Process for dyeing or printing and novel reactive dyes

Abstract

Process for dyeing or printing paper, films of plastic or fiber material containing hydroxyl groups or containing nitrogen with reactive dyes, which comprises using at least one reactive dye of the formula (1) from the following group a) and at least one reactive dye from the following groups b), c) and d): a) green- or blue-dyeing reactive dyes of the formula (1) b) blue-dyeing reactive dyes of the formula (2) or (3) c) red-dyeing reactive dyes of the formula (4) d) yellow- or orange-dyeing reactive dyes of the formula (5)

What is claimed is:  
     
         1 . A process for dyeing or printing paper, films of plastic or fibre material containing hydroxyl groups or containing nitrogen with reactive dyes, which comprises using at least one reactive dye of the formula (1) from the following group a) and at least one reactive dye from the following groups b), c) and d): 
 a) green- or blue-dyeing reactive dyes of the formula (1)  
                 
   in which    NiPhC is the radical of a nickel phthalocyanine,    R 1  is hydrogen or substituted or unsubstituted C 1 -C 4 alkyl,    V 1  is hydrogen or substituted or unsubstituted C 1 -C 8 alkyl, phenyl or naphthyl and    x is 2 to 4 and y is 1 to 2,    the reactive dye of the formula (1) containing at least one fibre-reactive group;    b) blue-dyeing reactive dyes of the formula (2) or (3)  
                 
   in which    (R 2 ) 0-3  is 0 to 3 C 1 -C 4 alkyl radicals which are identical or different from one another and    (R 3 ) 0-3  is 0 to 3 substituents, which are identical or different from another, from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl and sulfo,    X 1  is chlorine or fluorine and    R 4  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,  
                 
   in which    R 5  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,    X 2  is chlorine or fluorine,    Y 1  is hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato and uninterrupted or interrupted by oxygen, or phenyl or naphthyl which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo, and the benzene nuclei I, II and III contain no further substituents or are further substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or carboxyl;    c) red-dyeing reactive dyes of the formula (4)  
                 
   in which    R 6  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,    R 7  and R 8  independently of one another are hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo,    X 3  is chlorine or fluorine and    Y 2  is hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by hydroxyl, sulfo, sulfato or a radical of the formula —SO 2 —Z and is uninterrupted or interrupted by oxygen, or phenyl or naphthyl which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl, sulfo or a radical of the formula —SO 2 —Z or —CO—NH—(CH 2 ) 2-3 —SO 2 —Z, or the radical —N(R 6 )—Y 2  is morpholino, in which    Z is a radical of the formula —CH═CH 2  or —CH 2 —CH 2 —U 1  and U 1  is a leaving group;    d) yellow- or orange-dyeing reactive dyes of the formula (5)  
                 
   in which    R 9  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,    R 10  and R 11  independently of one another are hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo,    X 4  is chlorine or fluorine and    Y 3  is hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato and is uninterrupted or interrupted by oxygen, or phenyl or naphthyl which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl, sulfo or a halogenotriazinylamino radical which is unsubstituted or further substituted, or the radical —N(R 9 )—Y 3  is morpholino, and    K 1  is a radical of the formula  
                 
   in which    R 12  is hydroxyl or amino,    R 13  is methyl or carboxyl,    (R 14 ) 0-3  is 0 to 3 identical or different substituents from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl and sulfo,    R 15  and R 17  are C 1 -C 4 alkyl and    R 16  is cyano, carbamoyl or sulfomethyl.    
     
     
         2 . A process according to    claim 1   , wherein 
 R 1  is hydrogen or C 1 -C 4 alkyl and    V 1  is a radical of the formula  
                 
   in which    R′ is hydrogen or C 1 -C 4 alkyl,    X 5  is fluorine or chlorine,    Y 4  is hydrogen or phenyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo,    alkylene is C 1 -C 6 alkylene and    Z is as defined in    claim 1   .    
     
     
         3 . A process according to    claim 1   , wherein the reactive dye of the formula (1) used is a reactive dye of the formula  
                   
       in which 
 NiPhC, x and y are as defined in    claim 1   .  
 
     
     
         4 . A process according to    claim 1   , wherein 
 R 3  is sulfo,    R 4  is hydrogen or C 1 -C 4 alkyl and    X 1  is chlorine.    
     
     
         5 . A process according to    claim 1   , wherein the reactive dye of the formula (2) used is a reactive dye of the formula  
                   
     
     
         6 . A process according to    claim 1   , wherein the reactive dye of the formula (3) used is a reactive dye of the formula  
                   
       in which 
 R 5  is hydrogen or C 1 -C 4 alkyl and  
 X 2  and Y 1  are as defined in    claim 1   .  
 
     
     
         7 . A process according to    claim 1   , wherein 
 R 5  is hydrogen or C 1 -C 4 alkyl,    X 2  is chlorine and    Y 1  is hydrogen.    
     
     
         8 . A process according to    claim 1   , wherein 
 R 6  is hydrogen or C 1 -C 4 alkyl,    R 7  is sulfo,    R 8  is hydrogen or sulfo and    Y 2  is hydrogen, C 1 -C 8 alkyl, which is unsubstituted or substituted by hydroxyl, sulfo or sulfato and is uninterrupted or interrupted by oxygen, or phenyl or naphthyl which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo, or the radical —N(R 6 )—Y 2  is morpholino.    
     
     
         9 . A process according to    claim 1   , wherein the reactive dye of the formula (4) used is a reactive dye of the formula  
                   
       in which 
 R 6  is hydrogen or C 1 -C 4 alkyl,  
 R 7  is sulfo,  
 R 8  is hydrogen or sulfo and  
 Y 2  is C 1 -C 4 alkyl which is substituted by hydroxyl, sulfo or sulfato and is uninterrupted or interrupted by oxygen, or is phenyl which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo.  
 
     
     
         10 . A process according to    claim 1   , wherein 
 R 9  is hydrogen or C 1 -C 4 alkyl,    R 10  is sulfo,    R 11  is hydrogen or sulfo,    R 12  is hydroxyl,    R 13  is methyl,    R 16  is carbamoyl and    X 4  is chlorine.    
     
     
         11 . A process according to    claim 1   , wherein the reactive dye of the formula (5) used is a reactive dye of the formula  
                   
     
     
         12 . A process according to    claim 1   , wherein 
 at least one reactive dye of the formula (1) from group a) and    at least one reactive dye of the formula (4) from group c) are used.    
     
     
         13 . A process according to    claim 1   , wherein 
 at least one reactive dye of the formula (1) from group a) and    at least one reactive dye of the formula (5) from group d) are used.    
     
     
         14 . A process according to    claim 1   , wherein 
 at least one reactive dye of the formula (1) from group a),    at least one reactive dye of the formula (4) from group c) and    at least one reactive dye of the formula (5) from group d) are used.    
     
     
         15 . A process according to    claim 1   , wherein 
 at least one reactive dye of the formula (1) from group a),    at least one reactive dye of the formula (2) or (3) from group b),    at least one reactive dye of the formula (4) from group c) and    at least one reactive dye of the formula (5) from group d) are used.    
     
     
         16 . A process according to    claim 1   , wherein fibre material containing hydroxyl groups or containing nitrogen is printed.  
     
     
         17 . A process according to    claim 16   , wherein fibre material containing hydroxyl groups or containing nitrogen is printed by the ink jet printing process.  
     
     
         18 . A process according to    claim 17   , wherein the fibre material is printed with aqueous inks which comprise 5 to 35% by weight of the reactive dye.  
     
     
         19 . A process according to    claim 18   , wherein the aqueous inks comprise 5 to 30% by weight of 1,2-propylene glycol.  
     
     
         20 . A process according to    claim 1   , wherein fibre material containing hydroxyl groups or containing nitrogen is dyed by the exhaust method or the pad-dyeing method.  
     
     
         21 . A process according to    claim 1   , wherein the fibre material is fibre material containing hydroxyl groups.  
     
     
         22 . A process according to    claim 21   , wherein the fibre material is cellulosic fibre material.  
     
     
         23 . A process according to    claim 1   , wherein paper or films of plastic are printed.  
     
     
         24 . A reactive dye of the formula  
                   
       in which 
 R 6  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,  
 R 7  and R 8  independently of one another are hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo,  
 X 3  is fluorine and  
 Y 2  is hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato and is uninterrupted or interrupted by oxygen, or phenyl or naphthyl which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo, or the radical —N(R 6 )—Y 2  is morpholino.  
 
     
     
         25 . A dye mixture which comprises at least one reactive dye of the formula (2)  
                   
       in which 
 (R 2 ) 0-3  is 0 to 3 C 1 -C 4 alkyl radicals which are identical or different from one another and  
 (R 3 ) 0-3  is 0 to 3 substituents, which are identical or different from another, from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl and sulfo,  
 X 1  is chlorine or fluorine and  
 R 4  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,  
 and at least one reactive dye of the formula (3)  
                 
 
 in which  
 R 5  is hydrogen or C 1 -C 4 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato,  
 X 2  is chlorine or fluorine,  
 Y 1  is hydrogen, C 1 -C 8 alkyl which is unsubstituted or substituted by hydroxyl, sulfo or sulfato and uninterrupted or interrupted by oxygen, or phenyl or naphthyl which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl or sulfo, and the benzene nuclei I, II and III contain no further substituents or are further substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen or carboxyl.