Disazo dyes, and copper complexes thereof, for dyeing paper

Abstract

The dyes of formula (1) according to claim 1 and the copper complexes of dyes of formula (2) according to claim 9 or the mixtures of mono-copper complex with the bis-copper complex are excellently suitable for dyeing paper with good light-fastness properties.

1 . A solid dye preparation for dyeing paper comprising a copper complex of formula  
     
       
         
         
             
             
         
       
     
     wherein 
 Z 1  is NHR 6 ,  
 R 6  being a radical of formula CO—R 8 , CO—NH—R 8 , SO 2 -alkyl, SO 2 -aryl,  
                     
  COOR 8 ,  
 R 8  being hydrogen, alkyl or aryl and  
 R 7  being COOH or SO 3 H in the o-position to the NH 2  group,  
 Z 2  is as defined for Z 1  or is hydrogen, hydroxy, alkoxy or a radical NHR 5 ,  
 R 5  being hydrogen, alkyl, aryl, COR 8 , CO—NHR 8  or SO 2 R 8 ,  
 R 1  and R 3  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,  
 R 2  and R 4  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR 8  or NHCOR 8 ,  
 X is a direct bond in which case symmetrical compounds wherein Z 1  and Z 2  are NHCOCH 3 , NHCOOCH 3  or NHCO-phenyl are excluded, or is —C═C— in which case both Z 1  and Z 2  cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR 8 , —NR 8 CONR 9 — or a group of formula  
                     
 Y being hydroxy, alkoxy or NR 9 R 10 ,  
 R 9  and R 10  being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,  
 n and m are each independently of the other 1 or 2,  
 and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,  
 with the proviso that the compounds of formulae  
                     
 are excluded and optionally, further additives.  
 
   
   
       2 . A mono- or bis-copper complex of a dye of formula  
     
       
         
         
             
             
         
       
     
     wherein 
 R 1  and/or R 3  are hydroxy or alkoxy,  
 Z 1  is NHR 6 ,  
 R 6  being a radical of formula CO—R 8 , CO—NH—R 8 , SO 2 -alkyl, SO 2 -aryl,  
                     
  COOR 8 ,  
 R 8  being hydrogen, alkyl or aryl and  
 R 7  being COOH or SO 3 H in the o-position to the NH 2  group,  
 Z 2  is as defined for Z 1  or is hydrogen, hydroxy, alkoxy or a radical NHR 5 ,  
 R 5  being hydrogen, alkyl, aryl, COR 8 , CO—NHR 8  or SO 2 R 8 ,  
 R 2  and R 4  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR 8  or NHCOR 8 ,  
 X is a direct bond in which case symmetrical compounds wherein Z 1  and Z 2  are NHCOCH 3 , NHCOOCH 3  or NHCO-phenyl are excluded, or is —C═C— in which case both Z 1  and Z 2  cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR 8 , —NR 8 CONR 9 — or a group of formula  
                     
 Y being hydroxy, alkoxy or NR 9 R 10 ,  
 R 9  and R 10  being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,  
 n and m are each independently of the other 1 or 2,  
 and wherein the rings A and B may each independently of the other carry a fused-on benzene ring.  
 
   
   
       3 . A dye according to  claim 2 , wherein Z 2  is hydrogen, hydroxy, alkoxy, amino, NH—COO—C 1 -C 4 alkyl, or anilino which is unsubstituted or substituted by amino and/or by sulfo.  
   
   
       4 . A dye according to 2, wherein Z 1  is NH—COO—C 1 -C 4 alkyl or the 4-amino-3-sulfo-aniline radical.  
   
   
       5 . A dye according to 2, wherein Z 1  and Z 2  are identical and each is NH—COO—C 1 -C 4 alkyl or the 4-amino-3-sulfo-aniline radical.  
   
   
       6 . A dye according to  claim 2 , wherein R 2  and R 4  are each hydrogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.  
   
   
       7 . A mono-copper complex of a dye of formula  
     
       
         
         
             
             
         
       
     
     wherein 
 R 1  and/or R 3  are hydroxy or alkoxy,  
 Z 1  is NHR 6 ,  
 R 6  being a radical of formula CO—R 8 , CO—NH—R 8 , SO 2 -alkyl, SO 2 -aryl,  
                     
  COOR 8 ,  
 R 8  being hydrogen, alkyl or aryl and  
 R 7  being COOH or SO 3 H in the o-position to the NH 2  group,  
 Z 2  is as defined for Z 1  or is hydrogen, hydroxy, alkoxy or a radical NHR 5 , R 5  being hydrogen, alkyl, aryl, COR 8 , CO—NHR 8  or SO 2 R 8 ,  
 R 1  and R 3  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,  
 R 2  and R 4  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR 8  or NHCOR 8 ,  
 X is a direct bond in which case symmetrical compounds wherein Z 1  and Z 2  are NHCOCH 3 , NHCOOCH 3  or NHCO-phenyl are excluded, or is —C═C— in which case both Z 1  and Z 2  cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR 8 , —NR 8 CONR 9 — or a group of formula  
                     
 Y being hydroxy, alkoxy or NR 9 R 10 ,  
 R 9  and R 10  being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,  
 n and m are each independently of the other 1 or 2,  
 and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,  
 and  
 a mixture thereof with a bis-copper complex of a dye of formula (I)  
                     
 wherein the substituents are defined as above and optionally, further additives.  
 
   
   
       8 . A concentrated aqueous solution for dyeing paper, comprising a copper complex of a dye of formula (1)  
     
       
         
         
             
             
         
       
     
     wherein 
 Z 1  is NHR 6 ,  
 R 6  being a radical of formula CO—R 8 , CO—NH—R 8 , SO 2 -alkyl, SO 2 -aryl,  
                     
  COOR 8 ,  
 R 8  being hydrogen, alkyl or aryl and  
 R 7  being COOH or SO 3 H in the o-position to the NH 2  group,  
 Z 2  is as defined for Z 1  or is hydrogen, hydroxy, alkoxy or a radical NHR 5 ,  
 R 5  being hydrogen, alkyl, aryl, COR 8 , CO—NHR 8  or SO 2 R 8 ,  
 R 1  and R 3  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy,  
 R 2  and R 4  are each independently of the other hydrogen, hydroxy, alkyl or alkoxy, halogen, sulfo, carboxy, NHCONHR 8  or NHCOR 8 ,  
 X is a direct bond in which case symmetrical compounds wherein Z 1  and Z 2  are NHCOCH 3 , NHCOOCH 3  or NHCO-phenyl are excluded, or is —C═C— in which case both Z 1  and Z 2  cannot simultaneously be acetylamino, benzoylamino or 4-amino-3-sulfo-anilino, or is azo, azoxy, —NR 8 , —NR 8 CONR 9 — or a group of formula  
                     
 Y being hydroxy, alkoxy or NR 9 R 10 ,  
 R 9  and R 10  being each independently of the other hydrogen, unsubstituted or substituted alkyl or unsubstituted or substituted aryl,  
 n and m are each independently of the other 1 or 2,  
 and wherein the rings A and B may each independently of the other carry a fused-on benzene ring,  
 with the proviso that the compounds of formulae  
                     
 are excluded and optionally, further additives.  
 
   
   
       9 . Paper dyed using a solid dye of formula (1) according to  claim 1 .  
   
   
       10 . Paper dyed using a concentrated aqueous solution for dyeing paper according to  claim 8 .  
   
   
       11 . A concentrated aqueous solution for dyeing paper, comprising a dye according to  claim 2  and optionally, further additives.  
   
   
       12 . A solid dye preparation for dyeing paper, comprising a dye according to  claim 2  and optionally, further additives.  
   
   
       13 . Paper dyed using a dye according to  claim 2.