Blue phthalocyanine pigment composition and its preparation

1. A process for the preparation of a pigment composition, comprising the steps of:

wet-milling a mixture of α copper phthalocyanine and ε copper phthalocyanine, wherein the ratio of α copper phthalocyanine to ε copper phthalocyanine at the beginning of wet-milling is from 1:99 to 99:1, together with an aminomethyl-substituted phthalocyanine of formula (I), or a mixture thereof, and a milling aid in an organic liquid;

wherein M 1 is 2 H, Al(Cl), Al(OH), Bi(OH), Ca, Cd, Ce(Cl), Cr(OH), Co, Cu, Mn, Fe, Fe(Cl), Fe(OH), In(Cl), Mg, Mn(O), Ni, Os, Pb, Pd, Pt, Re, Rh, Rh(O), Ru, Si(Cl) 2 , Si(OC 1 -C 5 alkyl) 2 , Si(OH) 2 , Sn, Sr, Ti(O), V(O), Zn, Zr(O) or Zr(OH) 2 ;

R 1 is

R 2 is

 C 1 -C 20 alkyl, C 2 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 1-3 H, [C 2 -C 6 alkylen-O—] 1-3 C 1 -C 8 alkyl, [C 2 -C 6 alkylen-NH—] 1-3 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 1-3 C 1 -C 8 alkyl;

R 3 is H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 1-3 H, [C 2 -C 6 alkylen-O—] 1-3 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 1-3 C 1 -C 8 alkyl;

R 4 and R 5 are independently from one another H or C 1 -C 6 alkyl;

each R 6 is independently from all others H, C 1 -C 8 alkyl, Cl or NO 2 ; and

R 7 is H, COOH, CONH 2 , CONHC 1 -C 8 alkyl or CON(C 1 -C 8 alkyl) 2 ;

adding an ammonium sulfonato phthalocyanine of formula (II), or a mixture thereof, before the milling aid and the organic liquid are separated from the wet-milled mixture;

wherein M 2 is 2 H, Al(Cl), Al(OH), Bi(OH), Ca, Cd, Ce(Cl), Cr(OH), Co, Cu, Mn, Fe, Fe(Cl), Fe(OH), In(Cl), Mg, Mn(O), Ni, Os, Pb, Pd, Pt, Re, Rh, Rh(O), Ru, Si(Cl) 2 , Si(OC 1 -C 5 alkyl) 2 , Si(OH) 2 , Sn, Sr, Ti(O), V(O), Zn, Zr(O) or Zr(OH) 2 ;

R 8 and R 9 are each independently of one another H or C 1 -C 4 alkyl;

R 10 is H, phenyl, benzyl, 2-phenylethyl, naphthyl, C 1 -C 20 alkyl, C 8 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 1-6 H, [C 2 -C 6 alkylen-O—] 1-6 C 1 -C 8 alkyl, [C 2 -C 6 alkylen-NH—] 1-6 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 1-6 —C 1 -C 6 alkyl; and

R 11 is C 8 -C 20 alkyl, C 8 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 3-6 H, [C 2 -C 6 alkylen-O—] 3-6 C 1 -C 8 alkyl, [C 2 -C 6 alkylen-NH—] 3-6 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 3-6 C 1 -C 8 alkyl;

with the proviso that the total number of carbon atoms in R 8 , R 9 , R 10 and R 11 is from 8 to 30;

separating the milling aid and the organic liquid from the wet-milled mixture after addition of the ammonium salt of formula (II); and

isolating the pigment composition;

wherein the thus isolated pigment composition comprises, by weight based on the total content of components having a phthalocyanine core,

from 70 to 93% of ε copper phthalocyanine;

from 5 to 18% of the aminomethyl-substituted phthalocyanine of formula (I) or mixture thereof;

from 2 to 15% of the ammonium sulfonato phthalocyanine of formula (II) or mixture thereof; and

from 0 to 2% of other phthalocyanine compounds.

2. A process according to claim 1 , wherein the pigment composition comprises from 6 to 20% by weight, based on the total content of components having a phthalocyanine core, of the aminomethyl-substituted phthalocyanine of formula (I) or mixture thereof plus the ammonium sulfonato phthalocyanine of formula (II) or mixture thereof, and the molar ratio of the aminomethyl-substituted phthalocyanine of formula (I) or mixture thereof to the ammonium sulfonato phthalocyanine of formula (II) or mixture thereof is from 1:1 to 5:1.

3. A process according to claim 1 , wherein the ratio of α copper phthalocyanine to ε copper phthalocyanine at the beginning of wet-milling is from 1:4 to 20:1.

4. A process according to claim 1 , wherein the wet-milling step is performed in an agitated media pearl mill with an insoluble inert solid material or in a kneader with a crystalline organic compound or inorganic salt.

5. A process according to claim 4 , wherein the temperature during kneading is from 10 to 180° C.

6. A process according to claim 1 , wherein the ammonium sulfonato phthalocyanine of formula (II) is added before the end of the wet-milling.

7. A process according to claim 1 , wherein in formula I

M 1 is 2 H, Co, Cu or Ni;

R 4 and R 5 are both H or both methyl;

and in formula II

M 2 is 2 H, Co, Cu or Ni;

R 8 and R 9 are each independently of one another H or methyl; and

R 11 is C 8 -C 20 alkyl or C 8 -C 20 alkenyl.

8. A process according to claim 7 , wherein the ratio of α copper phthalocyanine to ε copper phthalocyanine at the beginning of wet-milling is from 1:4 to 20:1.

9. A process according to claim 1 , wherein the wet-milling step is performed in a kneader with an inorganic salt.

10. A pigment composition comprising, by weight based on the total content of components having a phthalocyanine core,

a from 70 to 93% of ε copper phthalocyanine;

from 5 to 18% of aminomethyl-substituted phthalocyanine of formula (I) or mixture thereof,

wherein M 1 is 2 H, Al(Cl), Al(OH), Bi(OH), Ca, Cd, Ce(Cl), Cr(OH), Co, Cu, Mn, Fe, Fe(Cl), Fe(OH), In(Cl), Mg, Mn(O), Ni, Os, Pb, Pd, Pt, Re, Rh, Rh(O), Ru, Si(Cl) 2 , Si(OC 1 -C 5 alkyl) 2 , Si(OH) 2 , Sn, Sr, Ti(O), V(O), Zn, Zr(O) or (OH) 2 ;

R 1 is

R 2 is

 C 1 -C 20 alkyl, C 2 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 1-3 H, [C 2 -C 6 alkylen-O—] 1-3 C 1 -C 8 alkyl, [C 2 -C 6 alkylen-NH—] 1-3 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 1-3 C 1 C 8 alkyl;

R 3 is H, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 1-3 H, [C 2 -C 6 alkylen-O—] 1-3 C 1 C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 1-3 C 1 -C 8 alkyl;

R 4 and R 5 are independently from one another H or C 1 -C 6 alkyl;

each R 6 is independently from all others H, C 1 -C 8 alkyl, Cl or NO 2 ; and

R 7 is H, COOH, CONH 2 , CONHC 1 -C 8 alkyl or CON(C 1 -C 8 alkyl) 2 ;

from 2 to 15% of ammonium sulfonato phthalocyanine of formula (II) or mixture thereof

wherein M 2 is 2 H, Al(Cl), Al(OH), Bi(OH), Ca, Cd, Ce(Cl), Cr(OH), Co, Cu, Mn, Fe, Fe(Cl), Fe(OH), In(Cl), Mg, Mn(O), Ni, Os, Pb, Pd, Pt, Re, Rh, Rh(O), Ru, Si(Cl) 2 , Si(OC 1 -C 5 alkyl) 2 , Si(OH) 2 , Sn, Sr, Ti(O), V(O), Zn, Zr(O) or Zr(O) 2 ;

R 8 and R 9 are each independently of one another H or C 1 -C 4 alkyl;

R 10 is H, phenyl, benzyl, 2-phenylethyl, naphthyl, C 1 -C 20 alkyl, C 8 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 1-6 H, [C 2 -C 6 alkylen-O—] 1-6 C 1 -C 8 alkyl, [C 2 -C 6 alkylen-NH—] 1-6 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 1-6 C 1 -C 8 alkyl; and

R 11 is C 8 -C 20 alkyl, C 8 -C 20 alkenyl, [C 2 -C 6 alkylen-O—] 3-6 H, [C 2 -C 6 alkylen-O—] 3-6 C 1 -C 8 alkyl, [C 2 -C 6 alkylen-NH—] 3-6 C 1 -C 8 alkyl or [C 2 -C 6 alkylen-N(C 1 -C 4 alkyl)-] 3-6 C 1 -C 8 alkyl;

with the proviso that the total number of carbon atoms in R 8 , R 9 , R 10 and R 11 is from 8 to 30; and

from 0 to 2% of other phthalocyanine compounds.

11. A pigment composition according to claim 10 , which has a specific surface area of from 50 to 110 m 2 /g, as determined by the BET method.

12. A composition according to claim 10 further comprising an organic material having a molecular weight in the range of 10 3 to 10 8 g/mol.

13. A composition comprising from 0.1 to 70% by weight of the phthalocyanine pigment composition according to claim 10 and a liquid medium comprising a binder or a polymerisable compound.

14. A pigment composition according to claim 10 , which has a specific surface area of from 80 to 110 m 2/ g.

15. A colour filter comprising a transparent substrate and one layer or multiple layers thereon, wherein at least one layer comprises from 1 to 75% by weight of the phthalocyanine pigment composition according to claim 10 based on the overall weight of the layer.