  
 n represents 1 or 2,  
 and at least one anionic and/or nonionic dyeing auxiliary.  
 
     
     
         2 . Trichromatic dyeing process according to  claim 1 , characterized in that it comprises using a dye mixture consisting of at least one blue-dyeing compound as per the formula (I) where A is a hydrogen atom or a discretionarily substituted alkyl or aryl radical, and of at least one yellow-dyeing compound as per the formula (II) where 
 B is hydrogen; alkyl; hydroxyl-, alkoxy-, alkanoyloxy or phenoxy-substituted alkyl,    R 4  is hydrogen or alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be substituted by hydroxyl, acyloxy, alkoxy, cyano, cycloalkoxy, aralkoxy or aroxy,    R 2  is hydrogen; alkyl of 1-8 carbon atoms which may be interrupted by oxygen atoms and may be aryl radicals of 7 to 15 carbon atoms and    Y is hydrogen; chlorine; bromine or —SO 3 H,    Y 2  is hydrogen; chlorine; bromine; methyl or —SO 3 H,    and of at least one red-dyeing compound as per the formula (III)    where                          R 5  is hydrogen or methyl,    R 6  is hydrogen; methyl; C 1-4 alkoxy; —NHCOCH 3  or —NHCONH 2 ,    R 7  is hydrogen; methyl and    R 8  is hydrogen; methyl; methoxy and                          where    R 9  is chlorine; hydroxyl or NHCN,    R 10  is hydrogen; chlorine or cyano,    R 11  is hydrogen; C 1-4 alkyl; hydroxyl-monosubstituted or -disubstituted C 2-4 alkyl; or phenyl and    R 12  is unsubstituted or phenyl-monosubstituted C 4-14 alkyl; —G1—O—C 6-12 alkyl, where G1 is linear C 2-3 alkylene; C 6-16 alkyl- or phenoxy-monosubstituted phenyl; phenyl(C 1-2 alkyl) whose phenyl ring is unsubstituted or monosubstituted by C 6-14 alkyl; or cyclohexyl substituted by one to three methyl groups,    and/or of a red-dyeing compound of the formula (IVb)                          and/or of at least one red-dyeing compound of the formula (Va)                          where    R 18  is hydrogen or substituted or unsubstituted C 1-4 alkyl,    R 19  independently has the same meanings as R 18 ,    n is 1 or 2,    and at least one anionic and/or nonionic dyeing auxiliary.    
     
     
         3 . Trichromatic dyeing process according to  claim 1  or  2 , characterized in that it comprises using a dyeing mixture consisting of at least one blue-dyeing compound as per the formula (I), where A is a hydrogen atom and R is a discretionarily substituted aryl radical and of at least one yellow-dyeing compound as per the formula (II) where 
 B is hydrogen or methyl,  
 R 4  is hydrogen or alkyl of 1-4 carbon atoms,  
 R 1  is hydrogen or alkyl of 1-4 carbon atoms,  
 R 2  is hydrogen; alkyl of 1-4 carbon atoms or aralkyl radicals of 7 to 15 carbon atoms,  
 R 3  is hydrogen or methyl  
 Y is hydrogen or chlorine,  
 Y 1  is hydrogen or chlorine,  
 Y 2  is hydrogen or —SO 3 H,  
 and of at least one red-dyeing compound as per the formula (III)  
 where  
                     
 R 5  is hydrogen or methyl,  
 R 6  is hydrogen or methyl,  
 R 8  is hydrogen or methyl and  
                     
 where  
 R 9  is chlorine or hydroxyl,  
 R 10  is hydrogen or methyl and  
 R 12  is unsubstituted or phenyl-monosubstituted C 4-14 alkyl,  
 and of a red-dyeing compound of the formula (IVb)  
                     
 and of at least one red-dyeing compound of the formula (Vb)  
                     
 where  
 R 18  is hydrogen or methyl,  
 R 19  independently has the same meanings as R 18    
 and at least one anionic and/or nonionic dyeing auxiliary.  
 
     
     
         4 . Trichromatic dyeing process according to  claim 1  or  2 , characterized in that it comprises using a dye mixture consisting of at least one blue component according to  claim 1  or  2 , and of at least one yellow component from  claim 1  or 2 and of a red component which constitutes a mixture of at least one compound of the formula (III) and at least one compound of the formula (IV), and at least one anionic and/or nonionic dyeing auxiliary.  
     
     
         5 . Trichromatic dyeing process according to  claim 1  or  2 , characterized in that it comprises using a dye mixture consisting of at least one blue component according to  claim 1  or  2 , and of at least one yellow component from  claim 1  or  2  and of a red component which constitutes a mixture of at least one compound of the formula (III) and at least one compound of the formula (V), and at least one anionic and/or nonionic dyeing auxiliary.  
     
     
         6 . Trichromatic dyeing process according to  claim 1  or  2 , characterized in that it comprises using a dye mixture consisting of at least one blue component according to  claim 1  or  2 , and of at least one yellow component from  claim 1  or  2  and of a red component which constitutes a mixture of at least one compound of the formula (IV) and at least one compound of the formula (V), and at least one anionic and/or nonionic dyeing auxiliary.  
     
     
         7 . Dye mixtures used in the processes of claims  1 - 6 .  
     
     
         8 . Substrates consisting of natural or synthetic polyamide or polyamidic substrates dyed or printed by a trichromatic dyeing process as claimed in any of claims  1 - 6 .