Mixed coupled azo pigments

Abstract

(1) A mixed coupled azo pigment prepared from: (A) 30% to 70% of two or more diazonium components, at least one derived from a monoaryl amine and (B) an organic coupled component, said pigment containing one or more COOH or . .SO H.!. .Iadd.SO 3 H .Iaddend.groups or esters, amides, alkali metal or alkali earth metal salts thereof or (2) A mixed coupled azo pigment prepared from: (A) 5% to 95% of two or more bis, tris or tetrakis diazonium components, at least one derived from a monoaryl amine and meeting certain specific critria and (B) an organic coupling component, said pigment comprising the same acid or salt groups of pigment (1).

It is claimed: 
     
       1. A mixed coupled azo pigment prepared from (A) a mixture comprising from about 30% to about 70% by weight of each of two bis-diazonium components derived from aromatic amines provided that at least one diazonium component is derived from a monoaryl amine; and   (B) an organic coupling component provided that at least one of the diazonium components or the coupling component contains one or more --COOH or --SO 3  H group or the esters or amides or alkali metal or alkaline earth metal salts thereof.   
     
     
       2. The azo pigment of claim 1 wherein the coupling component is selected from the group consisting of phenols, naphthols, aromatic amines, enolizable carbonyl-containing compounds and heterocyclic compounds selected from the group consisting of pyrroles, indoles and pyrazolones. 
     
     
       3. The azo pigment of claim 1 wherein the coupling component is an arylamide of acetoecetic acid. 
     
     
       4. A mixed coupled azo pigment prepared from (A) a mixture comprising from about 30% to about 70% by weight of each of two or more diazonium components derived from aromatic amines provided that at least one diazonium component is derived from a monoaryl amine; and   (B) an organic coupling component which is an enolizable carbonyl-containing compound characterized by the formula   XCH.sub.2 C(O)Y                                            (III)        wherein X is an electron-withdrawing group, and Y is a substituted or unsubstituted amino group provided that at least one of the diazonium components or the coupling component contains one or more --COOH or --SO 3  H group or the esters or amides or alkali metal or alkaline earth metal salts thereof.   
     
     
       5. The azo pigment of claim 4 wherein X is --COR, --COOH, --COOR or --CN wherein R is an alkyl or aryl group. 
     
     
       6. A mixed coupled azo pigment prepared from (A) a mixture comprising from about 30% to about 70% by weight of each of two or more diazonium components derived from aromatic amines wherein at least one of the diazonium components in the mixture is derived from an aromatic amine characterized by the formula ##STR7##  wherein each R is independently hydrogen or a halogen, hydrocarbyl, hydrocarbyloxy or nitro group; n is 0, 1 or 2; each Y is independently --COOH, --SO 3  H, or the esters or alkali metal salts thereof; and m is 1 or 2; and   (B) an organic coupling component which is an enolizable carbonyl-containing compound.   
     
     
       7. The azo pigment of claim 6 wherein the mixture (A) comprises from about 40% to about 60% each of the two diazonium components. 
     
     
       8. The azo pigment of claim 6 wherein the coupling component (B) is an enolizable carbonyl-containing compound characterized by the formula   XCH.sub.2 C(O)Y                                            (III)     wherein X is an electron-withdrawing group and Y is a substituted or unsubstituted amino group.   
     
     
       9. The azo pigment of claim 8 wherein the electron-withdrawing group is --COR, --COOH, --COOH, --COOR or --CN wherein R is an alkyl or an aryl group. 
     
     
       10. The azo pigment of claim 6 wherein n is 2, one R is a halogen, and the other R is an alkyl group. 
     
     
       11. The azo pigment of claim 6 wherein Y is --SO 3  H and m is 1. 
     
     
       12. The azo pigment of claim 6 wherein the mixture (A) contains two of the diazonium components in approximately equal amounts by weight. 
     
     
       13. The azo pigment of claim 6 wherein the coupling component is an arylamide of acetoacetic acid characterized by the formula ##STR8## wherein each R 2  is independently hydrogen halogen, nitro, alkyl group containing 1 to about 4 carbon atoms, alkoxy group containing 1 to about 4 carbon atoms, or --NHCOCH 3  and o is 0, 1, 2 or 3. 
     
     
       14. A metal salt of a mixed coupled azo pigment prepared by coupling a mixture comprising from about 30% to about 70% by weight of each of two or more diazonium components derived from aromatic amines with an organic coupling component which is an enolizable carbonyl-containing compound and wherein at least one of the diazonium components is derived from a monoarylamine and contains an acidic group, and the metal is an alkaline earth metal, a transition metal or aluminum, or combination thereof. 
     
     
       15. The metal salt of claim 14 wherein the acidic group is a carboxylic acid group or a sulfonic acid group. 
     
     
       16. The metal salt of claim 14 wherein at least one of the diazonium components is derived from an aromatic amine characterized by the formula ##STR9## wherein R is independently hydrogen or a halogen, hydrocarbyl, hydrocarbyloxy or nitro group; n is 0, 1 or 2; each Y is independently --COOH or --SO 3  H; and m is 1 or 2. 
     
     
       17. The metal salt of claim 14 wherein the metal is an alkaline earth metal. 
     
     
       18. The metal salt of claim 17 wherein the acidic group is a carboxylic or sulfonic acid group. 
     
     
       19. The metal salt of claim 17 wherein the acidic group is a sulfonic acid group. 
     
     
       20. The metal salt of claim 17 wherein the metal is calcium. 
     
     
       21. The metal salt of claim 17 wherein at least one of the diazonium components is derived from an aromatic amine characterized by the formula ##STR10## wherein R is independently hydrogen or a halogen, hydrocarbyl, hydrocarbyloxy or nitro group; n is 0, 1 or 2; each Y is independently --COOH or --SO 3  H; and m is 1 or 2. 
     
     
       22. The metal salt of claim 21 wherein m is 1. 
     
     
       23. The metal salt of claim 21 wherein Y is --SO 3  H and m is 1. 
     
     
       24. The metal salt of claim 14 wherein the coupling component is an enolizable carbonyl-containing compound characterized by the formula   XCH.sub.2 C(O)Y                                            (III)     wherein X is an electron-withdrawing group and Y is a substituted or unsubstituted amino group.   
     
     
       25. The metal salt of claim 24 wherein X is --COR, --COOH, --COOR, or --CN wherein R is an alkyl or aryl group. 
     
     
       26. The metal salt of claim 21 wherein the mixture comprises from about 40 to about 60% of two diazonium components. 
     
     
       27. A mixed coupled azo pigment prepared from (A) a minute comprising from about 5 to about 95% by weight of each of two or more diazonium components derived from aromatic amines wherein at least one of the diazonium components is a bis-, tris- or tetrakis-diazonium component provided that at least one diazonium component is derived from a monoaryl amine, and further provided:   (A-1) if one of the aromatic amines in the mixture contains a carboxamide group, then the other amine in the mixture is a diaryldiamine; or   (A-2) the mixture comprises about 20 to about 80% of each diazonium component when one of the aromatic amines contains a carboxylic acid, sulfonic acid, or salt thereof, and the other aromatic amine is a diaryldiamine; or   (A-3) the mixture comprises from about 30 to about 70% of each of the diazonium components when the aromatic amines in the mixture contain a nitro group; and   (B) an organic coupling component, provided that at least one of the diazonium component in (A) or the coupling component contains one or more --COOH or --SO 3  H group or the esters or amides or alkali metal or alkaline or metal salts thereof, and further provided that when the coupling component is a 2-naphthol characterized by the formula ##STR11##  wherein R 1  is hydrogen or --COOH, the mixture (A) may comprise from about 5 to about 95% by weight of each of two diazonium components derived from aromatic amine containing carboxamide groups, and the mixture does not have to contain a diaryldiamine. .Iadd.   
     
     
       28.  A mixed coupled azo pigment prepared from (A) a mixture comprising from about 40% to about 60% by weight of each of two diazonium components derived from aromatic amines which are free of hydrocarbyloxy groups and wherein at least one of the diazonium components in the mixture is derived from an aromatic amine characterized by the formula ##STR12##  wherein each R is independently hydrogen or a halogen, hydrocarbyl, or nitro group; n is 0, 1 or 2; each Y is independently --COOH, --SO 3  H, or the esters, alkali metal salts or alkaline earth metal salts thereof; and m is 1 or 2; and   (B) an organic coupling component which is a 2-naphthol characterized by the formula ##STR13##  wherein R 1  is hydrogen or --COOH, or the esters, alkali metal salts or alkaline earth metal salts thereof. .Iaddend..Iadd.   
     
     
       29.  The azo pigment of claim 28 wherein n is 2, one R is a halogen, and the other R is an alkyl group. .Iaddend..Iadd.30. The azo pigment of claim 28 wherein Y is --SO 3  H and m is 1. .Iaddend..Iadd.31. The azo pigment of claim 28 wherein Y is --SO 3  H, m is 1, n is 2 and one R is a halogen and the other R is an alkyl group. .Iaddend..Iadd.32. The azo pigment of claim 28 wherein R 1  is --COOH, an alkali metal or alkaline earth metal salt thereof, or mixtures of said metal salts. .Iaddend.