Red-shifted water dispersible napthalocyanine dyes
A naphthalocyanine dye of formula (I) is provided: wherein M is a metal group or is absent; R 1 and R 2 are independently selected from hydrogen or C 1-12 alkoxy; X is selected from O, S or —NH—; Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 are selected from phenyl, naphthyl, pyridyl, furanyl, pyrollyl, thiophenyl, each of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 being optionally substituted with 1, 2, 3, 4 or 5 groups, the or each group being independently selected from C 1-12 alkyl, C 1-12 alkoxy, C 1-12 arylalkyl, C 1-12 arylalkoxy, —(OCH 2 CH 2 ) d OR d , cyano, halogen, amino, hydroxyl, thiol, —SR v , —NR u R v , nitro, phenyl, phenoxy, —CO 2 R v , —C(O)R v , —OCOR v , —SO 2 R v , —OSO 2 R v , —NHC(O)R v , —CONR u R v , —CONR u R v , sulfonic acid, sulfonic acid salt and sulfonamide; d is an integer from 2 to 5000; R d is H, C 1-8 alkyl or C(O)C 1-8 alkyl; and R u and R v are independently selected from hydrogen, C 1-12 alkyl, phenyl or phenyl-C 1-8 alkyl.
1. A naphthalocyanine dye of formula (I):
wherein
M is a metal group or is absent;
R 1 and R 2 are independently selected from the group consisting of: hydrogen and C 1-12 alkoxy;
X is selected from the group consisting of: O, S and —NH—;
Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 are selected from the group consisting of: phenyl, naphthyl, pyridyl, furanyl, pyrollyl and thiophenyl, each of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 being optionally substituted with 1, 2, 3, 4 or 5 groups, each group being independently selected from the group consisting of: C 1-12 alkyl, C 1-12 alkoxy, C 1-12 arylalkyl, C 1-12 arylalkoxy, —(OCH 2 CH 2 ) d OR d , cyano, halogen, amino, hydroxyl, thiol, —SR v , —NR u R v , nitro, phenyl, phenoxy, —CO 2 R v , —C(O)R v , —OCOR v , —SO 2 R v , —OSO 2 R v , —NHC(O)R v , —CONR u R v , —CONR u R v , sulfonic acid, sulfonic acid salt and sulfonamide;
d is an integer from 2 to 5000;
R d is H, C 1-8 alkyl or C(O)C 1-8 alkyl; and
R u and R v are independently selected from the group consisting of: hydrogen, C 1-12 alkyl, phenyl or phenyl-C 1-8 alkyl;
and wherein at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 is substituted with a sulfonic acid or a sulfonic acid salt.
2. The dye of claim 1 , wherein at least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 is substituted with —SO 3 Z;
wherein:
Z is H, Li, Na, K or N + (R m )(R n )(R s )(R t ); and
R m , R n , R s , R t may be the same or different and are independently selected from the group consisting of: H, C 1-8 alkyl, C 6-12 arylalkyl and C 6-12 aryl.
3. The dye of claim 1 , wherein each of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 and Ar 8 is substituted with a sulfonic acid or a sulfonic acid salt.
4. The dye of claim 3 , which is of formula (III):
wherein:
Z is H, Li, Na, K or N + (R m )(R n )(R s )(R t ); and
R m , R n , R s , R t may be the same or different and are independently selected from the group consisting of: H, C 1-8 alkyl, C 6-12 arylalkyl and C 6-12 aryl.
5. The dye of claim 4 , wherein each —SO 3 Z group is at a para position.
6. The dye of claim 1 , which is of formula (IV[d2]):
wherein:
Z is H, Li, Na, K or N + (R m )(R n )(R s )(R t );
R m , R n , R s , R t may be the same or different and are independently selected from the group consisting of: H, C 1-8 alkyl, C 6-12 arylalkyl and C 6-12 aryl; and
R 3 is selected from the group consisting of: C 1-12 alkyl, C 1-12 alkoxy, C 1-12 arylalkyl, Cr 1-12 arylalkoxy, —(OCH 2 CH 2 ) d OR d , cyano, halogen, amino, hydroxyl, thiol, —SR v , —NR u R v , nitro, phenyl, phenoxy, —CO 2 R v , —C(O)R v , —OCOR v , —NHC(O)R v , —CONR u R v and —CONR u R v .
7. The dye of claim 6 , wherein R 3 is C 1-6 alkyl or C 1-6 alkoxy.
8. The dye of claim 1 , wherein M is SnCl 2 , Cu, V═O, or Ga(OH).
9. An inkjet ink comprising a dye according to claim 1 .