1:1 and 1:2 metal complexes of sulfo group-free azo compound having on average at least 1.3 basic water-solubilizing groups

Claim 2

A metal complex which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR197## (ii) a 1:2 metal complex of two dyes of said formula or (iii) a 1:2 metal complex of a dye of said formula and a further metallizable compound, wherein each A 1 is independently --OH or --NH 2 , each A 2 is independently --OH or --NH 2 , each A 3 is independently hydrogen or --OH, with the proviso that when c is 1, A 3 is --OH, and when c is 2, at least one A 3 is --OH, each D is independently a diazo component radical, each R 2 is independently hydrogen, nitro, --SO 2 NH 2 , --OH --SO 2 NHR 1 , --SO 2 NR 6 R 6a , --SO 2 --NH--(CH 2 ) p --Z 2 , --NH 2 , C 1-4 alkyl or C 1-4 alkoxy, wherein R 1 is C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --N(R 1a ) 2 , wherein each R 1a is independently propyl or butyl, R 6 is C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --N(R 6 ') 2 , wherein each R 6 ' is independently C 1-4 alkyl, R 6a is C 1-4 alkyl, 2-hydroxyethyl, --(CH 2 ) p --N(R 6 ') 2 or --CH 2 CH 2 --O--R 6 ', wherein R 6 ' is as defined above, each R 3 is independently hydrogen, nitro, --SO 2 NH 2 , --SO 2 NHR 1 , --SO 2 NR 6 R 6a , C 1-4 alkyl, C 1-4 alkoxy, ##STR198## --N═N--K 1 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 or --CH 2 --Z 2 , wherein K 1 is ##STR199## wherein R 9 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , R 10 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, acetamido or ureido, R 25 is C 1-4 alkyl, (C 1-4 alkoxy)carbonyl or carboxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 124 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , R 125 is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR200## wherein R 126 is hydrogen, --OH, C 1-4 alkoxy, --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --(CH 2 ) p --Z 2 or ##STR201## and R 151 is hydrogen or --(CH 2 ) p --Z 2 , each Wa is independently --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s *, wherein s is 1, 2, 3, 4, 5 or 6, and the asterisked end is bound to the nitrogen atom of the Z 2 group, Y a is hydrogen, C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , Y a ' is C 1-4 alkyl, and m is 0, 1 or 2, R 5 is hydrogen, C 1-4 alkyl or C 1-4 alkoxy, R 5 ' is C 1-4 alkyl, R 7 is hydrogen, --OH, C 1-4 alkyl, C 1-4 alkoxy, acetamido or ureido, R 8 is hydrogen, --NH--CO--(CH 2 ) p --Z 2 or ##STR202## n o is 1, 2 or an average between 1 and 2, each --CH 2 --Z 2 group attached to a benzothiazolylphenyl group is independently attached to ring J or ring K, and R 1 , R 6 and R 6a are as defined above, each R 100 is independently hydrogen, halo, hydroxy, C 1-4 alkyl, C 1-4 alkoxy or ureido, with the proviso that when a ring B' does not contain an R t " group, the R 100 on the adjacent ring C' must be hydrogen, each R t " is independently ##STR203## wherein R 4 is hydrogen, nitro, C 1-4 alkyl or C 1-4 alkoxy, each --CH 2 --Z 2 group attached to a benzothiazolylphenyl group is independently attached to ring J or ring K, and R 2 , R 3 , R 5 and n o are as defined above, each W is independently a direct bond or a bridging radical, X' is a direct bond, straight or branched C 1-4 alkylene, ##STR204## wherein R 11 is halo, C 1-4 alkyl or C 1-4 alkoxy, each R 12 is independently hydrogen or C 1-4 alkyl, R 13 is halo, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , R 14 is straight or branched C 1-4 alkylene, and each q is independently 1, 2, 3 or 4, each a is independently 1 or 2, each b is independently 1, 2 or an average between 1 and 2, both c's are 1 or 2, and each d' is independently 0 or 1, wherein each Z 2 is independently --NH 2 , --N(R o ) 2 , --N.sup.⊕ (R o ) 3 A.sup.⊖, ##STR205## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the provisos that (i) the dye of formula II' contains an average of at least 1.3 basic water-solubilizing groups, (ii) the dye of formula II' is free of sulfo groups, (iii) when c is 2, X' is not attached directly to a ring B' bearing an R t " group, (iv) when c is 2 and a ring B' bears a group of formula αα, X' is directly attached to said group of formula αα or to the ring C' linked to said ring B' through a --N═N-- radical, (v) each --N═N-- radical attached to a ring B' is ortho to at least one of A 1 and A 2 , (vi) when an A 1 and an A 3 form a metal-containing radical, said A 3 -bearing phenylazo group is ortho to said A 1 , (vii) the negative charge on the complexed metal ion of each 1:2 metal complex is balanced by hydrogen or a non-chromophoric cation, (viii) when the dye of formula II' is in 1:2 metal complex form with another metallizable compound, the other metallizable compound of the 1:2 metal complex also contains an average of at least 1.3 basic water-solubilizing groups, and (ix) when X' is attached to a ring C', at least one of R 2 , R 3 and R 100 on that ring is hydrogen.

Claim 3

A metal complex according to claim 1 which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR206## or (ii) a 1:2 metal complex of two dyes of said formula, wherein each [(Z 2 ) a --W] b --D-- is independently ##STR207## wherein R 15 is hydrogen, hydroxy, methyl, methoxy or chloro, R 16 is hydrogen or methyl, each Z 2 is independently ##STR208## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, A.sup.⊖ is a non-chromophoric anion, m is 0, 1 or 2, and p is 1, 2 or 3, n o ' is 1, 2 or an average between 1.0 and 1.7, each q o is independently 2, 3, 4 or 5, and each --CH 2 --Z 2 group attached to a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, with the proviso that the dye of formula II' contains at least two basic water-solubilizing groups.

Claim 4

A 1:1 metal complex according to claim 1 having the formula ##STR209## wherein A 1 ' is --O-- or --NH--, A 2 is --OH or --NH 2 , R 2a is hydrogen, nitro, --SO 2 NH 2 , --SO 2 NH--CH 3 , --SO 2 N(CH 3 ) 2 , --SO 2 --N(CH 3 )--CH 2 CH 2 --O--CH 3 , --SO 2 NH--CH 2 CH 2 OH, --SO 2 N(CH 2 CH 2 OH) 2 , --SO 2 N(CH 2 CH 2 --N(CH 3 ) 2 ) 2 or --SO 2 NH--(CH 2l ) 3 --Z 2 , R 3a is hydrogen, nitro, methyl, methoxy, --SO 2 NH 2 , --SO 2 NH--CH 3 , --SO 2 N(CH 3 ) 2 , --SO 2 --N(CH 3 )--CH 2 CH 2 OH, --SO 2 NH--CH 2 CH 2 OH, --SO 2 N(CH 2 CH 2 OH) 2 , --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 NH--(CH 2 ) p --Z 2 , --CH 2 --Z 2 , ##STR210## wherein K 1 ' is ##STR211## wherein R 9 ' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 9a is methyl, ethyl or C 2 H 4 --Z 2 , R 10a is hydrogen, methyl, methoxy, acetamido or ureido, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) 2 *, --CONH--(CH 2 ) s *-- or --SO 2 NH--(CH 2 ) s *--, wherein s is 1, 2, 3, 4, 5 or 6, and the asterisk indicates the end attached to the Z 2 group, and m is 0, 1 or 2, R 7a is hydrogen, hydroxy, methyl, methoxy, acetamido or ureido, R 8a is hydrogen, --NHCO--(CH 2 ) p --Z 2 or ##STR212## n o ' is 1, 2 or an average between 1 and 1.7, and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached tp ring J or ring K, R t "' is ##STR213## wherein R 4a is hydrogen, nitro, methyl or methoxy, R 2a , R 3a and n o ' are as defined above, and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, (Z 2 ) a --D 1 -- is ##STR214## wherein R 15 is hydrogen, hydroxy, methoxy, methyl or chloro, R 16 is hydrogen or methyl, n o ' is 1, 2 or an average between 1.0 and 1.7, each q o is independently 2, 3, 4 or 5 and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, and Me a is copper, cobalt, iron or chromium, and d' is 0 or 1, wherein each Z 2 is independently ##STR215## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the provisos that (i) the metal complex of formula IId contains an average of at least 1.3 basic water-solubilizing groups, and (ii) the R 2a -bearing phenylazo group is ortho to A 1 '.

Claim 5

A 1:1 metal complex according to claim 1 having the formula ##STR216## wherein each A 1 ' is independently --O-- or --NH--, each A 2 is independently --OH or --NH 2 , each R t iv is independently ##STR217## wherein R 2d is hydrogen, hydroxy, methyl or methoxy, R 3a is hydrogen, nitro, methyl, methoxy, --SO 2 NH 2 , --SO 2 NH--CH 3 , --SO 2 N(CH 3 ) 2 , --SO 2 --N(CH 3 )--CH 2 CH 2 OH, --SO 2 NH--CH 2 CH 2 OH, --SO 2 N(CH 2 CH 2 OH) 2 , --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 NH--(CH 2 ) p --Z 2 , --CH 2 --Z 2 , ##STR218## wherein K 1 ' is ##STR219## wherein R 9 ' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 9a is methyl, ethyl, or --C 2 H, R 10a is hydrogen, methyl, methoxy, acetamido or ureido, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s *--, --CONH--(CH 2 ) s *-- or --SO 2 NH--(CH 2 ) s *--, wherein s is 1, 2, 3, 4, 5 or 6, and the asterisk indicates the end attached to the Z 2 group, and m is 0, 1 or 2, R 7a is hydrogen, hydroxy, methyl, methoxy, acetamido or ureido, R 8a is hydrogen, --NHCO--(CH 2 ) p --Z 2 or ##STR220## n o ' is 1, 2 or an average between 1 and 1.7, and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, and R 4a is hydrogen, nitro, methyl or methoxy, n o ' is 1, 2 or an average between 1 and 1.7, and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, X a is a direct bond, ##STR221## wherein R 13a is chloro, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , and q is 1, 2, 3 or 4, each (Z 2 ) a --D 1 is independently ##STR222## wherein R 15 is hydrogen, hydroxy, methoxy, methyl or chloro, R 16 is hydrogen or methyl, n o ' is 1, 2 or an average between 1.0 and 1.7, each q o is independently 2, 3, 4, or 5 and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, each Me a independently is copper, cobalt, iron, or chromium, and each d' independently is 0 or 1, wherein each Z 2 is independently ##STR223## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, each p is independently 1, 2 or 3, with the provisos that (i) the metal complex of formula IIf contains an average of at least 1.3 basic water-solubilizing groups, and (ii) each X a -bearing phenylazo group is ortho to A 1 '.

Claim 6

A 1:1 metal complex according to claim 1 having the formula ##STR224## wherein each A 1 ' is independently --O-- or --NH--, each A 2 is independently --OH or --NH 2 , each R 3a is independently hydrogen, nitro, methyl, methoxy, --SO 2 NH 2 , --SO 2 NH--CH 3 , --SO 2 N(CH 3 ) 2 , --SO 2 --N(CH 3 )--CH 2 CH 2 OH, --SO 2 NH--CH 2 CH 2 OH, --SO 2 N(CH 2 CH 2 OH) 2 , --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 NH--(CH 2 ) p --Z 2 , --CH 2 --Z 2 , ##STR225## wherein K 1 ' is ##STR226## wherein R 9 ' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 9a is methyl, ethyl or --C 2 H 4 --Z 2 , R 10a is hydrogen, methyl, methoxy, acetamido or ureido, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s *--, --CONH--(CH 2 ) s *-- or --SO 2 NH--(CH 2 ) s *--, wherein s is 1,2,3,4,5 or 6, the asterisk indicates the end attached to the Z 2 group, and m is 0, 1 or 2, R 7a is hydrogen, hydroxy, methyl, methoxy, acetamido or uredio, R 8a is hydrogen, --NHCO--(CH 2 ) p --Z 2 or ##STR227## n o ' is 1, 2 or an average between 1 and 1.7, and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, each R 4a is independently hydrogen, nitro, methyl or methoxy, each R 70 is independently hydrogen, methyl or methoxy, X a is a direct bond, ##STR228## wherein R 13a is chloro, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , and q is 1, 2, 3 or 4, each (Z 2 ) a --D 1 -- is independently ##STR229## wherein R 15 is hydrogen, hydroxy, methoxy, methyl or chloro, R 16 is hydrogen or methyl, n o ' is 1, 2 or an average between 1.0 and 1.7, each q o is independently 2, 3, 4 or 5 and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, and each Me a is independently copper, cobalt, iron or chromium, wherein each Z 2 is independently ##STR230## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the provisos that (i) the metal complex contains an average of at least 1.3 basic water-solubilizing groups, and (ii) each R 3a -bearing phenylazo group is ortho to A 1 '.

Claim 7

A 1:2 metal complex according to claim 1 having the formula ##STR231## wherein each A 1 ' is independently --O-- or --NH--, A 2 is --OH or --NH 2 , each R 2a is independently hydrogen, nitro, --SO 2 NH 2 , --SO 2 NH--CH 3 , --SO 2 N(CH 3 ) 2 , --SO 2 --N(CH 3 )--CH 2 CH 2 --O--CH 3 , --SO 2 NH--CH 2 CH 2 OH, --SO 2 N(CH 2 CH 2 OH) 2 , --SO 2 N(CH 2 CH 2 --N(CH 3 ) 2 ) 2 or --SO 2 NH--(CH 2 ) 3 --Z 2 , R 2a ' is --OH, --NH 2 or R 2a , wherein R 2a is as defined above, each R 3a is independently hydrogen, nitro, methyl, methoxy, --SO 2 NH 2 , --SO 2 NH--CH 3 , --SO 2 N(CH 3 ) 2 , --SO 2 --N(CH 3 )--CH 2 CH 2 OH, --SO 2 NH--CH 2 CH 2 OH, --SO 2 N(CH 2 CH 2 OH) 2 , --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 NH--(CH 2 ) p --Z 2 , --CH 2 --Z 2 , ##STR232## wherein K 1 ' is ##STR233## wherein R 9a is methyl, ethyl or --C 2 H 4 --Z 2 , R 10a is hydrogen, methyl, methoxy, acetamido or ureido, and R 9 ', R 26 and Wa are as defined below, R 7a is hydrogen, hydroxy, methyl, methoxy, acetamido or ureido, R 8a is hydrogen, --NHCO--(CH 2 ) p --Z 2 or ##STR234## n o ' is 1, 2 or an average between 1 and 1.7, and each --CH 2 --Z 2 group on a methylbenzothiazolylphenyl group is independently attached to ring J or ring K, R 9 ' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 25 is C 1-4 alkyl, (C 1-4 alkoxy)carbonyl or --COOH, R 40 is hydrogen or (Z 2 ) a --D 1 --N═N--, wherein (Z 2 ) a --D 1 -- is as defined below, R 42 is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR235## wherein R 44 is hydrogen, --OH, C 1-4 alkoxy, --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , ##STR236## ps or --(CH 2 ) p --Z 2 , and R 45 is hydrogen or --(CH 2 ) p --Z 2 , R 43 is methyl, ethyl or --(CH 2 ) p --Z 2 , each R t " is independently ##STR237## wherein R 2 is hydrogen, nitro, --SO 2 NH 2 , --OH, --SO 2 NHR 1 , --SO 2 NR 6 R 6a , --SO 2 --NH--(CH 2 ) p --Z 2 , --NH 2 , C 1-4 alkyl or C 1-4 alkoxy, wherein R 1 is C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --N(R 1a ) 2 , wherein each R 1a is independently propyl or butyl, R 6 is C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --N(R 6 ') 2 , wherein each R 6 ' is independently C 1-4 alkyl, and R 6a is C 1-4 alkyl, 2-hydroxyethyl, --(CH 2 ) p --N(R 6 ') 2 or --CH 2 CH 2 --O--R 6 ', wherein R 6 ' is as defined above, R 3 is hydrogen, nitro, --SO 2 NH 2 , --SO 2 NHR 1 , --SO 2 NR 6 R 6a , C 1-4 alkyl, C 1-4 alkoxy, ##STR238## --N═N--K 1 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 or --CH 2 --Z 2 , wherein K 1 is ##STR239## wherein R 9 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , R 10 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, acetamido or ureido, R 25 is C 1-4 alkyl, (C 1-4 alkoxy)-- carbonyl or carboxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 124 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , R 125 is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR240## wherein R 126 is hydrogen, --OH, C 1-4 alkoxy, --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --(CH 2 ) p --Z 2 or ##STR241## and R 151 is hydrogen of --(CH 2 ) p --Z 2 , Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s *--, --CONH--(CH 2 ) s *-- or --SO 2 NH--(CH 2 ) s *--, wherein s is 1, 2, 3, 4, 5 or 6, and the asterisked end is bound to the nitrogen atom of the Z 2 group, Y a is hydrogen, C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , and Y a ' is C 1-4 alkyl, R 5 is hydrogen, C 1-4 alkyl or C 1-4 alkoxy, R 5 ' is C 1-4 alkyl, R 7 is hydrogen, --OH, C 1-4 alkyl, C 1-4 alkoxy, acetamido or ureido, R 8 is hydrogen, --NH--CO--(CH 2 ) p --Z 2 or ##STR242## n o is 1, 2 or an average between 1 and 2, each --CH 2 --Z 2 group on a benzothiazolylphenyl group is independently attached to ring J or ring K, and R 1 , R 6 and R 6a are as defined above, R 4 is hydrogen, nitro, C 1-4 alkyl or C 1-4 alkoxy, R 5 and n o are as defined above, and each --CH 2 --Z 2 group on a benzothiazolylphenyl group is independently attached to ring J or ring K, (Z 2 ) a --D 1 -- is ##STR243## wherein R 15 is hydrogen, hydroxy, methoxy, methyl or chloro, R 16 is hydrogen or methyl, n o ' is 1, 2 or an average between 1.0 and 1.7, and each q o is independently 2, 3, 4 or 5, Me g is cobalt, iron or chromium, and M.sup.⊕ is hydrogen or a monovalent non-chromophoric cation, wherein each Z 2 is independently ##STR244## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, and each R 127 is independently methyl or ethyl, each A.sup.⊖ is independently a non-chromophoric anion, each d' is independently 0 or 1, each m is independently 0, 1 or 2, and each p is independently 1, 2 or 3, with the provisos that (i) each metal-free azo compound of the 1:2 metal complex contains an average of at least 1.3 basic water-solubilizing groups, (ii) each --N═N-- radical on ring T is ortho or para to an --OH or --NH 2 group or to A 1 ' and meta to every other --N═N-- radical on said ring, (iii) the maximum number of --N═N-- radicals on ring T is 3, and (iv) each R.sub. 2a -bearing phenylazo group attached to an A 1 '-bearing ring is ortho to A 1 '.

Claim 8

A metal complex according to claim 6 wherein each metal-free compound of the 1:2 metal complex contains at least 2 basic water-solubilizing groups.

Claim 9

A metal complex according to claim 7 having the formula ##STR245##

Claim 10

A metal complex according to claim 7 having the formula ##STR246##

Claim 11

A metal complex according to claim 7 having the formula ##STR247##

Claim 12

A metal complex according to claim 7 having the formula ##STR248##

Claim 13

A metal complex which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR249## (ii) a 1:2 metal complex of two dyes of said formula or (iii) a 1:2 metal complex of a dye of said formula and a further metallizable compound, wherein A 4 is --OH, --NH 2 , --COOH or C 1-4 alkoxy, K 2 is ##STR250## wherein R 24 is hydrogen, C 1-4 alkyl, 2-hydroxyethyl, --(CH 2 ) p --Z 2 , benzyl, --N(R 30 ) 2 , --(CH 2 ) 3 --OCH 3 , --CH 2 --CH(CH 3 )--N(R 30 ) 2 or --CH 2 --C(CH 3 ) 2 --CH 2 --N(R 30 ) 2 , wherein each R 30 is independently hydrogen or C 1-4 alkyl, R 24a is C 1-4 alkyl, R 25 is C 1-4 alkyl, (C 1-4 alkoxy)carbonyl or carboxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 28 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 29 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, halo, --NH--(CH 2 ) s --Z 2 or --NHCH 2 CH 2 OH, R 32 is hydrogen, ##STR251## wherein R 5 is hydrogen, C 1-4 alkyl or C 1-4 alkoxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 33 is hydrogen, halo, C 1-4 alkyl, C 1-4 alkoxy, --SO 2 NH 2 or --SO 2 N(CH 3 ) 2 , Z o is --S--, --O-- or --NR 35 '--, wherein R 35 ' is hydrogen, C 1-4 alkyl or (C 1-4 alkoxy)carbonylmethyl, and Wa is defined below, R 35a is C 1-4 alkyl, R 152 is methyl or carboxy, R 153 is C 1-4 alkyl, T is ##STR252## --CO--NH 2 , --NH 2 , --N(CH 3 ) 2 , --N.sup.⊕ (CH 3 ) 3 A.sup.⊖ or --CN, wherein each R 127 and m are as defined below, and Z o is as defined above, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s --*, wherein the asterisked end is bound to the nitrogen atom of the Z 2 group, yo' is --OH or --NH 2 , and d' is 0 to 1, R 20 is hydrogen or nitro, R 21 is hydrogen, nitro, --NH--CO--(CH 2 ) s --Z 2 , --CH 2 --Z 2 , --SO 2 --NH--(CH 2 ) s --Z 2 , --SO 2 NH 2 , --CO--CH 2 --Z 2 , --CO--NH--(CH 2 ) s --Z 2 , ##STR253## R 22 is hydrogen, nitro, --SO 2 NH 2 , --SO 2 N(R 22a ) 2 , --SO 2 --NH--(CH 2 ) s --OH, --CH 2 --Z 2 , --SO 2 --NH--(CH 2 ) s --Z 2 , --CO--NH--(CH 2 ) s --Z 2 , --NH--CO--(CH 2 ) s --Z 2 , ##STR254## wherein each R 22a is independently C 1-4 alkyl, and R 23 is hydrogen or methyl, wherein each Z 2 is independently --NH 2 , --N(R o ) 2 , --N.sup.⊕ (R o ) 3 A.sup.⊖, ##STR255## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, each p is independently 1, 2 or 3, and each s is independently 1, 2, 3, 4, 5 or 6, with the provisos that (i) the dye of formula III contains at least two basic water-solubilizing groups, (ii) at least one of R 20 and R 21 is other than nitro, (iii) R 21 and R 22 are different unless both are hydrogen, (iv) R 20 is hydrogen when both R 21 and R 22 are hydrogen, (v) at least one of R 20 -R 23 is hydrogen, (vi) when K 2 is ##STR256## at least one of R 21 and R 22 contains at least one Z 2 group, (vii) the negative charge on the complexed metal ion of each 1:2 metal complex is balanced by hydrogen or a non-chromophoric cation, and (viii) when the dye of formula III is in 1:2 metal complex form with another metallizable compound, the other metallizable compound contains an average of at least 1.3 basic water-solubilizing groups.

Claim 14

A metal complex which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR249## (ii) a 1:2 metal complex of two dyes of said formula or (iii) a 1:2 metal complex of a dye of said formula and a further metallizable compound, wherein A 4 is --OH, --NH 2 , --COOH or C 1-4 alkoxy, K 2 is ##STR250## wherein R 24 is hydrogen, C 1-4 alkyl, 2-hydroxyethyl, --(CH 2 ) p --Z 2 , benzyl, --N(R 30 ) 2 , --(CH 2 ) 3 --OCH 3 , --CH 2 --CH(CH 3 )--N(R 30 ) 2 or --CH 2 --C(CH 3 ) 2 --CH 2 --N(R 30 ) 2 , wherein each R 30 is independently hydrogen or C 1-4 alkyl, R 24a is C 1-4 alkyl, R 25 is C 1-4 alkyl, (C 1-4 alkoxy)carbonyl or carboxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 28 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 29 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, halo, --NH--(CH 2 ) s --Z 2 or --NHCH 2 CH 2 OH, R 32 is hydrogen, ##STR251## wherein R 5 is hydrogen, C 1-4 alkyl or C 1-4 alkoxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 33 is hydrogen, halo, C 1-4 alkyl, C 1-4 alkoxy, --SO 2 NH 2 or --SO 2 N(CH 3 ) 2 , Z o is --S--, --O-- or --NR 35 '--, wherein R 35 ' is hydrogen, C 1-4 alkyl or (C 1-4 alkoxy)carbonylmethyl, and Wa is defined below, R 35a is C 1-4 alkyl, R 152 is methyl or carboxy, R 153 is C 1-4 alkyl, T is ##STR252## --CO--NH 2 , --NH 2 , --N(CH 3 ) 2 , --N.sup.⊕ (CH 3 ) 3 A.sup.⊖ or --CN, wherein each R 127 and m are as defined below, and Z o is as defined above, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s --*, wherein the asterisked end is bound to the nitrogen atom of the Z 2 group, yo' is --OH or --NH 2 , and d' is 0 to 1, R 20 is hydrogen or nitro, R 21 is hydrogen, nitro, --NH--CO--(CH 2 ) s --Z 2 , --CH 2 --Z 2 , --SO 2 --NH--(CH 2 ) s --Z 2 , --SO 2 NH 2 , --CO--CH 2 --Z 2 , --CO--NH--(CH 2 ) s --Z 2 , ##STR253## R 22 is hydrogen, nitro, --SO 2 NH 2 , --SO 2 N(R 22a ) 2 , --SO 2 --NH--(CH 2 ) s --OH, --CH 2 --Z 2 , --SO 2 --NH--(CH 2 ) s --Z 2 , --CO--NH--(CH 2 ) s --Z 2 , --NH--CO--(CH 2 ) s --Z 2 , ##STR254## wherein each R 22a is independently C 1-4 alkyl, and R 23 is hydrogen or methyl, wherein each Z 2 is independently --NH 2 , --N(R o ) 2 , --N.sup.⊕ (R o ) 3 A.sup.⊖, ##STR255## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, each p is independently 1, 2 or 3, and each s is independently 1, 2, 3, 4, 5 or 6, with the provisos that (i) the dye of formula III contains at least two basic water-solubilizing groups, (ii) at least one of R 20 and R 21 is other than nitro, (iii) R 21 and R 22 are different unless both are hydrogen, (iv) R 20 is hydrogen when both R 21 and R 22 are hydrogen, (v) at least one of R 20 -R 23 is hydrogen, (vi) when K 2 is ##STR256## at least one of R 21 and R 22 contains at least one Z 2 group, (vii) the negative charge on the complexed metal ion of each 1:2 metal complex is balanced by hydrogen or a non-chromophoric cation, and (viii) when the dye of formula III is in 1:2 metal complex form with another metallizable compound, the other metallizable compound contains an average of at least 1.3 basic water-solubilizing groups.

Claim 15

A metal complex according to claim 12 which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR257## or (ii) a 1:2 metal complex of two dyes of said formula.

Claim 16

A metal complex according to claim 13 with the proviso that the dye of formula III contains 2-6 basic water-solubilizing groups.

Claim 17

A metal complex according to claim 13 having the formula ##STR258## wherein R 21a is hydrogen, --CH 2 --Z 2 , --NH--CO--(CH 2 ) a --Z 2 , --CO--CH 2 --Z 2 , nitro, --SO 2 NH 2 , --CO--NH--(CH 2 ) m' --Z 2 , --SO 2 --NH--(CH 2 ) m' --Z 2 or ##STR259## R 22a is hydrogen, nitro, --SO 2 NH 2 , --SO 2 --NH--(CH 2 ) 2 --OH, --CH 2 Z 2 , --NH--CO--(CH 2 ) a --Z 2 , --SO 2 --NH--(CH 2 ) m' --Z 2 or ##STR260## R 23 is hydrogen or methyl, R 24 ' is hydrogen, --N(CH 3 ) 2 , methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, benzyl, 2-hydroxyethyl, --(CH 2 ) m' --Z 2 , --CH 2 --CH(CH 3 )--N(CH 3 ) 2 or --CH 2 --C(CH 3 ) 2 --CH 2 --N(CH 3 ) 2 , Me a is copper, cobalt, iron or chromium, and d' is 0 or 1, wherein each Z 2 is independently --NH 2 , --N(R o ) 2 , --N.sup.⊕ (R o ) 3 A.sup.⊖, ##STR261## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, m is 0, 1 or 2, and p is 1, 2 or 3, each A.sup.⊖ is independently a non-chromophoric anion, each a is independently 1 or 2, and each m' is independently 2 or 3, with the provisos that (i) the complex contains at least two basic water-soluvilizing groups, and (ii) R 21a and R 22a are different unless both are hydrogen.

Claim 18

A metal complex according to claim 13 having the formula ##STR262## wherein A 4 " is --O-- or --COO--, --O--K 5 -- is ##STR263## wherein R g "' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 3 , R 50 is hydrogen, chloro, bromo, methyl or methoxy, R 51 is --(CH 2 ) q --, --NHCO--(CH 2 ) q --*, --CONH--(CH 2 ) q --* or --SO 2 NH--(CH 2 ) q --*, wherein the asterisked end is bound to the nitrogen atom of the Z 3 group, R 52 is hydrogen, chloro, bromo, methyl or methoxy, R 53 is hydrogen, --NH--(CH 2 ) q --Z 3 , --NH--CH 2 CH 2 OH, chloro, bromo, methyl or methoxy, R 54 is hydrogen, ##STR264## wherein R 55 is hydrogen, chloro, bromo, methyl, methoxy, --SO 2 NH 2 or --SO 2 N(CH 3 ) 2 , and R 50 and R 51 are as defined above, and T z is ##STR265## or --CN, R 20 is hydrogen or nitro, R 21d is hydrogen, nitro, --NH--CO--(CH 2 ) q --Z 3 , --CH 2 --Z 3 , --SO 2 NH 2 , --SO 2 --NH--(CH 2 ) q --Z 3 , ##STR266## R 22d is hydrogen, --CH 2 --Z 3 , --SO 2 N(CH 3 ) 2 , nitro, --SO 2 --NH--(CH 2 ) q --OH, ##STR267## --SO 2 --NH--(CH 2 ) q --Z 3 , --CO--NH-(CH 2 ) q --Z 3 or --NH--CO--(CH 2 ) q --Z 3 , and Me a is copper, cobalt, iron or chromium, wherein each Z 3 is independently ##STR268## and each A.sup.⊖ is independently a non-chromophoric anion, each d' is independently 0 or 1, and each p is independently 1, 2 or 3, each q is independently 1, 2, 3 or 4, with the provisos that (i) the complex contains at least two basic water-solubilizing groups, (ii) at least one of R 20 and R 21d is other than nitro, (iii) R 21d and R 22d are different unless both are hydrogen, (iv) R 20 is hydrogen when both R 21d and R 22d are hydrogen, and (v) when --O--K 5 -- is a radical of formula IIIbf, at least one of R 21d and R 22d contains at least one Z 3 group.

Claim 19

A metal complex according to claim 13 having the formula ##STR269## wherein each R 21a is independently hydrogen, --CH 2 --Z 2 , --NH--CO--(CH 2 ) a --Z 2 , --CO--CH 2 --Z 2 , nitro, --SO 2 --NH 2 , --CO--NH--(CH 2 ) m' --Z 2 , --SO 2 --NH--(CH 2 ) m' --Z 2 or ##STR270## each R 22a is independently hydrogen, nitro, --SO 2 NH 2 , --SO 2 --NH--(CH 2 ) 2 --OH, --CH 2 --Z 2 , --NH--CO--(CH 2 ) a --Z 2 , --SO 2 --NH--(CH 2 ) m' --Z 2 or ##STR271## each R 23 is independently hydrogen or methyl, each T x is independently ##STR272## wherein R 24 ' is hydrogen, --N(CH 3 ) 2 , methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, benzyl, 2-hydroxyethyl, --(CH 2 ) m' --Z 2 , --CH 2 --CH(CH 3 )--N(CH 3 ) 2 or --CH 2 --C(CH 3 ) 2 --CH 2 --N(CH 3 ) 2 , and d' is 0 or 1, M.sup.⊕ is hydrogen or a monovalent non-chromophoric cation, and Me g is chromium, iron or cobalt, wherein each Z 2 is independently ##STR273## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, m is 0, 1 or 2, and p is 1, 2 or 3, each A.sup.⊖ is independently a non-chromophoric anion, each a is independently 1 or 2, and each m' is independently 2 or 3, with the provisos that (i) each metal-free dye of the 1:2 metal complex contains at least two basic water-solubilizing groups, and (ii) R 21a and R 22a on the same ring are different unless both are hydrogen.

Claim 20

A metal complex according to claim 17 with the provisos that (i) each disazo dye of the metal complex contains 2-4 basic water-solubilizing groups, and (ii) at least one of R 21a and R 22a on the same ring is hydrogen.

Claim 21

A metal complex according to claim 13 having the formula ##STR274## wherein each A 4 " is independently --O-- or --COO--, each --O--K 5 -- is independently ##STR275## wherein R g "' is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 3 , R 50 is hydrogen, chloro, bromo, methyl or methoxy, R 51 is --(CH 2 ) q-- , --NHCO--(CH 2 ) q --*, --CONH--(CH 2 ) q --* or --SO 2 NH--(CH 2 ) q --*, wherein the asterisked end is bound to the nitrogen atom of the Z 3 group, R 52 is hydrogen, chloro, bromo, methyl or methoxy, R 53 is hydrogen, --NH--(CH 2 ) q --Z 3 , --NH--CH 2 CH 2 OH, chloro, bromo, methyl or methoxy, R 54 is hydrogen, ##STR276## wherein R 55 is hydrogen, chloro, bromo, methyl, methoxy, --SO 2 NH 2 or --SO 2 N(CH 3 ) 2 , and R 50 and R 51 are as defined above, and T z is ##STR277## or --CN, each R 20 is independently hydrogen or nitro, each R 21d is independently hydrogen, nitro, --NH--CO--(CH 2 ) q --Z 3 , --CH 2 --Z 3 , --SO 2 NH 2 , --SO 2 --NH--(CH 2 ) q --Z 3 , ##STR278## or --CO--NH--(CH 2 ) q --Z 3 , each R 22d is independently hydrogen, --CH 2 --Z 3 , --SO 2 N(CH 3 ) 2 , nitro, --S 2 --NH--(CH 2 ) q --OH, ##STR279## --SO 2 --NH--(CH 2 ) q --Z 3 , --CO--NH--(CH 2 ) q --Z 3 or --NH--CO--(CH 2 ) q --Z 3 , and M.sup.⊕ is hydrogen or a non-chromophoric monovalent cation, and Me g is chromium, iron or cobalt, wherein each Z 3 is independently ##STR280## each A.sup.⊖ is independently a non-chromophoric anion, each p is independently 1, 2 or 3, and each d' is independently 0 or 1, each q is independently 1, 2, 3 or 4, with the provisos that (i) each metal-free dye of the 1:2 metal complex contains at least two basic water-solubilizing groups, (ii) at least one of R 20 and R 21d on the same ring is other than nitro, (iii) R 21d and R 22d on the same ring are different unless both are hydrogen, (iv) R 20 is hydrogen when both R 21d and R 22d on the same ring are hydrogen, and (v) when an --O--K 5 -- is a radical of formula IIIbf, at least one of R 21d and R 22d on the same monoazo compound contains at least one Z 3 group.

Claim 22

A metal complex which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR281## (ii) a 1:2 metal complex of two dyes of said formula or (iii) a 1:2 metal complex of a dye of said formula and a further metallizable compound, wherein A 1 is --OH or --NH 2 , A 2 is --OH or --NH 2 , A 5 is --OH, --COOH or C 1-4 alkoxy, B 2 is ##STR282## wherein X' is a direct bond, straight or branched C 1-4 alkylene, ##STR283## wherein R 11 is halo, C 1-4 alkyl or C 1-4 alkoxy, each R 12 is independently hydrogen or C 1-4 alkyl, R 13 is halo, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , R 14 is straight or branched C 1-4 alkylene, and each q is independently 1, 2, 3 or 4, B 3 is ##STR284## wherein each R 65 is independently hydrogen, C 1-4 alkyl or C 1-4 alkoxy, K 7 is ##STR285## wherein R 9 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , R 10 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, acetamido or ureido, R 25 is C 1-4 alkyl, (C 1-4 alkoxy)carbonyl or carboxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 66 is hydrogen, C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 66 ' is C 1-4 alkyl, R 67 is --N(CH 3 ) 2 or --N.sup.⊕ (CH 3 ) 3 A.sup.⊖, R 68 is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR286## wherein R 71 is hydrogen, --OH, C 1-4 alkoxy, --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --(CH 2 ) p --Z 2 or ##STR287## and R 72 is hydrogen or --(CH 2 ) p --Z 2 , R 69 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , with the proviso that at least one of R 68 and R 69 contains at least one Z 2 group, Ta is ##STR288## wherein R 127 and m are as defined below, T 1a is --CN or --CONH 2 , and Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s --*, wherein the asterisk indicates the end attached to the nitrogen atom of the Z 2 group, and s is 1, 2, 3, 4, 5 or 6, R 60 is hydrogen or nitro, each of R 61 and R 62 is independently hydrogen, nitro, --CH 2 --Z 2 , --SO 2 --NH 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --SO 2 --NH--C 2 H 4 OH, --SO 2 --N(R 62 ') 2 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 ##STR289## wherein each R 62 ' is independently C 1-4 alkyl, each R 63 is independently --SO 2 --NH--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 , ##STR290## or --CH 2 --Z 2 , R 64 is hydrogen or C 1-4 alkoxy, both e's are 0 or 1, and q' is 1 or 2, with the proviso that q' must be 2 when an R 63 is --CONH--(CH 2 ) p --Z 2 , wherein each Z 2 is independently ##STR291## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the provisos that (i) the dye of formula IV contains at least two basic water-solubilizing groups, (ii) at least one of R 60 and R 61 is other than nitro, (iii) R 60 is hydrogen when both R 61 and R 62 are hydrogen, (iv) R 61 and R 62 are different unless both are hydrogen, (v) the negative charge on the complexed metal ion of each 1:2 metal complex is balanced by hydrogen or a non-chromophoric cation, and (vi) when the dye of formula IV is in 1:2 metal complex form with another metallizable compound, the other metallizable compound contains an average of at least 1.3 basic water-solubilizing groups.

Claim 23

A metal complex which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR281## (ii) a 1:2 metal complex of two dyes of said formula or (iii) a 1:2 metal complex of a dye of said formula and a further metallizable compound, wherein A 1 is --OH or --NH 2 , A 2 is --OH or --NH 2 , A 5 is --OH, --COOH or C 1-4 alkoxy, B 2 is ##STR282## wherein X' is a direct bond, straight or branched C 1-4 alkylene, ##STR283## wherein R 11 is halo, C 1-4 alkyl or C 1-4 alkoxy, each R 12 is independently hydrogen or C 1-4 alkyl, R 13 is halo, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , R 14 is straight or branched C 1-4 alkylene, and each q is independently 1, 2, 3 or 4, B 3 is ##STR284## wherein each R 65 is independently hydrogen, C 1-4 alkyl or C 1-4 alkoxy, K 7 is ##STR285## wherein R 9 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , R 10 is hydrogen, C 1-4 alkyl, C 1-4 alkoxy, acetamido or ureido, R 25 is C 1-4 alkyl, (C 1-4 alkoxy)carbonyl or carboxy, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 66 is hydrogen, C 1-4 alkyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 66 ' is C 1-4 alkyl, R 67 is --N(CH 3 ) 2 or --N.sup.⊕ (CH 3 ) 3 A.sup.⊖, R 68 is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR286## wherein R 71 is hydrogen, --OH, C 1-4 alkoxy, --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --(CH 2 ) p --Z 2 or ##STR287## and R 72 is hydrogen or --(CH 2 ) p --Z 2 , R 69 is C 1-4 alkyl or --(CH 2 ) p --Z 2 , with the proviso that at least one of R 68 and R 69 contains at least one Z 2 group, Ta is ##STR288## wherein R 127 and m are as defined below, T 1a is --CN or --CONH 2 , and Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s --*, wherein the asterisk indicates the end attached to the nitrogen atom of the Z 2 group, and s is 1, 2, 3, 4, 5 or 6, R 60 is hydrogen or nitro, each of R 61 and R 62 is independently hydrogen, nitro, --CH 2 --Z 2 , --SO 2 --NH 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --SO 2 --NH--C 2 H 4 OH, --SO 2 --N(R 62 ') 2 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 ##STR289## wherein each R 62 ' is independently C 1-4 alkyl, each R 63 is independently --SO 2 --NH--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 , ##STR290## or --CH 2 --Z 2 , R 64 is hydrogen or C 1-4 alkoxy, both e's are 0 or 1, and q' is 1 or 2, with the proviso that q' must be 2 when an R 63 is --CONH--(CH 2 ) p --Z 2 , wherein each Z 2 is independently ##STR291## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, and each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the provisos that (i) the dye of formula IV contains at least two basic water-solubilizing groups, (ii) at least one of R 60 and R 61 is other than nitro, (iii) R 60 is hydrogen when both R 61 and R 62 are hydrogen, (iv) R 61 and R 62 are different unless both are hydrogen, (v) the negative charge on the complexed metal ion of each 1:2 metal complex is balanced by hydrogen or a non-chromophoric cation, and (vi) when the dye of formula IV is in 1:2 metal complex form with another metallizable compound, the other metallizable compound contains an average of at least 1.3 basic water-solubilizing groups.

Claim 24

A metal complex according to claim 20 which is (i) a 1:1 or 1:2 metal complex of a dye of the formula ##STR292## or (ii) a 1:2 metal complex of two dyes of said formula.

Claim 25

A metal complex according to claim 21 with the proviso that the dye of formula IV contains 2-6 basic water-solubilizing groups.

Claim 26

A 1:2 metal complex according to claim 21 having the formula ##STR293## wherein A 1 ' is --O-- or --NH--, A 2 is --OH or --NH 2 , A 5 " is --O-- or --COO--, R 60 is hydrogen or nitro, R 61a is hydrogen, --NO 2 , --CH 2 --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --SO 2 NH 2 , --NH--CO--(CH 2 ) p --Z 2 , ##STR294## R 62a is hydrogen, --NO 2 , --CH 2 --Z 2 , --SO 2 --NH 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 , ##STR295## B 2 ' is ##STR296## X a is a direct bond, ##STR297## wherein R 13a is chloro, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , and and q is 1, 2, 3 or 4, K 7 ' is ##STR298## wherein R 9a is methyl, ethyl or --CH 2 CH 2 --Z 2 , R 10a is hydrogen, methyl, methoxy, acetamido or ureido, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 66a is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 67 is --N(CH 3 ) 2 or --N.sup.⊕ (CH 3 ) 3 A.sup.⊖, R 68a is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR299## wherein R 71a is hydrogen, --OH, --OCH 3 , --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 or ##STR300## and R 72a is hydrogen or --(CH 2 ) p --Z 2 , R 69a is methyl, ethyl or --(CH 2 ) p --Z 2 , with the proviso that at least one of R 68a and R 69a contains at least one Z 2 group, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s --*, wherein s is 1, 2, 3, 4, 5, or 6 and the asterisk indicates the end attached to the Z 2 group d' is 0 or 1, and Me c is copper, cobalt or chromium, wherein each Z 2 is independently ##STR301## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the provisos that (i) the metal complex of formula IVc contains at least two basic water-solubilizing groups, (ii) at least one of R 60 and R 61a is other than nitro, (iii) R 60 is hydrogen when both R 61a and R 62a are hydrogen, (iv) R 61a and R 62a are different unless both are hydrogen, and (v) the A 5 "-bearing phenylazo group is ortho to A 1 '.

Claim 27

A 1:1 metal complex according to claim 21 having the formula ##STR302## wherein A 1 ' is --O-- or --NH--, A 2 is --OH or --NH 2 , A 5 " is --O-- or --COO--, R 60 is hydrogen or nitro, R 61a ' is hydrogen, nitro, --NH--CO--(CH 2 ) a --Z 2 or ##STR303## R 62a ' is hydrogen, nitro, --SO 2 NH 2 , --SO 2 N(CH 3 ) 2 , --SO 2 N(C 2 H 5 ) 2 , --SO 2 NH--CH 2 CH 2 OH, --SO 2 NH--(CH 2 ) m' --Z 2 , --CO--NH--(CH 2 ) m' --Z 2 , --NH--CO--(CH 2 ) a --Z 2 or ##STR304## with the proviso that R 62a ' may be --CO--NH--(CH 2 ) m' --Z 2 , --NH--CO--(CH 2 ) a --Z 2 or ##STR305## only when R 60 and R 61 ' are both hydrogen, each R 63a is independently --SO 2 --NH--(CH 2 ) m' --Z 2 , --CO--NH--(CH 2 ) m' --Z 2 , --NH--CO--(CH 2 ) a --Z 2 , --CH 2 --Z 2 or ##STR306## R 64a is hydrogen or methoxy, each R 65a is independently methyl, ethyl, methoxy, or ethoxy, Me a is copper, cobalt, iron or chromium, and k is 1 or 2, with the proviso that k must be 2 when an R 63a is --CO--NH--(CH 2 ) m' --Z 2 , wherein each Z 2 is independently ##STR307## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, each A.sup.⊖ is independently a non-chromophoric anion, and m is 0, 1 or 2, each a is independently 1 or 2, and each m' is independently 2 or 3, with the provisos that (i) the metal complex of formula IVg contains at least two basic water-solubilizing groups, (ii) at least one of R 60 and R 61a ' is other than nitro, (iii) R 60 is hydrogen when both R 61a ' and R 62a ' are hydrogen, (iv) R 61a ' and R 62a ' are different unless both are hydrogen, and (v) the A 5 "-bearing phenylazo group is ortho to A 1 '.

Claim 28

A 1:2 metal complex according to claim 21 having the formula ##STR308## wherein each A 1 ' is independently --O-- or --NH--, each A 2 is independently --OH or --NH 2 , each A 5 " is independently --O-- or --COO--, each R 60 is independently hydrogen or nitro, each R 61a is independently hydrogen, --NO 2 , --CH 2 --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --SO 2 NH, --NH--CO--(CH 2 ) p --Z 2 , ##STR309## R 62a is independently hydrogen, --NO 2 , --CH 2 --Z 2 , --SO 2 --NH 2 , --SO 2 --NH--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --NH--CO--(CH 2 ) p --Z 2 , ##STR310## each B 2 ' is independently, ##STR311## wherein X a is a direct bond, ##STR312## wherein R 13a is chloro, --NHCH 2 CH 2 OH or --N(CH 2 CH 2 OH) 2 , and and q is 1, 2, 3 or 4, each K 7 ' is independently ##STR313## wherein R 9a is methyl, ethyl or --CH 2 CH 2 --Z 2 , R 10a is hydrogen, methyl, methoxy, acetamido or ureido, R 26 is hydrogen, halo, C 1-4 alkyl or C 1-4 alkoxy, R 66a is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, 2-hydroxyethyl or --(CH 2 ) p --Z 2 , R 67 is --N(CH 3 ) 2 or --N.sup.⊕ (CH 3 ) 3 A.sup.⊖, R 68a is --(CH 2 ) p --Z 2 , --NH--(CH 2 ) p --Z 2 or ##STR314## wherein R 71a is hydrogen, --OH, --OCH 3 , --NH--CO--(CH 2 ) p --Z 2 , --CO--NH--(CH 2 ) p --Z 2 , --SO 2 --NH--(CH 2 ) p --Z 2 or ##STR315## and R 72a is hydrogen or --(CH 2 ) p --Z 2 , R 69a is methyl, ethyl or --(CH 2 ) p --Z 2 , with the proviso that at least one of R 68a and R 69a contains at least one Z 2 group, Wa is --(CH 2 ) s --, --NHCO--(CH 2 ) s --*, --CONH--(CH 2 ) s --* or --SO 2 NH--(CH 2 ) s --*, wherein s is 1, 2, 3, 4, 5 or 6 and the asterisk indicates the end attached to the Z 2 group, d' is 0 or 1, Me is chromium, iron or cobalt, and M.sup.⊕ is hydrogen or a monovalent non-chromophoric cation, wherein each Z 2 is independently ##STR316## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contains more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, and m is 0, 1 or 2, each A.sup.⊖ is independently a non-chromophoric anion, and each p is independently 1, 2 or 3, with the proviso that (i) each metal-free dye of the 1:2 metal complex of formula IVi contains at least two basic water-solubilizing groups. (ii) at least one of R 60 and R 61a on the same ring is other than nitro, (iii) R 60 is hydrogen when both R 61a and R 62a on the same ring are hydrogen, (iv) R 61a and R 62a on the same ring are different unless both are hydrogen and (v) each A 5 "-bearing phenylazo group is ortho to A 1 '.

Claim 29

A 1:2 metal complex according to claim 21 having the formula ##STR317## wherein each A 1 ' is independently --O-- or --NH--, each A 2 is independently --OH or --NH 2 , each A 5 " is independently --O-- or --COO--, each R 60 is independently hydrogen or nitro, R 61a ' is independently hydrogen, nitro, --NH--CO--(CH 2 ) a --Z 2 or ##STR318## R 62a ' is independently hydrogen, nitro, --SO 2 NH 2 , --SO 2 N(CH 3 ) 2 , --SO 2 N(C 2 H 5 ) 2 , --SO 2 NH--CH 2 CH 2 OH, --CO--NH--(CH 2 ) m' --Z 2 , --NH--CO--(CH 2 ) a --Z 2 or ##STR319## with the proviso that R 62a ' may be --CO--NH--(CH 2 ) m' --Z 2 , --NH--CO--(CH 2 ) a --Z 2 or ##STR320## only when R 60 and R 61a ' on the same ring are both hydrogen, each R 63a is independently --SO 2 --NH--(CH 2 ) m' --Z 2 , --CO--NH--(CH 2 ) m' --Z 2 , --NH--CO--(CH 2 ) a --Z 2 , --CH 2 --Z 2 or ##STR321## each R 64a is independently hydrogen or methoxy, each R 65a is independently methyl, ethyl, methoxy or ethoxy, Me g is cobalt, or iron or chromium M⊕ is hydrogen or a monovalent non-chromophoric cation, and each k is independently 1 or 2, with the proviso that k must be 2 when an R 63a on that ring is --CO--NH--(CH 2 ) m' Z 2 , wherein each Z 2 is independently ##STR322## wherein each R o is independently methyl, ethyl, 2-hydroxyethyl, benzyl, acetylmethyl or benzoylmethyl, with the proviso that no nitrogen atom contain more than one member of the group consisting of benzyl, acetylmethyl and benzoylmethyl, and no nitrogen atom contains more than two 2-hydroxyethyl groups, each R 127 is independently methyl or ethyl, each A.sup.⊖ is independently a non-chromophoric anion, and m is 0, 1 or 2, each a is independently 1 or 2, and each m' is independently 2 or 3, with the provisos that (i) each metal-free dye of the 1:2 metal complex of formula IV1 contains at least two basic water-solubilizing groups, (ii) at least one of R 60 and R 61a ' on the same ring is other than nitro, (iii) R 60 is hydrogen when both R 61a ' and R 62a ' on the same ring are hydrogen, (iv) R 61a ' and R 62a ' on the same ring are different unless both are hydrogen, and (v) each A 5 "-bearing phenylazo group is ortho to A 1 '.

Claim 30

A metal complex according to claim 15 having the formula ##STR323## wherein each of R 21b and R 22b is independently hydrogen, nitro, --CH 2 --Z 3 , --SO 2 NH 2 , --NH--CO--CH 2 --Z 3 , --SO 2 --NH--(CH 2 ) m' --Z 3 or ##STR324## R 24 " is hydrogen, methyl, ethyl, 2-hydroxyethyl or --(CH 2 ) m' --Z 3 , and Me c is copper, cobalt or chromium, wherein each Z 3 is independently ##STR325## wherein p is 1, 2 or 3, each A.sup.⊖ is independently a non-chromophoric anion, each d' is independently 0 or 1, and each m' is independently 2 or 3, with the provisos that (i) the complex contains at least two basic water-solubilizing groups, (ii) R 21b and R 22b are different or R 21b and R 22b are both hydrogen, and (iii) the --N═N-- radical attached to ring E is in the 3- or 4-position thereof.

Claim 31

A metal complex according to claim 27 having the formula ##STR326## wherein each of R 21c and R 22c is independently hydrogen, nitro, --CH 2 --Z 5 , --SO 2 NH 2 , --NH--CO--CH 2 --Z 5 , --SO 2 --NH--(CH 2 ) m' --Z 5 or ##STR327## wherein each Z 5 is independently --N(CH 3 ) 2 , --N(C 2 H 5 ) 2 , --N.sup.⊕ (CH 3 ) 3 A.sup.⊖ or ##STR328## and each m' is independently 2 or 3, and R 24 "' is hydrogen, 2-hydroxyethyl, --(CH 2 ) 3 --N(CH 3 ) 2 , --(CH 2 ) 3 --N(C 2 H 5 ) 2 or --(CH 2 ) 3 --N.sup.⊕ (CH 3 ) 3 A.sup.⊖, wherein each A.sup.⊖ is independently a non-chromophoric anion, with the provisos that (i) the complex contains at least two basic water-solubilizing groups, (ii) R 21c and R 22c are different or R 21c and R 22c are both hydrogen, and (iii) the --N═N-- radical attached to ring E is in the 3- or 4-position thereof.

Claim 32

A metal complex according to claim 28 wherein R 21c is hydrogen, R 22c is nitro, R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , and the --N═N-- radical attached to ring E is in the 3-position thereof.

Claim 33

The metal complex according to claim 29 wherein A.sup.⊖ is chloride.

Claim 34

A metal complex according to claim 17 having the formula ##STR329## wherein each R 21b and R 22b is independently hydrogen, nitro, --CH 2 --Z 3 , --SO 2 NH 2 , --NH--CO--CH 2 --Z 3 , --SO 2 --NH--(CH 2 ) m' --Z 3 or ##STR330## each T x ' is independently ##STR331## wherein R 24 " is hydrogen, methyl, ethyl, 2-hydroxyethyl or --(CH 2 ) m' --Z 3 , M.sup.⊕ is hydrogen or a non-chromophoric monovalent cation, and Me g is chromium, iron or cobalt, wherein each Z 3 is independently ##STR332## wherein p is 1, 2 or 3, each A.sup.⊖ is independently a non-chromophoric anion, each d' is independently 0 or 1, and each m' is independently 2 or 3, with the provisos that (i) each metal-free disazo compound of the 1:2 metal complex contains at least two basic water-solubilizing groups, (ii) R 21b and R 22b on the same ring are different or R 21b and R 22b on the same ring are both hydrogen, and (iii) each --N═N-- radical attached to a ring E is in the 3- or 4-position thereof.

Claim 35

A metal complex according to claim 31 having the formula ##STR333## wherein each R 21c and R 22c is independently hydrogen, nitro, --CH 2 --Z 5 , --SO 2 NH 2 , --NH--CO--CH 2 --Z 5 , --SO 2 --NH--(CH 2 ) m' --Z 5 or ##STR334## wherein each Z 5 is independently --N(CH 3 ) 2 , --N(C 2 H 5 ) 2 , --N.sup.⊕ (CH 3 ) 3 A.sup.⊖ or ##STR335## and each m' is independently 2 3, each T x " is independently ##STR336## wherein R 24 "' is hydrogen, 2-hydroxyethyl, --(CH 2 ) 3 --N(CH 3 ) 2 , --(CH 2 ) 3 --N(C 2 H 5 ) 2 or --(CH 2 ) 3 --N.sup.⊕ (CH 3 ) 3 A.sup.⊖, M.sup.⊕ is hydrogen or a non-chromophoric monovalent cation, and Me g is chromium, iron or cobalt, wherein each A.sup.⊖ is independently a non-chromophoric anion, with the provisos that (i) each metal-free disazo compound of the 1:2 metal complex contains at least two basic water-solubilizing groups, (ii) R 21c and R 22c on the same ring are different or R 21c and R 22c on the same ring are both hydrogen, and (iii) each --N═N-- radical attached to a ring E is in the 3- or 4-position thereof.

Claim 36

A metal complex according to claim 32 wherein the two metal-free disazo compounds are identical.

Claim 37

A metal complex according to claim 33 wherein each R 21c is hydrogen, each R 22c is nitro, each R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , Me g is chromium, and each --N═N-- radical attached to a ring E is in the 4-position thereof.

Claim 38

The metal complex according to claim 33 wherein M.sup.⊕ is sodium, and each A.sup.⊖ is chloride.

Claim 39

A metal complex according to claim 33 wherein each R 21c is hydrogen, each R 22c is nitro, each R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , Me g is iron, and each --N═N-- radical attached to a ring E is in the 4-position thereof.

Claim 40

The metal complex according to claim 36 wherein M.sup.⊕ is sodium, and each A.sup.⊖ is chloride.

Claim 41

A metal complex according to claim 33 wherein each R 21c is nitro, each R 22c is hydrogen, each R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , Me g is iron, and each --N═N-- radical attached to a ring E is in the 4-position thereof.

Claim 42

The metal complex according to claim 38 wherein M.sup.⊕ is sodium, and each A.sup.⊖ is chloride.

Claim 43

A metal complex according to claim 33 wherein each R 21c is nitro, each R 22c is hydrogen, each R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , Me g is chromium, and each --N═N-- radical attached to a ring E is in the 4-position thereof.

Claim 44

The metal complex according to claim 40 wherein M.sup.⊕ is sodium, and each A.sup.⊖ is chloride.

Claim 45

A metal complex according to claim 33 wherein each R 21c is nitro, each R 22c is hydrogen, each R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , Me g is iron, and each --N═N-- radical attached to a ring E is in the 3-position thereof.

Claim 46

The metal complex according to claim 42 wherein M.sup.⊕ is sodium, and each A.sup.⊖ is chloride.

Claim 47

A metal complex according to claim 33 wherein each R 21c is hydrogen, each R 22c is --SO 2 NH 2 , each R 24 "' is --(CH 2 ) 3 --N(CH 3 ) 2 , Me g is iron, and each --N═N-- radical attached to a ring E is in the 3-position thereof.

Claim 48

The metal complex according to claim 44 wherein M.sup.⊕ is sodium, and each A.sup.⊖ is chloride.

Claim 49

A metal complex according to claim 26 wherein each A 1 ' is --O--, each A 2 is --OH, each A 5 " is --O--, each R 61a ' is independently hydrogen, nitro, --NH--CO--CH 2 --Z 3 or ##STR337## each R 62a' is independently hydrogen, nitro, --SO 2 NH 2 , --SO 2 N(CH 3 ) 2 , --SO 2 --NH--(CH 2 ) m' --Z 3 , --SO 2 --NH--C 2 H 4 OH, --CO--NH--(CH 2 ) m' --Z 3 , --NH--CO--CH 2 --Z 3 or ##STR338## with the proviso that R 62a ' may be --CO--NH--(CH 2 ) m '--Z 3 , --NH--CO--CH 2 --Z 3 or ##STR339## only when R 60 and R 61a ' on the same ring are both hydrogen, each R 65a is independently methyl or methoxy, wherein each Z 3 is independently ##STR340## wherein p is 1, 2 or 3, d' is 0 or 1, and each A.sup.⊖ is independently a non-chromophoric anion, and each m' is independently 2 or 3.

Claim 50

A metal complex according to claim 46 wherein the two metal-free trisazo compounds are identical.

Claim 51

A metal complex according to claim 47 wherein each R 60 is hydrogen, each R 61a ' is hydrogen, each R 62a ' is --SO 2 NH 2 , each R 63a is ##STR341## each R 64a is hydrogen, each R 65a is methyl, Me g is iron, and each k is 1.

Claim 52

A metal complex according to claim 48 wherein M.sup.⊕ is sodium.

Claim 53

A metal complex according to claim 47 wherein each R 60 is hydrogen, each R 61a ' is hydrogen, each R 62a ' is --SO 2 NH 2 each R 63a is ##STR342## each R 64a is hydrogen, each R 65a is methoxy, Me g is iron, and each k is 1.

Claim 54

A metal complex according to claim 50 wherein M.sup.⊕ is sodium.