Black colorant mixture

1. A colorant mixture comprising

(a) a bis-oxodihydro-indolylene-benzodifuranone colorant of formula

or an isomer or tautomer or a mixture thereof, wherein

R 1 and R 2 are independently of each other H, CH 3 , CF 3 , F or Cl;

R 3 and R 7 are independently of each other H, F, Cl, R 13 or OR 13 ;

R 4 , R 5 , R 6 , R 8 , R 9 and R 10 are independently of each other H, F, Cl, Br, COOH, COOR 13 , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, COR 13 , SO 3 H, SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14 , SO 2 R 13 , NO 2 ,

R 13 , OR 13 , SR 13 , NR 13 R 14 , NHCOR 13 or

 or

R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , R 7 and R 8 , R 8 and R 9 , and/or R 9 and R 10 together form a C 1 -C 6 -alkylenedioxy, C 3 -C 6 -alkylene, C 3 -C 6 -alkenylene or 1,4-butadienylene radical, each of which is unsubstituted, mono- or polysubstituted by F, OR 13 , NO 2 , oxo, thioxo or SO 3 H;

R 11 and R 12 are independently from each other H;

C 1 -C 18 -alkyl, C 3 -C 18 -cycloalkyl, C 3 -C 18 -alkenyl, C 3 -C 18 -cycloalkenyl, C 3 -C 18 -alkynyl or C 2 -C 12 -heterocycloalkyl, each of which is unsubstituted, mono- or polysubstituted by F, oxo or thioxo and uninterrupted or interrupted one or more times by O, S or NR 13 ; or

is C 7 -C 18 -aralkyl, C 1 -C 12 -heteroaryl-C 1 -C 8 -alkyl, C 6 -C 18 -aryl or C 1 -C 12 -heteroaryl, each of which is unsubstituted, mono- or polysubstituted by oxo, thioxo, F, Cl, Br, COOH, COOR 13 , CONH 2 , CONHR 13 , CONR 13 R 14 , CN, COR 13 , SO 3 H, SO 2 NH 2 , SO 2 NHR 13 , SO 2 NR 13 R 14 , SO 2 R 13 , NO 2 ,

R 13 , OR 13 , SR 13 , NR 13 R 14 , NHCOR 13 or

R 13 and R 14 are independently of each other C 1 -C 18 -alkyl, C 3 -C 18 -cycloalkyl, C 3 -C 18 -alkenyl, C 3 -C 18 -cycloalkenyl, C 3 -C 18 -alkynyl or C 2 -C 12 -heterocycloalkyl, each of which is unsubstituted, mono- or polysubstituted by F, oxo, thioxo, OR 15 , SR 15 or NR 15 R 16 ; or

is C 7 -C 18 -aralkyl, C 1 -C 12 -heteroaryl-C 1 -C 8 -alkyl, C 6 -C 18 aryl or C 1 -C 12 -heteroaryl, each of which is unsubstituted, mono—or polysubstituted by oxo, F, Cl, Br, COOH, CONH 2 , CONHR 15 , CONR 15 R 16 , SO 3 H, SO 2 NH 2 , SO 2 NHR 15 , SO 2 NR 15 R 16 , SO 2 R 15 , CN, NO 2 , OR 15 , SR 15 , NR 15 R 16 , NHCOR 15 or

or two vicinal radicals of R 13 and/or R 14 together form —O—CO—O—, —O—CS—O—, —CO—NCO—, —N—CO—N—, —N═S═N—, —N—C═C—, —O—C═C—, —S—C═C—, —O—C═N—, —S—C═N—, —N—N═N—, —N═C—C═C—, —C═N—C═C—, —N═C—C═N—, —C═N—N═C—, —C═N—C═N— or —C═C—C═C—, in which —C═ and —N— are independently of each other substituted by H or R 15 ;

or two geminal or vicinal radicals of R 13 and/or R 14 together form a C 3 -C 8 -alkylene or C 3 -C 8 -alkenylene radical, each of which is unsubstituted, mono- or polysubstituted by F, oxo or thioxo, and in which 0, 1 or 2 non-vicinal methylene units are be replaced by O, S or NR 15 ;

R 15 and R 16 are independently of each other C 1 -C 8 -alkyl, C 3 -C 6 -cycloalkyl or benzyl, each of which is unsubstituted, mono- or polysubstituted by oxo, thioxo, F or C 1 -C 8 -alkoxy; or is phenyl or C 1 -C 5 -heteroaryl, each of which is unsubstituted, mono or polysubstituted by F, Cl, Br, CO-C 1 -C 8 -alkyl, COOH, CONH 2 , CONHC 1 -C 8 -alkyl, CON(C 1 -C 8 -alkyl) 2 , SO 3 H, SO 2 NH 2 , SO 2 NHC 1 -C 8 -alkyl, SO 2 N(C 1 -C 8 -alkyl) 2 , CN, NO 2 , C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, C 1 -C 8 -thioalkoxy or N(C 1 -C 8 -alkyl) 2 ;

or two vicinal radicals of R 15 and/or R 16 together form —O—CO—O—, —O—CS—O—, —CO—N—CO—, —N—CO—N—, N═S═N—, —N—C═C—, —O—C═C—, —S—C═C—, —O—C═N—, —S—C═N—, —N—N═N—, —N═C—C═C—, —C═N—C═C—, —N═C—C═N—, —C═N—N═C—, —C═N—C═N— or —C═C—C═C—, in which —C═ and —N— are independently of each other substituted by H, F, C 1 -C 8 -alkyl or C 1 -C 8 -alkoxy;

or two geminal or vicinal radicals of R 15 and/or R 16 together form a C 3 -C 8 -alkylene or C 3 -C 8 -alkenylene radical, each of which is unsubstituted, mono- or polysubstituted by oxo or thioxo, and in which 0, 1 or 2 non-vicinal methylene units are replaced by O, S or N(C 1 -C 8 -alkyl); and

(b) a perylene colorant of formula

or a mixture thereof, wherein

R′ 7 and R 18 are independently of each other phenylene, naphthylene or pyridylene, each of which is unsubstituted, mono- or polysubstituted by C 1 -C 18 alkyl, C 1 -C 18 alkoxy, OH, NO 2 , F, Cl, or Br;

X is F, Cl, or Br; and

n is 0, 1, 2, 3 or 4.

2. The colorant mixture according to claim 1 , wherein in the (a) bis-oxodihydro-indolylene-benzodifuranone colorant of formula (I),

R 1 , R 2 , R 3 , and R 7 are H;

R 4 and R 8 are independently of each other H, F, Cl, Br, COOH, CN, SO 3 H, NO 2 , R 13 , OR 13 , NR 13 R 14 , NHCOR 13 ;

R 5 and R 9 are independently of each other H, NO 2 , CN, COOH or SO 3 H;

R 6 and R 10 are independently of each other H, F, Cl, R 13 , OR' 3 ; or

R 5 and R 6 , and/or R 9 and R 10 together form a 1,4-butadienylene radical;

R 11 and R 12 are H; and

R 13 and R 14 are independently of each other C 1 -C 12 -alkyl, each of which is unsubstituted, mono- or polysubstituted by F; or

two geminal radicals of R 13 and R 14 together form a C 5 -C 7 -alkylene radical, each of which is unsubstituted, mono- or polysubstituted by F; and

(b) the perylene colorant is a pigment of formula (II) or (III) or a mixture thereof, wherein

R 17 and R 18 are independently of each other phenylene or naphthylene, each of which is unsubstituted, mono- or polysubstituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, OH, NO 2 , Cl or Br;

and n is 0.

3. A color filter comprising pixels composed of at least three colors and a black matrix, wherein said black matrix separating the pixels contains the colorant mixture of claim 2 .

4. A liquid crystal display device, an organic light emitting diode display device or an e-paper display device containing the color filter of claim 3 .

5. A liquid crystal display device comprising a black column spacer, which column spacer contains the colorant mixture of claim 2 .

6. The colorant mixture according to claim 1 , wherein

(a) the bis-oxodihydro-indolylene-benzodifuranone colorant is a pigment of formula

 and

in (b) the perylene colorant is a pigment of foimula (II) or (III) or a mixture thereof, R 17 and R 18 are the same and are each unsubstituted phenylene or naphthylene; and n is 0.

7. The colorant mixture according to claim 1 , wherein the ratio of colorant (a) to colorant (b) is of from 80:20 to 10:90 by weight.

8. The colorant mixture according to claim 1 , wherein

(c) at least one further colorant is present in an amount of ≦50% by weight, based on the total weight of the colorant mixture (a) and (b),

with the proviso that the amount for carbon black as a colorant is ≦30% by weight.

9. The colorant mixture according to claim 1 , wherein

(d) a polymeric dispersant is present in an amount of ≦40% by weight, and

(e) a pigment derivative is present in an amount of ≦25% by weight, based on the total weight of the colorants (a), (b) and (c), if present.

10. A composition comprising

(A) the colorant mixture as defined in claim 1 , and

(B) a high molecular weight organic material.

11. A photosensitive resist formulation comprising the composition according to claim 10 and further comprising

(B) a binder,

(C) an ethylenically unsaturated monomer, and

(D) optionally a photoinitiator.

12. A coating film formed by curing the photosensitive resist formulation as defined in claim 11 , which film is a black matrix for a color filter or a black column spacer in a liquid crystal display device.

13. A color filter comprising pixels composed of at least three colors and a black matrix, wherein said black matrix separating the pixels contains the coating film of claim 12 .

14. A liquid crystal display device, an organic light emitting diode display device or an e-paper display device containing the color filter of claim 13 .

15. A liquid crystal display device comprising a black column spacer, which column spacer contains the coating film of claim 12 .

16. The photosensitive resist formulation according to claim 11 , wherein the binder is an alkali soluble resin.

17. A coating film formed by curing the photosensitive resist formulation as defined in claim 16 , which film is a black matrix for a color filter or a black column spacer in a liquid crystal display device.

18. A display device equipped with a touch sensor, wherein a bezel of the device contains the colorant mixture of claim 1 .