U.S. patent application number 10/158879 was filed with the patent office on 2003-08-21 for reactive dyes containing a halobenzene nucleus.
This patent application is currently assigned to BASF Akiengesellschaft. Invention is credited to Ebenezer, Warren James, Greenwood, David, Hutchings, Michael Gordon, Rabjohns, Michael Alan, Zamponi, Andrea Maria.
Application Number | 20030158395 10/158879 |
Document ID | / |
Family ID | 10821975 |
Filed Date | 2003-08-21 |
United States Patent
Application |
20030158395 |
Kind Code |
A1 |
Ebenezer, Warren James ; et
al. |
August 21, 2003 |
Reactive dyes containing a halobenzene nucleus
Abstract
1. A dye contains at least one chromophore D; at least a first,
halobenzene, reactive group Z.sup.1, of the formula (I) 1 in which:
n is 1 or 2 X, or each X independently, is an electron withdrawing
group; and Y is a halogen atom; at least a second reactive group
Z.sup.2 selected from (1) a group of the formula (I), given and
defined above, but selected independently thereof; (2) a group of
the formula (II) 2 wherein m is 1 or 2; p is 0 or 1; when m is 1, p
is 1; and when m is 2, p is 0; Y.sup.1 or each Y.sup.1
independently, is a halogen atom or an optionally substituted
pyridinium group; and T is C.sub.1-4alkoxy, C.sub.1-4thioalkoxy or
N(R.sup.1) (R.sup.2), in which each of R.sup.1 and R.sup.2
independently is hydrogen, optionally substituted C.sub.1-4alkyl or
optionally substituted aryl; (3) a group of the formula (III) 3
wherein: x is 1, 2 or 3; y is zero, 1 or 2; and x+y.ltoreq.3;
Y.sup.2, or each Y.sup.2 independently, is a halogen atom or an
optionally substituted pyridinium group; and U or each U
independently, is C.sub.1-4alkyl or C.sub.1-4alkylsulphonyl; (4) a
group of the formula (IV) --SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV)
wherein X.sup.1 is an eliminatable group; (5) a group of the
formula (V) --SO.sub.2(CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V) wherein z
is zero or 1; and (6) a group of formula (VI)
--W--C(R.sup.10).dbd.CH.sub.2 (VI) wherein: R.sup.10 is hydrogen,
C.sub.1-4alkyl or halogen; and W is --OC(.dbd.O)-- or
--N(R.sup.11)C(.dbd.O)-- in which R.sup.11 is hydrogen or C14
alkyl; at least a first linking group L.sup.1, linking the said
first, halobenzene, reactive group Z.sup.1 to one of components (i)
the or a chromophore D and (ii) the second reactive group Z.sup.2,
which said first linking group L.sup.1 presents an amino nitrogen
to the reactive group Z.sup.1 and to the component (i) or (ii) or,
when component (i) contains a heterocyclic nitrogen atom, is linked
directly to the nitrogen atom and which said first linking group
L.sup.1 optionally includes a hydrocarbon bridging group, which
hydrocarbon bridging group B has at least two carbon atoms, is
optionally substituted, optionally includes at least one hetero
atom and is optionally a chromophore; and when Z.sup.2 is selected
from the said groups (I)-(III), at least a second linking group
L.sup.2 linking the second reactive group Z.sup.2 to one of (i) the
or a chromophore D and (ii) the said first reactive group Z.sup.1,
which said linking group L.sup.2 is selected from (1) a linking
group L.sup.1, but selected independently thereof; or (2) an amide
linkage; and (3) a sulphonamide linkage; and optionally at least
one aromatic group Ar which, when Z.sup.2 is selected from the said
groups (IV)-(VI), may carry the said reactive group Z.sup.2.
Inventors: |
Ebenezer, Warren James;
(Bramhall, GB) ; Greenwood, David; (Shaw, GB)
; Hutchings, Michael Gordon; (Bury, GB) ;
Rabjohns, Michael Alan; (Manchester, GB) ; Zamponi,
Andrea Maria; (Mannheim, DE) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
BASF Akiengesellschaft
Ludwigshafen
DE
|
Family ID: |
10821975 |
Appl. No.: |
10/158879 |
Filed: |
June 3, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10158879 |
Jun 3, 2002 |
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09554325 |
Jul 24, 2000 |
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6399751 |
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09554325 |
Jul 24, 2000 |
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PCT/GB98/03406 |
Nov 12, 1998 |
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Current U.S.
Class: |
534/630 ;
534/632 |
Current CPC
Class: |
C09B 62/78 20130101;
C09B 62/4401 20130101; C09B 62/443 20130101 |
Class at
Publication: |
534/630 ;
534/632 |
International
Class: |
C09B 062/026; C09B
062/347 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 12, 1997 |
GB |
9723924.8 |
Claims
1. A dye containing a at least one chromophore D; at least a first,
halobenzene, reactive group Z.sup.1, of the formula (I) 355 in
which: n is 1 or 2 X, or each X: independently, is an electron
withdrawing group; and Y is a halogen atom; at least a second
reactive group Z.sup.2 selected from (1) a group of the formula
(I), given and defined above, but selected independently thereof;
(2) a group of the formula (II) 356 wherein m is 1 or 2; p is 0 or
1; when m is 1, p is 1; and when m is 2, p is 0; Y.sup.1, or each
Y.sup.1 independently, is a halogen atom or an optionally
substituted pyridinium group; and T is C.sub.1-4alkoxy,
C.sub.1-4thioalkoxy or N(R.sup.1) (R.sup.2), in which each of
R.sup.1 and R.sup.2 independently is hydrogen, optionally
substituted C.sub.1-4alkyl or optionally substituted aryl; (3) a
group of the formula (III) 357 wherein: x is 1, 2 or 3; y is zero,
1 or 2; and x+y.ltoreq.3; Y.sup.2, or each Y.sup.2 independently,
is a halogen atom or an optionally substituted pyridinium group;
and U or each U independently, is C.sub.1-4alkyl or
C.sub.1-4alkylsulphonyl; (4) a group of the formula (IV)
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV) wherein X.sup.1 is an
eliminatable group; (5) a group of the formula (V) --SO.sub.2
(CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V) wherein z is zero or 1; and (6)
a group of formula (VI) --W--C(R.sup.10).dbd.CH.sub.2 (VI) wherein:
R.sup.10 is hydrogen, C.sub.1-4alkyl or halogen; and W is
--OC(.dbd.O)-- or --N(R.sup.11)C(.dbd.O)-- in which R.sup.11 is
hydrogen or C.sub.1-4 alkyl; at least a first linking group
L.sup.1, linking the said first, halobenzene, reactive group
Z.sup.1 to one of components (i) the or a chromophore D and (ii)
the second reactive group Z.sup.2, which said first linking group
L.sup.1 presents an amino nitrogen to the reactive group Z.sup.1
and to the component (i) or (ii) or, when component (i) contains a
heterocyclic nitrogen atom, is linked directly to the nitrogen atom
and which said first linking group L.sup.1 optionally includes a
hydrocarbon bridging group, which hydrocarbon bridging group B has
at least two carbon atoms, is optionally substituted, optionally
includes at least one hetero atom and is optionally a chromophore;
and when Z.sup.2 is selected from the said groups (I)-(III), at
least a second linking group L.sup.2 linking the second reactive
group Z.sup.2 to one of (i) the or a chromophore D and (ii) the
said first reactive group Z.sup.1, which said linking group L.sup.2
is selected from (1) a linking group L.sup.1, but selected
independently thereof; or (2) an amide linkage; and (3) a
sulphonamide linkage; and optionally at least one aromatic group Ar
which, when Z.sup.2 is selected from the said groups (IV)-(VI), may
carry the said reactive group Z.sup.2.
2. A dye according to claim 1, wherein the linking group L.sup.1
has the formula (VII).sup.1 N(R) (VII).sup.1 wherein R is hydrogen
or optionally substituted C.sub.1-4alkyl, such that the same amino
group presents itself to each of the reactive group Z.sup.1 and the
component (i) or (ii), as defined in claim 1.
3. A dye according to claim 1, wherein the linking group L.sup.1 is
a piperazinoalkylamino group of the formula (VII).sup.2 358wherein
each R, independently, is as defined in claim 2, such that
respective amino nitrogens, one of the piperazine group and the
other of the alkylamino group, present themselves respectively, to
the reactive group Z.sup.1 and to the component (i) or (ii), as
defined in claim 1.
4. A dye according to claim 1, wherein the linking group L.sup.1
has the formula (VII).sup.3 --N(R)BN(R)-- (VII).sup.3 wherein B is
a hydrocarbon bridging group as defined in claim 1, each R,
independently, is as defined in claim 1 and B is optionally linked
additionally to at least one additional group --N(R).
5. A dye according to claim 4, wherein the hydrocarbon bridging
group B is an optionally substituted aryl group.
6. A dye according to any preceding claim, of the formula (VIII)
Z.sup.1-L.sup.1-D-(L.sup.2).sub.a-Z.sup.2 (VIII) wherein: D is a
chromophore; each of L.sup.1 and L.sup.2 is an amine or piperazine
linkage of the formula --N(R)-- (VII).sup.1; 359--N(R)BN(R)--
(VII).sup.3 wherein: R, or each R independently, is hydrogen or
C.sub.1-4 alkyl; B is a hydrocarbon bridging group which has at
least two carbon atoms, is optionally substituted, optionally
includes at least one hetero atom and is optionally a chromophore;
a is zero or 1; and b is from 2 to 6 inclusive; Z.sup.1 is a group
360 in which: n is 1 or 2; X, or each X independently, is an
electron withdrawing group; and Y is a halogen atom; and when a is
1, Z.sup.2 is: a group of the formula (I), given and defined above
but selected independently thereof; or a group of the formula (II)
361 wherein: m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and
when m is 2, p is 0; Y.sup.1, or each Y.sup.1 independently, is a
halogen atom or an optionally substituted pyridinium group; and T
is C.sub.1-4 alkoxy, thioalkoxy or N(R.sup.1) (R.sup.2) in which
R.sup.1 is hydrogen, optionally substituted C.sub.1-4 alkyl or
optionally substituted aryl and R.sup.2 is hydrogen or optionally
substituted C.sub.1-4 alkyl; or a group of the formula (III) 362
wherein: x is 1, 2 or 3; y is zero, 1 or 2; and x+y.ltoreq.3;
Y.sup.2, or each Y.sup.2 independently, is a halogen atom; and U,
or each U independently, is C.sub.1-4 alkyl or C.sub.1-4
alkylsulphonyl; and when a is zero, Z.sup.2 is:
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV) in which X.sup.1 is an
eliminatable group; or --SO.sub.2 (CH.sub.2).sub.ZCH.dbd.CH.sub.2
(V) wherein z is zero or 1; or a group of formula (VI)
--W--C(R.sup.10).dbd.CH.sub.2 (VI) wherein: R.sup.10 is hydrogen,
C.sub.1-4alkyl or halogen; and W is --OC(.dbd.O)-- or
--N(R.sup.11)C(.dbd.O)-- in which R is hydrogen or C.sub.1-4
alkyl.
7. A dye according to any preceding claim, wherein, in formula (I),
X, or each X independently, is selected from nitro, cyano,
alkylsulphonyl, dialkylaminosulphonyl and sulphonic acid or a salt
thereof.
8. A dye according to any preceding claim, wherein a group of the
formula (II) is present, in which Y.sup.1, or each Y independently,
is fluorine, chlorine or optionally substituted pyridinium.
9. A dye according to any one of claims 2 to 8, wherein R, or each
R independently, is hydrogen.
10. A dye according to any preceding claim, wherein each of Z.sup.1
and Z.sup.2, independently, is a group: 363wherein each of X, n and
Y is as defined in claim 1.
11. A dye according to claim 10, wherein each of Z.sup.1 and
Z.sup.2 is the same as the other.
12. A dye according to any one of claims 1 to 9, wherein a is 1 and
Z.sup.2 is 364wherein Y.sup.1,m, T and p are as defined in claim
1.
13. A dye according to any one of claims 1 to 9, wherein a is 1 and
Z.sup.2 is 365where Y.sup.2, x, U and y are as defined in claim
1.
14. A dye according to any one of claims 1 to 9, wherein a is zero
and Z.sup.2 is --SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV) where X.sup.1
is as defined in claim 1; or --SO.sub.2
(CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V) wherein z is as defined in
claim 1.
15. A dye according to any preceding claim, wherein D is an azo
chromophore.
16. A dye according to claim 15, wherein D is a monoazo
chromophore.
17. A dye according to claim 16, which has the formula (XVII)
366wherein: each R independently and a is as defined in claim 1;
one of Z.sup.3 and Z.sup.4 is a group Z.sup.1 and the other is is a
group Z.sup.2; the group Z.sup.4 is selected from the groups of the
formulae (I)-(III), given and defined in claim 1; Ar is a benzene
or naphthalene nucleus; R.sup.3, or each R.sup.3 independently, is
C.sub.1-4 alkyl, nitro, halo or sulphonic acid or salt thereof; c
is zero or 1-4; R.sup.4, or each R.sup.4 independently, is a
sulphonic acid or a salt thereof; and d is 1 or 2.
18. A dye according to claim 15, wherein D is a disazo
chromophore.
19. A dye according to claim 18, which has the formula (XVIII)
367wherein: one of Z.sup.5 and Z.sup.6 is a group X and the other
is a group Z.sup.2; each of f and g independently is zero or 1;
when Z.sup.5 or Z.sup.6 is any of the groups of the formulae
(I)-(III), given and defined claim 1, f or g respectively is 1 and
when Z.sup.5 or Z.sup.6 is any of the groups of the formulae
(IV)-(VI), given and defined in claim 1, f or g respectively is
zero; each of c and e, independently, is zero or 1-4; d is 1 or 2;
each R independently is as defined in claim 1; each of Ar.sup.1 and
Ar.sup.2 is an optionally substituted aryl group; and each of
R.sup.3 and R.sup.4 is as defined in claim 17.
20. A dye according to claim 19, wherein each of Z.sup.5 and
Z.sup.6 is the same group 368wherein X, Y and n are as defined in
claim 1.
21. A dye according to claim 19, wherein one of Z.sup.5 and Z.sup.6
is a group of the formula (I), given and defined in claim 1, and
the other of Z.sup.5 and Z.sup.6 is selected from groups of the
formulae (II) and (III), given and defined in claim 1.
22. A dye according to claim 18, which dye has the formula
369wherein: B is a hydrocarbon bridging group as defined in claim
1; one of G.sup.1 and G.sup.2 is OH and the other is NH.sub.2; each
of X, Y, Y.sup.1 and n is as defined in claim 1; each of Ar.sup.1,
Ar.sup.2, R.sup.3, R.sup.4, c and d is as defined in claim 19; and
each of R.sup.5 and e is as defined in claim 19.
23. A dye according to claim 22, wherein B is an optionally
substituted aryl group.
24. A dye according to claim 19, wherein one of Z.sup.5 and Z.sup.6
is a group 370wherein: X, Y and n are as defined in claim 1 and the
other of Z.sup.5 and Z.sup.6 is the group
--SO.sub.2CH.sub.2CH.sub.2OSO.sub.3H or
--SO.sub.2CH.dbd.CH.sub.2.
25. A dye according to claim 24, which has the formula 371wherein
G.sup.3 is C.sub.2H.sub.4OSO.sub.3H or a salt thereof or
--CH.dbd.CH.sub.2; G.sup.1 and G.sup.2 are as defined in claim 22;
R.sup.4 and d are as defined in claim 17; and each of h and i,
independently, is zero, 1 or 2.
26. A dye according to claim 25, which has the formula 372where
each of G.sup.1 and G.sup.2 is as defined in claim 22 and G.sup.3
is as defined in claim 25.
27. A dye according to claim 1, of the formula
Z.sup.1-L.sup.1-D[L.sup.3].-
sub.q-[Z.sup.3-L.sup.4.sub.r[J.sup.1].sub.s[L.sup.2].sub.aZ.sup.2[L.sup.5--
J.sup.2].sub.t wherein: Z.sup.3 is a third reactive group selected
from the groups of the formulae (I)-(III), given and defined in
claim 1; each of J.sup.1 and J.sup.2, independently, is an
optionally substituted aryl group or a chromophore; L.sup.3 is a
linking group linking Z.sup.3 and D; L.sup.4 is a linking group
linking Z.sup.3 and J.sup.1; L.sup.5 is a linking group linking
Z.sup.2 and J.sup.2; each of q, r, s and t independently, is zero
or 1; each of Z.sup.1, Z.sup.2, L.sup.1, L.sup.2 and a is as
defined in claim 1; and when at least one of a and t is 1, Z.sup.2
is selected from the groups of the formulae (I)-(III), given and
defined in claim 1.
28. A dye according to claim 27, wherein q is 1, r is 1, s is 1,
each of a and t is zero and Z.sup.2 is selected from the groups of
the formulae (Iv)-(VI), given and defined in claim 1.
29. A dye according to claim 27, wherein q is 1, r is 1, s is zero,
a is zero and t is 1.
30. A dye according to any one of claims 27 to 29 wherein each of
L.sup.3 and L.sup.4, independently, is selected from one of the
groups of the formulae (VII).sup.1, (VII).sup.2 and (VII).sup.3,
given and defined in claim 6.
31. A dye according to claim 30, wherein each of L.sup.3 and
L.sup.4 is a group of the formulae (VII).sup.1, given and defined
in claim 6.
32. A dye according to claim 27, wherein q is 1, r is zero, s is 1,
a is zero and t is zero.
33. A dye according to claim 32, wherein L.sup.3 is a group of the
formula (VII).sup.3 --N(R)BN(R)-- (VII).sup.3 wherein B is a
triazine group substituted by a non-reactive group.
34. A dye according to any one of claims 27 to 33, wherein the
chromophore D is an azo chromophore derived from
1-hydroxy-8-aminonaphthalene substituted by at least one sulphonic
acid group.
35. A dye according to claim 1 of the formula
Z.sup.1-L.sup.1-D.sup.1[L.su-
p.3-Z.sup.3(L.sup.4-Z.sup.4).sub.1L.sup.5-D.sup.2].sub.k[L.sup.2].sub.aZ.s-
up.2 wherein: D.sup.1 is a first chromophore; D.sup.2 is a second
chromophore; Z.sup.3, when present, is a third reactive group
selected from the groups of the formulae (I)-(III), given and
defined in claim 1; Z.sup.4, when present, is a fourth reactive
group selected from the groups of the formulae (I)-(III), given and
defined in claim 1; L.sup.3 is a linking group linking Z.sup.3 to
D.sup.1; L.sup.4 is a linking group linking Z.sup.3 to Z.sup.4;
L.sup.5 is a linking group linking D.sup.2 to one of Z.sup.3 and
Z.sup.4; each of k and l, independently, is zero or l; and each of
Z.sup.1, Z.sup.2, L.sup.1, L.sup.2 and a is as defined in claim
1.
36. A dye according to claim 35 wherein a is 1, Z.sup.2 is a group
of the formula (I), given and defined in claim 1, k is zero and
D.sup.1 is a tetrakisazo chromophore containing two residues of
H-acid linked together by a group forming part of the
chromophore.
37. A dye according to claim 35, wherein a is 1, each of Z.sup.1
and Z.sup.2 is a group of the formula (I), given and defined in
claim 1, each of k and l is 1; each of D.sup.1 and D.sup.2 is a
disazo chromophore containing a respective residue of H-acid, each
of Z.sup.3 and Z.sup.4 is a group of the formula (II), given and
defined in claim 1, and L.sup.4 is a linking group of the formula
(VII).sup.2 or (VII).sup.3, given and defined in claim 6.
38. A dye according to claim 35, wherein a is 1, Z.sup.2 is a group
of the formula (I), given and defined in claim 1, k is 1 and l is
1.
39. A dye according to claim 35, wherein a is 1, Z.sup.2 is a group
of the formula (I), given and defined in claim 1, k is 1 and l is
zero.
40. A dye according to claim 1, of the formula
Z.sup.1-L.sup.1-Z.sup.3-L.s- up.3D-Z.sup.2 wherein: Z.sup.3 is a
third reactive group selected from the groups (I)-(III), given and
defined in claim 1; and L.sup.3 is a third linking group selected
from the groups (VII).sup.1, (VII).sup.2 and (VII).sup.3, given and
defined in claim 6; Z.sup.2 is a second reactive group selected
from the groups (IV)-(VI), given and defined in claim 1; and each
of Z.sup.1 and L.sup.1 is as defined in claim 1.
41. A dye according to claim 40, wherein L.sup.1 is a linking group
of the formula (VII).sup.2 or (VII).sup.3, given and defined in
claim 6.
42. A dye according to claim 40 or claim 41, wherein Z.sup.3 is a
group of the formula (II), given and defined in claim 1.
43. A dye according to claim 1, of the formula
D-L.sup.2-Z.sup.2-L.sup.1-Z- .sup.1 wherein: Z.sup.2 is selected
from groups of the formulae I-(III), given and defined in claim 1;
and each of D, Z.sup.1, L.sup.1 and L.sup.2 is as defined in claim
1.
44. A dye according to claim 43, wherein Z.sup.2 is a group of the
formula (II), given and defined in claim 1.
45. A dye according to claim 43 or claim 44, wherein L.sup.2 is a
linking group selected from the groups (VII).sup.1, (VII).sup.2 and
(VII).sup.3, given and defined in claim 6.
46. A dye according to claim 43, wherein L.sup.2 is a linking group
of the formula (VII).sup.2 or (VII).sup.3, given and defined in
claim 6.
47. A dye according to any one of claims 43 to 46, wherein L.sup.1
is a group of the formula (VII.sup.3), given and defined in claim
6, in which B is an optionally substituted aryl group.
48. A dye according to any one of claims 43 to 46, wherein L.sup.1
is a group of the formula (VII.sup.3), given and defined in claim
6, in which B is a chromophoric bridging group.
49. A dye according to any one of claims 40 to 48, wherein the
chromophore D is a disazo dye containing a residue derived from
H-acid and having azo groups at the 2- and 7-positions.
50. A dye according to any one of claims 43 to 48, wherein D is a
group of the formula 373
51. A dye according to claim 1, of the formula
D.sup.2-L.sup.2-Z.sup.2-L.s- up.3-D.sup.1-L.sup.1-Z.sup.1 wherein:
each of D.sup.1 and D.sup.2, independently, is a chromophore;
L.sup.3 is a linking group selected from groups of the formula
(I)-(III), given and defined in claim 1; and each of Z.sup.1,
Z.sup.2, L.sup.1 and L.sup.2 is as defined in claim 1.
52. A dye according to claim 1, of the formula 374wherein: each of
D.sup.1 and D.sup.2, independently, is a chromophore; L.sup.3 is a
linking group selected from the groups of the formulae (I)-(III),
given and defined in claim 1; and each of Z.sup.1, Z.sup.2, L.sup.1
and L.sup.2 is as defined in claim 1.
53. A dye according to claim 1, of the formula. 375wherein: one of
Z.sup.3 and Z.sup.4 is a reactive group Z.sup.2; each of Z.sup.3
and Z.sup.4.sub.1 independently, is a reactive group selected from
the formulae (IV)-(VI), given and defined in claim 1; each of t and
u, independently, is zero or 1 and at least one of t and u is 1; D
is a chromophore; Ar is an optionally substituted aryl group;
L.sup.1 is a group of the formula 376wherein each R, independently,
is as defined in claim; and Z.sup.1 is as defined in claim 1.
54. A dye according to claim 53, wherein D is a disazo dye
containing a residue derived from H-acid.
55. A dye according to claim 1, wherein the or a chromophore D
contains a heterocyclic nitrogen atom and the linking group has the
formula 377wherein each of B, R and b is as defined in claim 6 and
the bond {circle over (1)} is linked to the heterocyclic nitrogen
atom of the chromophore.
56. A dye according to claim 55, of the formula
Z.sup.1-L.sup.1-D.sup.NL.s- up.2.sub.aZ.sup.2L.sup.5-Ar].sub.t
wherein: D.sup.N is a chromophore containing a heterocyclic group
including a nitrogen atom; L.sup.1 is a group of the formula
(VII).sup.4 or (VII).sup.5, given and defined in claim 55, directly
attached via the bond {circle over (1)}, to the nitrogen atom of
the said chromophore D.sup.N; Ar is an optionally substituted aryl
group; and each of Z.sup.1, Z.sup.2, L.sup.2, L.sup.5, a and t is
as defined in claim 27.
57. A dye according to claim 56, wherein the chromophore D has the
formula 378
58. A dye according to any one of claims 27 to 56, which is an azo
dye having at least two azo groups therein.
59. A dye according to claim 15, wherein D is a trisazo or
tetrakisazo chromophore.
60. A dye according to claim 1, wherein the chromophore D is an
anthraquinone.
61. A dye according to claim 60, which is of the formula
D.sup.A-L.sup.3-Ar-L.sup.2-Z.sup.2-L.sup.1-Z.sup.1 wherein: D.sup.A
is an anthraquinone chromophore; L.sup.3 is a linking of the
formula (VII).sup.1, given and defined in claim 6; Ar is an
optionally substituted aryl group; and each of Z.sup.1, Z.sup.2,
L.sup.1 and L.sup.2 is as defined in claim 1.
62. A dye according to claim 61, wherein each of L.sup.1 and
L.sup.2, independently, is a linking group of the formula
(VII).sup.1, (VII).sup.2 or (VII).sup.3, given and defined in claim
6.
63. A dye according to claim 62, wherein each of L.sup.1 and
L.sup.2, independently is a group of the formula (VII).sup.3, given
and defined in claim 6, in which B is an optionally substituted
aryl group.
64. A dye according to claim 1, wherein the chromophore D is a
metal phthalocyanine.
65. A dye according to claim 64, of the formula 379wherein: Cu Pc
is a copper phthalocyanine chromophore; X+Y+Z.ltoreq.4; each of
R.sup.21 and R.sup.22 independently, is hydrogen or optionally
substituted C.sub.1-4alkyl; B is a hydrocarbon bridging group; and
Z.sup.1 is as defined in claim 1.
66. A dye according to claim 1, wherein the chromophore D is a
triphendioxazine chromophore.
67. A dye according to claim 66, which is of the formula
Z.sup.1-L.sup.1-Z.sup.3-L.sup.3].sub.q-D.sup.T-[Z.sup.4].sub.r-L.sup.2-Z.-
sup.2 wherein: D.sup.T is a triphendioxazine chromophore; each of
L.sup.2, L.sup.3 and L.sup.4, independently, is a linking group of
the formula (VII).sup.1, (VII).sup.2 or (VII).sup.3, given and
defined in claim 6; each of Z.sup.2, Z.sup.3 and Z.sup.4 is a
reactive group selected from groups of the formulae (I)-(III),
given and defined in claim 1; each of q and r is zero or 1; and
each of Z.sup.1 and L.sup.1 is as defined in claim 1.
68. A dye according to claim 67, wherein Z.sup.2 is a group of the
formula (I), given and defined in claim 1 and each of Z.sup.3 and
Z.sup.4 is a group of the formula (II), given and defined in claim
1.
69. A dye according to claim 67 or claim 68, wherein each of
L.sup.1, L.sup.2, L.sup.3 and L.sup.4 is a group of the formula
(VII).sup.3, given and defined in claim 6.
70. A dye according to claim 1, wherein the chromophore D is a
formazan chromophore.
71. A dye according to claim 70, of the formula
[Z.sup.A].sub.a-D.sup.F-L-- Z.sup.B-L.sup.1-Z.sup.1 wherein:
D.sup.F is a formazan chromophore; one of Z.sup.A and Z.sup.B is a
group Z.sup.2, given and defined in claim 1; L is a linking group
of the formula (VII).sup.1, (VII).sup.2 or (VII).sup.3, given and
defined in claim 6; each of Z.sup.1 and L.sup.1 is as defined in
claim 1; a is zero or 1; Z.sup.A is selected from groups of the
formulae (IV)-(VI), given and defined in claim 1; and Z.sup.B is
selected from groups of the formulae (I)-(III), given and defined
in claim 1. 380381
78. A process for preparing a dye of the formula (VIII).sup.1
Z.sup.1-L.sup.1-D-L.sup.2-Z.sup.2 (VIII).sup.1 wherein: D is a
chromophore; each of L.sup.1 and L.sup.2 independently, is N(R);
each R, independently, is hydrogen or C.sub.1-4alkyl; each of
Z.sup.1 and Z.sup.2 is a group 382 in which: n is 1 or 2 X, or each
X independently, is an electron withdrawing group; and Y is a
halogen atom, which process comprises reacting a chromophoric
compound of the formula (XX) H(R)N-D-N(R)H (XX) wherein each of D
and R is as defined above, with at least two moles, per mole of the
chromophoric compound of the formula (XX), of a dihalobenzene
component comprising at least one dihalobenzene compound of the
formula (XXI) 383 wherein each of X, Y and n is as defined above,
to obtain the dye of the formula (VIII).sup.1.
79. A process for preparing a dye of the formula (VIII).sup.1
Z.sup.1-L.sup.1-D-L.sup.2-Z.sup.2 (VIII).sup.2 wherein: D is a
chromophore; each of L.sup.1 and L.sup.2 independently, is N(R),
each R, independently, is hydrogen or C.sub.1-4alkyl; Z.sup.1 is a
group 384 in which: n is 1 or 2 X, or each X independently, is an
electron withdrawing group; and Y is a halogen atom; and Z.sup.2 is
selected from the groups (II) and (III) given and defined in claim
1; which process comprises reacting a chromophoric compound of the
formula (XX) H(R)N-D-N(R)H (XX) wherein each of D and R is as
defined above, with one mole, per mole of the chromophoric compound
of the formula (XX), of each of (a) a dihalobenzene compound of the
formula (XXI) 385 wherein each of Z, X, Y and n is as defined
above; and (b) a compound selected from 386 wherein: m is 1 or 2; p
is 0 or 1; when m is 1, p is 1; and when m is 2, p is 0; Y.sup.1,
or each Y.sup.1 independently, is a halogen atom or an optionally
substituted pyridinium group; and T is C.sub.1-4alkoxy,
C.sub.14thioalkoxy or N(R.sup.1) (R.sup.2) in which each of R.sup.1
and R.sup.2 independently is hydrogen, optionally substituted
C.sub.1-4alkyl or optionally substituted aryl; x is 1, 2 or 3; y is
zero, 1 or 2; and x+y.ltoreq.3; Y.sup.2, or each Y.sup.2
independently, is a halogen atom or an optionally substituted
pyridinium group; U or each U independently, is C.sub.1,-alkyl or
C.sub.1-4alkylsulphonyl; and Y is as defined above; the said
reactions of the compound of the formula (XX) with each of the
respective compounds of the formulae (XII) and (XIII) being carried
out simultaneously or one before the other, in either order, to
obtain a dye of the formula (VIII).sup.2.
80. A process for preparing a dye of the formula (VIII).sup.3
Z.sup.1-L.sup.1-D-Z.sup.2 (VIII).sup.3 wherein: D is a chromophore
L.sup.1 is N(R), in which R is hydrogen or C.sub.1-4alkyl; Z.sup.1
is a group 387 in which n is 1 or 2; X, or each X independently, is
an electron withdrawing group; and Y is a hydrogen atom; and
Z.sup.2 is a group of the formula (IV)
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV)
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV) wherein X.sup.1 is an
eliminatable group; a group of the formula (V)
--SO.sub.2(CH.sub.2).sub.Z- CH.dbd.CH.sub.2 (V) wherein z is zero
or 1; and a group of formula (VI) --W--C(R.sup.10).dbd.CH.sub.2
(VI) wherein: R.sup.10 is hydrogen, C.sub.1-4alkyl or halogen; and
W is --OC(.dbd.O)-- or --N(R.sup.11)C(.dbd.O)--in which R.sup.11 is
hydrogen or C.sub.1-4alkyl; which process comprises reacting a
chromophoric compound of the formula (XXIV) H(R)N-D-Z.sup.2 (XXIV)
wherein D and Z.sup.2 are as defined above, with a dihalobenzene
compound of the formula (XXI) 388wherein each of X, Y and n is as
defined above, to obtain the dye of the formula (VIII).sup.3.
81. A process for the colouration of a substrate, which process
comprises applying to the substrate a dye according to any one of
claims 1 to 77.
82. A process according to claim 81, wherein the dye is applied to
the substrate by exhaust dyeing, padding or printing.
83. A process according to claim 82, wherein the dye is applied by
ink jet printing.
Description
[0001] This invention relates to reactive dyes containing a
halobenzene nucleus and, in particular, reactive dyes of this type
containing two or more reactive components.
[0002] Dyes are known which contain a halobenzene nucleus linked
via an azo group to another aromatic nucleus such that the
halobenzene nucleus forms part of the chromophoric chain (see for
example GB-A-882001). Dyes of this type which contain two such
halobenzene nuclei are disclosed in CA64,14316d (1966), which is an
English language abstract of an article by Matsui et al, Yuki Gosei
Kagaku Kyokai Shi (1966), 24(2), 132-136.
[0003] Dyes are also known in which the halobonzene nucleus is
attached to a chromophoric group by a sulphonamide or amide
linkage; see, for example, GB-A-978162 and CA59,12949 g (1963),
which is an English language abstract of an article by Matsui et al
in Yuki Gosei Kagaku Kyokai Shi (1962), 20,1100-1112. Again dyes of
this type may contain two such halobenzene nuclei; see
GB-A-978162.
[0004] In other known dyes the halobenzene nucleus is linked to a
chromophoric group by an amine linkage; see U.S. Pat. No. 3,301,847
and CA61,16193f (1964) which is an English language abstract of an
article by Matsui et al in Kogyo Kagaku Zasshi, (1964),
67(1),94-97. However, such dyes contain only one reactive
group.
[0005] We have now found surprisingly that dyes having at least one
halobenzene nucleus linked to a chromophoric group via an amino
linkage and additionally containing a second reactive group have
particularly high build up, especially in warm dyeing
applications.
[0006] According to the invention there is provided a dye
containing
[0007] at least one chromophore D;
[0008] at least a first, halobenzene, reactive group Z.sup.1, of
the formula (I) 4
[0009] in which:
[0010] n is 1 or 2
[0011] X, or each X independently, is an electron withdrawing
group; and
[0012] Y is a halogen atom;
[0013] at least a second reactive group Z.sup.2 selected from
[0014] (1) a group of the formula (I), given and defined above, but
selected independently thereof;
[0015] (2) a group of the formula (II) 5
[0016] wherein m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and
when m is 2, p is 0;
[0017] Y.sup.1, or each Y.sup.1 independently, is a halogen atom or
an optionally substituted pyridinium group; and
[0018] T is C.sub.1-4alkoxy, C.sub.1-4thioalkoxy or N(R.sup.1)
(R.sup.2), in which each of R.sup.1 and R.sup.2 independently is
hydrogen, optionally substituted C.sub.1-4alkyl or optionally
substituted aryl;
[0019] (3) a group of the formula (III) 6
[0020] wherein:
[0021] x is 1, 2 or 3; y is zero, 1 or 2; and
[0022] x+y.ltoreq.3;
[0023] Y.sup.2, or each Y.sup.2 independently, is a halogen atom or
an optionally substituted pyridinium group; and
[0024] U or each U independently, is C.sub.1-4alkyl or
C.sub.1-4alkylsulphonyl;
[0025] (4) a group of the formula (IV)
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV)
[0026] wherein X.sup.1 is an eliminatable group;
[0027] (5) a group of the formula (V)
--SO.sub.2 (CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V)
[0028] wherein z is zero or 1; and
[0029] (6) a group of formula (VI)
--W--C(R.sup.10).dbd.CH.sub.2 (VI)
[0030] wherein:
[0031] R.sup.10 is hydrogen, C.sub.1-4alkyl or halogen; and
[0032] W is --OC(.dbd.O)-- or --N(R.sup.11)C(.dbd.O)-- in which
R.sup.11 is hydrogen or C.sub.1-4 alkyl;
[0033] at least a first linking group L.sup.1, linking the said
first, halobenzene, reactive group Z.sup.1 to one of components (i)
the or a chromophore D and (ii) the second reactive group Z.sup.2,
which said first linking group L.sup.1 presents an amino nitrogen
to the reactive group Z.sup.1 and to the component (i) or (ii) or,
when component (i) contains a heterocyclic nitrogen atom, is linked
directly to the nitrogen atom and which said first linking group
L.sup.1 optionally includes a hydrocarbon bridging group, which
hydrocarbon bridging group B has at least two carbon atoms, is
optionally substituted, optionally includes at least one hetero
atom and is optionally a chromophore; and
[0034] when Z.sup.2 is selected from the said groups (I)-(III), at
least a second linking group L.sup.2 linking the second reactive
group Z.sup.2 to one of (i) the or a chromophore D and (ii) the
said first reactive group Z.sup.1, which said linking group L.sup.2
is selected from
[0035] (1) a linking group L.sup.1, but selected independently
thereof; or
[0036] (2) an amide linkage; and
[0037] (3) a sulphonamide linkage; and
[0038] optionally at least one aromatic group Ar which, when
Z.sup.2 is selected from the said groups (IV)-(VI), may carry the
said reactive group Z.sup.2.
[0039] Preferably, the linking group L.sup.1 has the formula
(VII).sup.1
N(R) (VII).sup.1
[0040] wherein R is hydrogen or optionally substituted
C.sub.1-4alkyl, such that the same amino group presents itself to
each of the reactive group Z.sup.1 and the component (i) or (ii),
as defined above; or
[0041] is a piperazinoalkylamino group of the formula (VII).sup.2
7
[0042] wherein each R, independently, is as defined above, such
that respective amino nitrogens, one of the piperazine group and
the other of the alkylamino group, present themselves respectively,
to the reactive group Z.sup.1 and to the component (i) or (ii), as
defined above; or
[0043] has the formula (VII).sup.3
--N(R)BN(R)-- (VII).sup.3
[0044] wherein B is a hydrocarbon bridging group as defined above,
each R, independently, is as defined above and B is optionally
linked additionally to at least one additional group --N(R).
[0045] The hydrocarbon bridging group B may be a straight or
branched, optionally substituted, C.sub.2-6alkylene group
optionally interrupted by at least one hetero atom, for example, O,
S or N. Optional substituents are OH alkoxy, carboxy, carboxylic
ester or carboxamide. Alternatively the bonding group B may be an
optionally substituted arylene especially phenylene group. Optional
substituents are SO.sub.3H and salts thereof, C.sub.1-4alkyl,
C.sub.1-4alkoxy and chloro. The bridging group B is especially
preferably an optionally substituted aryl group.
[0046] An especially preferred dye embodying the invention has the
formula (VIII)
Z.sup.1-L.sup.1-D-(L.sup.2).sub.a-Z.sup.2 (VIII)
[0047] wherein:
[0048] D is a chromophore;
[0049] each of L.sup.1 and L.sup.2 is an amine or piperazine
linkage of the formula
--N(R)-- (VII).sup.1; 8
--N(R)BN(R)-- (VII).sup.3
[0050] wherein:
[0051] R, or each R independently, is hydrogen or C.sub.1-4
alkyl;
[0052] B is a hydrocarbon bridging group which has at least two
carbon atoms, is optionally substituted, optionally includes at
least one hetero atom and is optionally a chromophore;
[0053] a is zero or 1; and
[0054] b is from 2 to 6 inclusive;
[0055] Z.sup.1 is a group 9
[0056] in which:
[0057] n is 1 or 2;
[0058] X, or each X independently, is an electron withdrawing
group; and
[0059] Y is a halogen atom; and
[0060] when a is 1, Z.sup.2 is:
[0061] a group of the formula (I), given and defined above but
selected independently thereof; or
[0062] a group of the formula (II) 10
[0063] wherein:
[0064] m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is
2, p is 0;
[0065] Y.sup.1, or each Y.sup.1 independently, is a halogen atom or
an optionally substituted pyridinium group; and
[0066] T is C.sub.1-4 alkoxy, thioalkoxy or N(R.sup.1) (R.sup.2) in
which R.sup.1 is hydrogen, optionally substituted C.sub.1-4 alkyl
or optionally substituted aryl and
[0067] R.sup.2 is hydrogen or optionally substituted C.sub.1-4
alkyl; or
[0068] a group of the formula (III) 11
[0069] wherein:
[0070] x is 1, 2 or 3; y is zero, 1 or 2; and x+y.ltoreq.3;
[0071] Y.sup.2, or each Y.sup.2 independently, is a halogen atom;
and
[0072] U, or each U independently, is C.sub.1-4 alkyl or C.sub.1-4
alkylsulphonyl; and
[0073] when a is zero, Z.sup.2 is:
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV)
[0074] in which X.sup.1 is an eliminatable group; or
--SO.sub.2 (CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V)
[0075] wherein z is zero or 1; or
[0076] a group of formula (VI)
--W--C(R.sup.10).dbd.CH.sub.2 (VI)
[0077] wherein:
[0078] R.sup.10 is hydrogen, C.sub.1-4alkyl or halogen; and
[0079] W is --OC(.dbd.O)-- or --N(R.sup.11)C(.dbd.O)-- in which
R.sup.11 is hydrogen or C.sub.1-4 alkyl.
[0080] In the halobenzene nucleus of the formula (I), X or each X
independently, may be selected from nitro, cyano, alkylsulphonyl,
dialkylaminosulphonyl and sulphonic acid groups and salts thereof.
Preferably, X or each X independently, is selected from nitro and
cyano.
[0081] The halogen atom in the halobenzene nucleus of formula (I)
is preferably fluorine or chlorine.
[0082] The group R in the linking group L.sup.1 of formulae (1)-(3)
may be any of hydrogen, methyl, ethyl, n- or i-propyl or n-, s- or
t-butyl, but is preferably hydrogen.
[0083] In the dye of formula (VII), each of Z.sup.1 and Z.sup.2,
independently, is preferably a group of the above mentioned formula
(I). Moreover, it is even more preferred that each of Z.sup.1 and
Z.sup.2 is the same group as the other.
[0084] However, alternatively, Z.sup.1 may be a halobenzene nucleus
of the formula (I), A may be zero and Z.sup.2 a group of the
formula
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV)
[0085] in which X.sup.1 is an eliminatable group such as
OSO.sub.3H, OPO.sub.3H.sub.2 and salts of any of these, and Cl, a
preferred group (IV) being
--SO.sub.2CH.sub.2CH.sub.2OSO.sub.3H (or a salt thereof)
or
SO.sub.2 (CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V)
[0086] wherein z is zero or 1.
[0087] In an other alternative range of dyes, Z.sup.1 is a
halobenzene nucleus of the formula (I) above and Z.sup.2 is a
halotriazine nucleus of the formula (II) 12
[0088] wherein m is 1 or 2, p is 0 or 1,
[0089] when m is 1, p is 1 and
[0090] when m is 2, p is 0;
[0091] Y.sup.1, or each Y.sup.1 independently, is a halogen atom or
an optionally substituted pyridinium group; and
[0092] T is C.sub.1-4 alkoxy, C.sub.1-4thioalkoxy or N(R.sup.1)
(R.sup.2) in which R.sup.1 is hydrogen, optionally substituted
C.sub.1-4 alkyl or optionally substituted aryl; and
[0093] R.sup.2 is hydrogen or optionally substituted
C.sub.1-4alkyl.
[0094] In the above formula (II), Y.sup.1 is preferably fluorine,
chlorine or optionally substituted pyridinium which may be derived
from, for example, nicotinic or isonicotinic acid or their
carboxamides.
[0095] Each of R.sup.1 and R.sup.2 is preferably hydrogen, but at
least one of R.sup.1 and R.sup.2 may be a C.sub.1-4 alkyl group and
indeed R.sup.1 may additionally be an optionally substituted aryl,
preferably phenyl, group.
[0096] When such a C.sub.1-4 alkyl or aryl group is substituted, a
preferred substituent is hydroxyl, amino, halo, carboxy or
sulpho.
[0097] In yet another alternative dye in accordance with the
invention, Z.sup.1 is a halobenzene nucleus of the formula (I) and
Z.sup.2 is a halopyrimidine nucleus of the formula 13
[0098] wherein x is 1, 2 or 3; y is 0, 1 or 2; and
x+y.ltoreq.3;
[0099] Y.sup.2, or each Y.sup.2 independently, is halogen atom;
and
[0100] U, or each U independently, is C.sub.1-4alkyl or
C.sub.1-4alkylsulphonyl.
[0101] In the above formula (III) Y.sup.2 is preferably fluorine or
chlorine.
[0102] A preferred range of dyes embodying the invention has the
formula (XXX)
Z.sup.1-L.sup.1-D[L.sup.3].sub.q-[Z.sup.3-L.sup.4.sub.r[J.sup.1].sub.s[L.s-
up.2].sub.aZ.sup.2[L.sup.5-J.sup.2].sub.t (XXX)
[0103] wherein:
[0104] Z.sup.3 is a third reactive group selected from the groups
of the formulae (I)-(III), given and defined above;
[0105] each of J.sup.1 and J.sup.2, independently, is an optionally
substituted aryl group or a chromophore;
[0106] L.sup.3 is a linking group linking Z.sup.3 and D;
[0107] L.sup.4 is a linking group linking Z.sup.3 and J.sup.1;
[0108] L.sup.5 is a linking group linking Z.sup.2 and J.sup.2;
[0109] each of q, r, s and t independently, is zero or 1;
[0110] each of Z.sup.1, Z.sup.2, L.sup.1, L.sup.2 and a is as
defined above; and
[0111] when at least one of a and t is 1, Z.sup.2 is selected from
the groups of the formulae (I)-(III), given and defined above.
[0112] In one such range of dyes, q is 1, r is 1, s is 1, each of a
and t is zero and Z.sup.2 is selected from the groups of the
formulae (IV)-(VI), given and defined above.
[0113] In another such range, q is 1, r is 1, s is zero, a is zero
and t is 1.
[0114] In a dye of the formula (XXX), each of L.sup.3 and L.sup.4,
independently, is preferably selected from one of the groups of the
formulae (VII).sup.1, (VII).sup.2 and (VII).sup.3, given and
defined above;
[0115] each of L.sup.3 and L.sup.4 is preferably a group of the
formulae (VII).sup.1, given and defined above.
[0116] In one preferred range of dyes of the formula (XXX), q is 1,
r is zero, s is 1, a is zero and t is zero and in such a range
L.sup.3 is preferably a group of the formula (VII).sup.3
--N(R)BN(R)-- (VII).sup.3
[0117] wherein B is a triazine group substituted by a non-reactive
group.
[0118] In a dye of the formula (XXX), the chromophore D is
preferably an azo chromophore derived from
1-hydroxy-8-aminonaphthalene substituted by at least one sulphonic
acid group.
[0119] Yet another range of dyes embodying the invention has the
formula
Z.sup.1-L.sup.1-D.sup.1[L.sup.3-Z.sup.3(L.sup.4-Z.sup.4).sub.1L.sup.5-D.su-
p.2].sub.k[L.sup.2].sub.aZ.sup.2
[0120] wherein:
[0121] D.sup.1 is a first chromophore;
[0122] D.sup.2 is a second chromophore;
[0123] Z.sup.3, when present, is a third reactive group selected
from the groups of the formulae (I)-(III), given and defined in
claim 1;
[0124] Z.sup.4, when present, is a fourth reactive group selected
from the groups of the formulae (I)-(III), given and defined in
claim 1;
[0125] L.sup.3 is a linking group linking Z.sup.3 to D.sup.1;
[0126] L.sup.4 is a linking group linking Z.sup.3 to Z.sup.4;
[0127] L.sup.5 is a linking group linking D.sup.2 to one of Z.sup.3
and Z.sup.4;
[0128] each of k and l, independently, is zero or 1; and
[0129] each of Z.sup.1, Z.sup.2, L.sup.1, L.sup.2 and a is as
defined in claim 1.
[0130] In one range of such dye of formula (XXXI), a is 1, Z.sup.2
is a group of the formula (I), given and defined above, k is zero
and D.sup.1 is a tetrakisazo chromophore containing two residues of
H-acid linked together by a group forming part of the
chromophore.
[0131] In another such range, a is 1, each of Z.sup.1 and Z.sup.2
is a group of the formula (I), given and defined above, each of k
and l is 1;
[0132] each of D.sup.1 and D.sup.2 is a disazo chromophore
containing a respective residue of H-acid,
[0133] each of Z.sup.3 and Z.sup.4 is a group of the formula (II),
given and defined above, and
[0134] L.sup.4 is a linking group of the formula (VII).sup.2 or
(VII).sup.3, given and defined above.
[0135] In still further such ranges
[0136] (i) a is 1, Z.sup.2 is a group of the formula (I), given and
defined above, k is 1 and l is 1; or
[0137] (ii) a is 1, Z.sup.2 is a group of the formula (I), given
and defined above, k is 1 and l is zero.
[0138] Yet another preferred range of dyes embodying the invention
has the formula (XXXII)
Z.sup.1-L.sup.1-Z.sup.3-Z.sup.3-D-Z.sup.2 (XXXII)
[0139] wherein:
[0140] Z.sup.3 is a third reactive group selected from the groups
(I)-(III), given and defined above; and
[0141] L.sup.3 is a third linking group selected from the groups
(VII).sup.1, (VII).sup.2 and (VII).sup.3, given and defined
above;
[0142] Z.sup.2 is a second reactive group selected from the groups
(IV)-(VI), given and defined above; and
[0143] each of Z.sup.1 and L.sup.1 is as defined above.
[0144] In such dyes of the formula (XXXII), L.sup.1 is preferably a
linking group of the formula (VII).sup.2 or (VII).sup.3, given and
defined above and Z.sup.3 is preferably a group of the formula
(II), given and defined above.
[0145] Another range of dyes embodying the invention has the
formula (XXXIII)
D-L.sup.2-Z.sup.2-L.sup.1-Z.sup.1 (XXXIII)
[0146] wherein:
[0147] Z.sup.2 is selected from groups-of the formulae I-(III),
given and defined above; and
[0148] each of D, Z.sup.1, L.sup.1 and L.sup.2 is as defined
above.
[0149] In such dyes of the formula (XXXIII), Z.sup.2 is preferably
a group of the formula (II), given and defined above and L.sup.2 is
preferably a linking group selected from the groups (VII).sup.1,
(VII).sup.2 and (VII).sup.3, given and defined above, more
preferably a group of the formula (VII).sup.2 or
[0150] (VII).sup.3, given and defined above; and
[0151] L.sup.1 is a group of the formula (VII).sup.3, given and
defined above, in which B is an optionally substituted aryl group,
or is alternatively a chromophoric bridging group.
[0152] In the range of dyes of formulae (XXXII), a preferred
chromophore D is a disazo dye containing a residue derived from
H-acid and having azo groups at the 2- and 7-positions.
[0153] Another preferred chromophore D is a group of the formula
14
[0154] Other ranges of dyes embodying the invention are of the
respective formulae
D.sup.2-L.sup.2-Z.sup.2-L.sup.3-D.sup.1-L.sup.1-Z.sup.1 (XXXIV)
[0155] wherein:
[0156] each of D.sup.1 and D.sup.2, independently, is a
chromophore;
[0157] L.sup.3 is a linking group selected from groups of the
formula (I)-(III), given and defined above; and
[0158] each of Z.sup.1, Z.sup.2, L.sup.1 and L.sup.2 is as defined
above; and 15
[0159] wherein:
[0160] each of D.sup.1 and D.sup.2, independently, is a
chromophore;
[0161] L.sup.1 is a linking group selected from the groups of the
formulae (I)-(III), given and defined above; and
[0162] each of Z.sup.1, Z.sup.2, L.sup.1 and L.sup.2 is as defined
above; and 16
[0163] wherein:
[0164] one of Z.sup.3 and Z.sup.4 is a reactive group Z.sup.2;
[0165] each of Z.sup.3 and Z.sup.4, independently, is a reactive
group selected from the formulae (IV)-(VI), given and defined
above;
[0166] each of t and u, independently, is zero or 1 and at least
one of t and u is 1;
[0167] D is a chromophore;
[0168] Ar is an optionally substituted aryl group;
[0169] L.sup.1 is a group of the formula 17
[0170] wherein each R, independently, is as defined in claim;
and
[0171] Z.sup.1 is as defined above.
[0172] In such dyes of formulae (XXXVI), D is preferably a disazo
dye containing a residue derived from H-acid.
[0173] In a dye embodying the invention, the or a chromophore D may
contain a heterocyclic nitrogen atom, in which case the linking
group may have the formula 18
[0174] wherein each of B, R and b is as defined above and the bond
{circle over (1)}, is linked to the heterocyclic nitrogen atom of
the chromophore.
[0175] Such dyes, may have the formula
Z.sup.1-L.sup.1-D.sup.NL.sup.2Z.sup.2L.sup.5-Ar].sub.t
[0176] wherein:
[0177] D.sup.N is a chromophore containing a heterocyclic group
including a nitrogen atom;
[0178] L.sup.1 is a group of the formula (VII).sup.4 or
(VII).sup.5, given and defined above, directly attached via the
bond {circle over (1)}, to the nitrogen atom of the said
chromophore D.sup.N;
[0179] Ar is an optionally substituted aryl group;
[0180] and each of Z.sup.1, Z.sup.2, L.sup.2, L.sup.5, a and t is
as defined above.
[0181] A typical chromophore D containing a heterocyclic nitrogen
atom has the formula 19
[0182] In the above formulae, wherever L.sup.5-L.sup.5, J.sup.1,
J.sup.2 or B is or has an optionally substituted phenyl group,
optional substituents are SO.sub.3H or a salt thereof,
C.sub.1-4alkyl, especially methyl and chloro, especially
SO.sub.3H.
[0183] Again, in all of the above formulae, where the groups
Z.sup.2 is any of the groups of the formulae (I)-(III), it is most
preferably of the formula (II).
[0184] Likewise in all such formulae, where Z.sup.2 is any of the
groups (IV)-(VI), it is most preferably of the formula (IV) or (V)
wherein Z is zero.
[0185] In a dye according to the invention, in general, the or each
chromophoric group independently preferably comprises an azo (which
may be a monoazo, polyazo or metal complex azo), anthraquinone,
hydrazone, phthalocyanine, triphenodioxazine or formazan group.
Examples of chromophoric groups which may be present are those
given as types (a)-(g) of the group "D.sub.1," in formula (I) of
U.S. Pat. No. 5,484,899, which is incorporated herein by
reference.
[0186] Preferred azo groups are monoazo and disazo groups.
Preferred monoazo groups have the formula
--Ar.sup.1-N.dbd.N--Ar.sup.2
[0187] wherein Ar.sup.1 is an aryl or heteroaryl group and Ar.sup.2
is an aryl group.
[0188] It is preferred that each aryl group independently is a
mono- or di-cyclic aryl group. Preferred aryl groups are optionally
substituted phenyl and optionally substituted naphthyl. Preferred
heteroaryl groups are pyridonyl and pyrazolonyl.
[0189] A first preferred monoazo group is of the Formula (IX) (or
salt thereof) 20
[0190] wherein:
[0191] Ar.sup.1 is an aryl group, preferably a benzene or
naphthalene nucleus;
[0192] R.sup.3, or each R.sup.3 independently, is C.sub.1-4 alkyl,
nitro, halo or sulphonic acid or a salt thereof;
[0193] c is zero or 1 to 4;
[0194] R.sup.4, or each R.sup.4 independently, is a sulphonic acid
or a salt thereof; and
[0195] d is 1 or 2;
[0196] and is more preferably of the formula: 21
[0197] wherein each of Ar.sup.1, R.sup.3 and a are as defined
above, R.sup.4 is sulpho and c is zero or 1.
[0198] Ar.sup.1 is preferably optionally substituted phenyl or
naphthyl, especially a phenyl or naphthyl group having at least one
sulpho substituent. Further optional substituents which may be
present on Ar include a halogen atom, especially chlorine; an alkyl
radical, especially C.sub.1-4 alkyl, more especially methyl; an
acylamido radical, especially-acetylamino, benzamido or sulphonated
benzamido; amino; hydroxy; and an alkoxy radical, especially
C.sub.1-4 alkoxy, more especially methoxy.
[0199] As examples of phenyl groups having at least one sulpho
substituent there may be mentioned 2-, 3- or 4-sulphophenyl;
2-sulpho-4-nitrophenyl; 2-sulpho-5-nitrophenyl;
4-sulpho-2-methylphenyl; 5-sulpho-2-methylphenyl;
2-sulpho-4-methylphenyl; 5-sulpho-2-methoxyphenyl;
2-sulpho-4-methoxyphenyl; 4-sulpho-2-chlorophenyl;
5-acetamido-2-sulphophenyl; 5-sulpho-2-carboxyphenyl;
2,4-disulphophenyl; 2,5-disulphophenyl; and 3,5-disulphophenyl.
[0200] As examples of naphthyl groups having at least one sulpho
substituent there may be mentioned 1-sulphonaphth-2-yl;
1,5-disulphonaphth-2-yl; 1,5,7-trisulphonaphth-2-yl;
3,6,8-trisulphonaphth-2-yl; 5,7-disulphonaphth-2-yl;
6-sulphonaphth-2-yl; 4-,5-,6-, or 7-sulphonaphth-1-yl;
4,8-disulphonaphth-1-yl; 3,8-disulphonaphth-1-yl;
2,5,7-trisulphonaphth-1-yl; and 3,5,7-trisulphonaphth-1-yl.
[0201] Preferred optional substituents which may be present on the
naphthalene nucleus of Formula (IX) are those mentioned above for
Ar.sup.1.
[0202] Groups of the Formula (IX) are preferably linked to a group
L.sup.1 or L.sup.2 at the 6-, 7- or 8-position, especially the 6-
or 8-position. When L.sup.1 or L.sup.2 is to be linked at the
8-position, it is preferred that R.sup.5 is a sulpho group at the
5- or 6-position.
[0203] Thus a preferred monoazo dye embodying the invention has the
formula (XVII) 22
[0204] wherein:
[0205] each R independently and a is as defined above;
[0206] one of Z.sup.3 and Z.sup.4 is a group Z.sup.1 and the other
is a group Z.sup.2;
[0207] the group Z.sup.4 is selected from the groups of the
formulae (I)-(III), given and defined above.
[0208] Ar.sup.1 is a benzene or naphthalene nucleus;
[0209] R.sup.3, or each R.sup.1 independently, is C.sub.1-4 alkyl,
nitro, halo or sulphonic acid or salt thereof;
[0210] c is zero or 1-4;
[0211] R.sup.4, or each R.sup.4 independently, is a sulphonic acid
or a salt thereof; and
[0212] d is 1 or 2.
[0213] A preferred disazo group is of the Formula (XI) (or salt
thereof):
Ar.sup.1-N.dbd.N-M-N.dbd.N-E (XI)
[0214] wherein:
[0215] M and E are each independently optionally substituted
phenylene or naphthalene; and
[0216] Ar.sup.1 is as defined above.
[0217] It is preferred-that E is optionally substituted naphthalene
and M is optionally substituted phenylene. The optional
substituents which may be present on M or E are preferably
independently selected from halo, especially chloro; alkoxy,
especially C.sub.1-4 alkoxy; alkyl, especially methyl; sulpho;
carboxy; hydroxy; amino; acylamino, especially acetamido, benzamido
and sulphonated benzamido, and pyrimidinylamino or triazinylamino
cellulose-reactive groups.
[0218] As Examples of groups represented by M and E, there may be
mentioned phenylene, 2-methyl-1,4-phenylene, sulphophenylene,
ureidophenylene, 7-sulpho-1,4-naphthalene,
6-sulpho-1,4-naphthalene; 8-sulpho-1,4-naphthalene and
6-hydroxy-4-sulpho-1,5-naphthalene.
[0219] An especially preferred range of disazo-dyes has the formula
(XVIII) 23
[0220] wherein:
[0221] one of Z.sup.5 and Z.sup.6 is a group Z.sup.1 and the other
is a group Z.sup.2;
[0222] each of f and g independently is zero or 1;
[0223] when Z.sup.5 or Z.sup.6 is any of the groups of the formulae
(I)-(III), given and defined above, f or q respectively is 1 and
when Z.sup.5 or Z.sup.6 is any of the groups of the formulae
(IV)-(VI), given and defined above, f or g respectively is
zero;
[0224] each of c and e, independently, is zero or 1-4;
[0225] d is 1 or 2;
[0226] each R independently is as defined above;
[0227] each of Ar.sup.1 and Ar.sup.2 independently is an optionally
substituted aryl group; and
[0228] each of R.sup.3 and R.sup.4 is as defined above.
[0229] In a dye of the formula (XVIII), each of Z.sup.5 and Z.sup.6
may be the same group 24
[0230] wherein X, Y and n are as defined above.
[0231] Alternatively, one of Z.sup.5 and Z.sup.6 may be a group of
the formula (I), given and defined above, and the other of Z.sup.5
and Z.sup.6 may be selected from groups of the formulae (II) and
(III), given and defined above. In such a dye it is preferred that
one of Z.sup.5 and Z.sup.6 is a group of the formula (I), given and
defined above, and the other of Z.sup.5 and Z.sup.6 is a group of
the formula (II).
[0232] Another especially preferred range of disazo dyes has the
formula 25
[0233] wherein:
[0234] B is a hydrocarbon bridging group as defined above, and
preferably an optionally substituted aryl group;
[0235] one of G.sup.1 and G.sup.2 is OH and the other is
NH.sub.2;
[0236] each of X, Y, Y.sup.1,Ar.sup.1, Ar.sup.2, R.sup.3, R.sup.4,
R.sup.5, c, d and
[0237] e is as defined above.
[0238] In a dye of the formula (XVIII), one of Z.sup.5 and Z.sup.6
may be a group 26
[0239] wherein:
[0240] X, Y and n are as defined in claim 1 and the other of
Z.sup.5 and Z.sup.6 is the group
--SO.sub.2CH.sub.2CH.sub.2OSO.sub.3H or
--SO.sub.2CH.dbd.CH.sub.2.
[0241] Typically such a dye has the formula 27
[0242] wherein G.sup.3 is C.sub.2H.sub.4OSO.sub.3H or a salt
thereof or --CH.dbd.CH.sub.2;
[0243] G.sup.1 and G.sup.2 are as defined above;
[0244] R.sup.4 and d are as defined above; and
[0245] each of h and i, independently, is zero, 1 or 2.
[0246] A more preferred range of such dyes has the formula 28
[0247] where each of G.sup.1G.sup.2 and G.sup.3 is as defined
above.
[0248] When the chromophore D is an anthraquinone, a preferred
anthraquinone group is of the Formula (XII) (or a salt thereof).
29
[0249] wherein the anthraquinone nucleus optionally contains a
sulphonic acid group in the 5-, 6-, 7-, or 8-position and V is a
divalent organic linking group, preferably of the benzene
series.
[0250] V is a bridging group B, preferably phenylene, diphenylene,
or 4,4'-divalent stilbene or azobenzene radicals which are
optionally sulphonated. It is preferred that V contains one
sulphonic acid group for each benzene ring present therein.
[0251] A preferred anthraquinone dye of has the formula
D.sup.A-L.sup.3-Ar-L.sup.2-Z.sup.2-L.sup.1Z.sup.1
[0252] wherein:
[0253] D.sup.A is an anthraquinone chromophore;
[0254] L.sup.3 is a linking of the formula (VII).sup.1, given and
defined above;
[0255] Ar is an optionally substituted aryl group; and each of
Z.sup.1, Z.sup.2, L.sup.1 and L.sup.2 is as defined above.
[0256] More preferably each of L.sup.1 and L.sup.2 independently,
is a linking group of the formula (VII).sup.1, (VII).sup.2 or
(VII).sup.3, given and defined above; and still more preferably,
each of L.sup.1 and L.sup.2, independently is a group of the
formula (VII).sup.3, given and defined above, in which B is an
optionally substituted aryl group.
[0257] When the chromophore D is a phthalocyanine, a preferred
phthalocyanine group is of the Formula (XIII) (or a salt thereof).
30
[0258] wherein Pc is a metallo-phthalocyanine nucleus, preferably
copper or nickel phthalocyanine; L is as hereinbefore defined; each
W independently is a hydroxy or a substituted or unsubstituted
amino group, V.sup.1 is a divalent organic linking group,
preferably a C.sub.14-alkylene or phenylene linking group; and a
and b are each independently 1, 2 or 3 provided that a+b is not
greater than 4.
[0259] Preferably such a metal phthalocyanine dye has the formula
31
[0260] wherein:
[0261] Cu Pc is a copper phthalocyanine chromophore;
[0262] X+Y+Z.ltoreq.4;
[0263] each of R.sup.21 and R.sup.22, independently, is hydrogen or
optionally substituted C.sub.1-4alkyl;
[0264] B is a hydrocarbon bridging group; and
[0265] Z.sup.1 is as defined above.
[0266] When the chromophore D is a triohenodioxazine a preferred
triphenodioxazine group is of the Formula (XIV) (or a salt
thereof). 32
[0267] wherein:
[0268] each Y.sup.3 independently is a covalent bond,
C.sub.2-4-alkylene, phenylene or sulphophenylene;
[0269] U.sup.1 is H or SO.sub.3H; and
[0270] T.sup.1 and T.sup.2 are halo, especially chloro,
C.sub.1-4-alkyl, or C.sub.1-4 alkoxy.
[0271] Each Y.sup.3 is preferably --C.sub.2H.sub.4-- or
--C.sub.3H.sub.6--, U.sup.1 is preferably SO.sub.3H and T.sup.1 and
T.sup.2 are preferably Cl, methyl or ethyl.
[0272] Preferably such a triphendioxazine dye has the formula
Z.sup.1-L.sup.1-[Z.sup.3-L.sup.3].sub.q-D.sup.T[Z.sup.4].sub.r-L.sup.2-Z.s-
up.2
[0273] wherein:
[0274] D.sup.T is a triphendioxazine chromophore;
[0275] each of L.sup.2, L.sup.3 and L.sup.4, independently, is a
linking group of the formula (VII).sup.1, (VII).sup.2 or
(VII).sup.3, given and defined above;
[0276] each of Z.sup.2, Z.sup.3 and Z.sup.4 is a reactive group
selected from groups of the formulae (I)-(III), given and defined
above;
[0277] each of q and r is zero or 1; and
[0278] each of Z.sup.1 and L.sup.1 is as defined above.
[0279] In such a dye, Z.sup.2 is preferably a group of the formula
(I), given and defined above and each of Z.sup.3 and Z.sup.4 is a
group of the formula (II), given and defined above; and each of
L.sup.1, L.sup.2, L.sup.3 and L.sup.4 is preferably a group of the
formula (VII).sup.3, given and defined above.
[0280] When the chromophore D is a formazan, a preferred group is
of the Formula (XV) (or a salt thereof) 33
[0281] wherein:
[0282] X.sup.1 is H, SO.sub.3H or Cl; and
[0283] each r independently has a value of 0, 1 or 2.
[0284] provided that the formazan group has at least one, and
preferably at least two, sulpho groups.
[0285] It is preferred that each r has a value of 1.
[0286] Preferably such a formazan dye has the formula
[Z.sup.A].sub.a-D.sup.F-L-Z.sup.B-L.sup.1-Z.sup.1
[0287] wherein:
[0288] D.sup.F is a formazan chromophore;
[0289] one of Z.sup.A and Z.sup.B is a group Z.sup.2, given and
defined above;
[0290] each of L.sup.1 and L.sup.4 is a linking group of the
formula (VII).sup.1, (VII).sup.2 or (VII).sup.3, given and defined
above;
[0291] each of Z.sup.1 and L.sup.1 is as defined above;
[0292] a is zero or 1;
[0293] Z.sup.A is selected from groups of the formulae (IV)-(VI),
given and defined above; and
[0294] Z.sup.B is selected from groups of the formulae (I)-(III),
given and defined above.
[0295] According to one process aspect, the invention provides a
process for preparing a dye of the formula (VIII)
Z.sup.1-L.sup.1-D-L.sup.2-Z.sup.2 (VIII)
[0296] wherein:
[0297] D is a chromophore;
[0298] each of L.sup.1 and L.sup.2 independently, is N(R);
[0299] each R, independently, is hydrogen or C.sub.1-4alkyl;
[0300] each of Z.sup.1 and Z.sup.2 is a group 34
[0301] in which:
[0302] n is 1 or 2
[0303] X, or each X independently, is an electron withdrawing
group; and
[0304] Y is a halogen atom,
[0305] which process comprises reacting a chromophoric compound of
the formula (XX)
H(R)N-D-N(R)H (XX)
[0306] wherein each of D and R is as defined above, with at least
two moles, per mole of the chromophoric compound of the formula
(XX), of a dihalobenzene component comprising at least one
dihalobenzene compound of the formula (XXI) 35
[0307] wherein each of X, Y and n is as defined above, to obtain
the dye of the formula (VIII).sup.1.
[0308] When the dye is of the formula (XVIII) given above, the
chromophoric compound of the formula (XX) can be prepared by
protecting one amino group of a phenylene diamine sulphonic acid
and then diazotising this and coupling a first portion of the
diazotised phenylene diamine sulphonic acid to the naphthalene
nucleus under acid conditions so as to couple on to the benzene
ring of the naphthalene nucleus containing an amino group and then
taking a second portion of the same diazotised and protected
phenylene diamine sulphonic acid compound referred to above (or a
different such compound) and coupling this under neutral or
alkaline conditions to the benzene ring of the naphthalene nucleus
containing a hydroxyl group to obtain a diamine dyestuff having
respective protected amino groups. The protective group can then be
removed by hydrolysis.
[0309] According to another process aspect, the invention provides
a process for preparing a dye of the formula (VIII).sup.1
Z.sup.1-L.sup.1-D-L.sup.2-Z.sup.2 (VIII).sup.2
[0310] wherein:
[0311] D is a chromophore;
[0312] each of L.sup.1 and L.sup.2 independently, is N(R);
[0313] each R, independently, is hydrogen or C.sub.1-4alkyl;
[0314] Z.sup.1 is a group 36
[0315] in which:
[0316] n is 1 or 2
[0317] X, or each X independently, is an electron withdrawing
group; and
[0318] Y is a halogen atom; and
[0319] Z.sup.2 is selected from the groups (II) and (III) defined
above;
[0320] which process comprises reacting a chromophoric compound of
the formula (XX)
H(R)N-D-N(R)H (XX)
[0321] wherein each of D and R is as defined above, with one mole,
per mole of the chromophoric compound of the formula (XX), of each
of
[0322] (a) a dihalobenzene compound of the formula (XXI) 37
[0323] wherein each of Z, X, Y and n is as defined above; and
[0324] (b) a compound selected from 38
[0325] wherein:
[0326] m is 1 or 2; p is 0 or 1; when m is 1, p is 1; and when m is
2, p is 0;
[0327] Y.sup.1, or each Y.sup.1 independently, is a halogen atom or
an optionally substituted pyridinium group; and
[0328] T is C.sub.1-4alkoxy, C.sub.1-4thioalkoxy or N(R.sup.1)
(R.sup.2) in which each of R.sup.1 and R.sup.2 independently is
hydrogen, optionally substituted C.sub.1-4alkyl or optionally
substituted aryl;
[0329] x is 1, 2 or 3; y is zero, 1 or 2; and x+y.ltoreq.3;
[0330] Y.sup.2, or each Y.sup.2 independently, is a halogen atom or
an optionally substituted pyridinium group;
[0331] U or each U independently, is C.sub.1-4alkyl or
C.sub.1-4alkylsulphonyl; and
[0332] Y is as defined above;
[0333] the said reactions of the compound of the formula (XX) with
each of the respective compounds of the formulae (XII) and (XIII)
being carried out simultaneously or one before the other, in either
order, to obtain a dye of the formula (VIII).sup.2.
[0334] According to yet another process aspect, the invention
provides a process for preparing a dye of the formula
(VIII).sup.3
Z.sup.1-L.sup.1-D-Z.sup.2 (VIII).sup.3
[0335] wherein:
[0336] D is a chromophore
[0337] L.sup.1 is N(R), in which R is hydrogen or
C.sub.1-4alkyl;
[0338] Z.sup.1 is a group 39
[0339] in which n is 1 or 2; X, or each X independently, is an
electron withdrawing group; and Y is a hydrogen atom; and Z.sup.2
is a group of the formula (IV)
--SO.sub.2CH.sub.2CH.sub.2X.sup.1 (IV)
[0340] wherein X.sup.1 is an eliminatable group;
[0341] a group of the formula (V)
--SO.sub.2(CH.sub.2).sub.ZCH.dbd.CH.sub.2 (V)
[0342] wherein z is zero or 1; and
[0343] a group of formula (VI)
--W--C(R.sup.10).dbd.CH.sub.2 (VI)
[0344] wherein:
[0345] R.sup.10 is hydrogen, C.sub.1-4alkyl or halogen; and
[0346] W is --OC(.dbd.O)-- or --N(R.sup.11)C(.dbd.O)-- in which
R.sup.11 is hydrogen or C.sub.1-4alkyl;
[0347] which process comprises reacting a chromophoric compound of
the formula (XXIV)
H(R)N-D-Z.sup.2 (XXIV)
[0348] wherein D and Z.sup.2 are as defined above, with a
dihalobenzene compound of the formula (XXI) 40
[0349] wherein each of X, Y and n is as defined above, to obtain
the dye of the formula (VIII).sup.3.
[0350] Although dye formulae have been shown in the form of their
free acid in this specification, the invention also includes dyes
and processes using dyes in the salt form, particularly their salts
with alkali metals such as the potassium, sodium, lithium or mixed
sodium/lithium salt and their salts with tetraalkylammonium
ions.
[0351] The dyes may be used for dyeing, printing or ink-jet
printing, for example, of textile materials and paper.
[0352] The process for colouration is preferably performed at a pH
of 7.1 to 13, more preferably 10 to 12. pH levels above 7 can be
achieved by performing the process for colouration in the presence
of an acid-binding agent.
[0353] The substrate may be any of a textile material, leather,
paper, hair or film, but is preferably a natural or artificial
textile material containing amino or hydroxyl groups, for example
textile material such as wool, silk, polyamides and modified
polyacrylonitrile fibres, and more preferably a cellulosic
material, especially cotton, viscose and regenerated cellulose, for
example, that commercially available as Tencel. For this purpose
the dyes can be applied to the textile materials at a pH above 7
by, for example, exhaust dyeing, padding or printing, including
ink-jet printing. Textile materials are coloured bright shades and
possess good fastness to light and wet treatments such as
washing.
[0354] The new dyes are particularly valuable for colouring
cellulosic textile materials. For this purpose, the dyes are
preferably applied to the cellulosic textile material at a pH above
7 in conjunction with a treatment with an acid binding agent.
[0355] Preferred acid-binding agents include alkali metal
carbonates, bicarbonates, hydroxides, metasilicates and mixtures
thereof, for example sodium bicarbonate, sodium carbonate, sodium
metasilicate, sodium hydroxide and the corresponding potassium
salts. The dyes benefit from the excellent build-up and high
fixation.
[0356] At least for cellulosic materials, exhaust dyeing can be
carried out at a relatively low temperature of about 50-70.degree.
C., especially about 60.degree. C.
[0357] The new dyes can be applied to textile material containing
amine groups, such as wool and polyamide textile materials, from a
neutral to mildly alkaline dyebath. The dyeing process can be
carried out at a constant or substantially constant pH, that is to
say that the pH of the dyebath remains constant or substantially
constant during the dyeing process, or if desired the pH of the
dyebath can be altered at any stage of the dyeing process.
[0358] The dyes may be in a liquid form, or solid form, for example
in granular or powdered form.
[0359] We find surprisingly that such dyes give a much higher build
up, as compared with known dyestuffs, particularly in warm dyeing
applications at about 60.degree. C.
[0360] In addition, a wide selection of dye backbones is possible,
giving the potential to provide high fastness dyes.
[0361] Dyes embodying the invention are especially useful for
application to substrates by ink-jet technologies. Substrates which
are particularly useful are cellulosic textiles and paper.
[0362] The dye used in the ink is preferably purified by removal of
substantially all the inorganic salts and by-products which are
generally present in a commercial dye at the end of its synthesis.
Such purification assists in the preparation of a low viscosity
aqueous solution suitable for use in an ink jet printer.
[0363] To assist in the achievement of heavy depths of shades the
dye should preferably have a water-solubility of at least 5%, and
more preferably from 5% to 25%, by weight. Solubility of the dye
can be enhanced by converting the sodium salt, in which form it is
normally synthesised, either partially or wholly, into the lithium
or ammonium salt. Purification and ion exchange can conveniently be
effected by use of membrane separation processes which permit the
separation of unwanted inorganic materials and by-products directly
from an aqueous solution or dispersion of the dye followed by
partial or complete exchange of the counter-ion. The ink preferably
contains up to 20% by weight of dye and more preferably from 2% to
10%, especially from 3% to 8%.
[0364] The ink may also contain a humectant, which may also
function as a water miscible solvent, which preferably comprises a
glycol or dihydroxyglycolether, or mixture thereof, in which one or
both hydroxy groups are secondary hydroxy groups, such as
propane-1,2-diol, butane-1,3-diol and
3-(3-hydroxy-prop-2-oxy)propan-2-ol.
[0365] Where the humectant has a primary hydroxy group this is
prefereably attached to a carbon atom adjacent to a carbon atom
carrying a secondary or tertiary hydroxy group. The humectant may
comprise up to a total of 10% by weight of a polyol, especially a
glycol or dihydroxyglycolether, having two or more primary hydroxy
groups, such as ethyleneglycol, propane-1,3-diol,
butane-1,4-diol,2-(2-hydroxyethoxy)ethanol and
2-(2-[2-hydroxyethoxy)ethanol and/or an alcohol with a primary
hydroxy group, such as ethanol, n-propanol and n-butanol. However,
it preferably contains not more than 5% by weight, and is more
preferably free from, such compounds. In the context of the
humectant, the term "alcohol" means a compound having only one
hydroxy group attached to an aliphatic carbon atom. The ink
preferably contains from 5% to 25%, by weight, more especially from
10% to 20%, of humectant.
[0366] If desired, the ink may be buffered to a pH from 5 to 8,
especially to a pH from 6 to 7, with a buffer such as the sodium
salt of metanilic acid or an alkali metal phosphate, or di- or
triethanolamine.
[0367] The ink preferably also contains one or more preservatives
to inhibit the growth of fungi, bacteria and/or algae because these
can block the jet of the ink jet printing equipment. Where the ink
jet printing technique involves the charging and electrically
controlled deflection of drops the solution preferably contains a
conducting material such as an ionised salt to enhance the
accumulation of charge on the drop. Suitable salts for this purpose
are alkali metal salts of mineral acids. The remainder of the ink
is preferably water, especially de-ionised water to avoid the
introduction of impurities into the ink.
[0368] Especially preferred embodiments of the invention will now
be described in more detail with reference to the following
Examples in which all parts and percentages are by weight unless
otherwise stated. Although preparation and dyeing with any single
dye is exemplified, particular advantage could be seen when dyeing
with mixtures of dyes.
PREPARATIVE EXAMPLES
Example 1
[0369] 2-amino-4-(N-acetyl)aminobenzene-1-sulphonic acid (0.5M, 182
g) was dissolved in water (600 ml) at pH 7 and 2M sodium nitrite
solution added (0.526M, 263 ml). This solution was added dropwise
to a mixture of hydrochloric acid 35% (1.13M, 100 ml, SG=1.18) and
ice (1 Kg), maintaining a temperature of 0-5.degree. C. The mixture
was stirred for 0.5 hrs with excess nitrous acid at 0-5.degree. C.
A solution of sulphamic acid (10%) was added to remove excess
nitrous acid to obtain a suspension of a diazotized diamine for
coupling.
[0370] H-Acid (0.475M, 183 g) was dissolved in water (800 ml) at pH
7.5. This solution was added dropwise to the above diazo suspension
with good agitation over 1 hr at 0-2.degree. C. The mixture was
then stirred at 0-2.degree. C. for a further 2 hrs at pH 2-3, and
allowed to warm to room temperature over 18 hrs.
[0371] The viscous suspension was adjusted to pH 6 using sodium
hydroxide solution (46/48%) and a solution of a monoazo dye was
thereby obtained.
[0372] The above monoazo dye solution was cooled to 0-5.degree. C.
and a batch of the diazotized diamine prepared as above was added.
The mixture was stirred at 0-5.degree. C. and pH 6-7 for 2 hrs and
subsequently over 18 hrs at room temperature while maintaining the
pH at 6-7 using 2M sodium carbonate solution, thereby obtaining a
disazo dye solution.
[0373] Hydrolysis was then carried out by adding sodium hydroxide
solution (46/48%, 800 g) to the above disazo dye solution (vol=5L)
and heating at 70-75.degree. C. for 1.5 hrs.
[0374] The reaction mixture was cooled to 20.degree. C. and
neutralised by controlled addition of 35% hydrochloric acid. After
screening to remove a small amount of impurity sodium chloride was
added (15% w/v) and stirring continued to allow precipitation of
the resultant diaminodisazo product. This was collected by
filtration and dried at 40.degree. C. (285 g; 0.242M; strength
=68.3%).
[0375] The above diaminodisazo dye (0.01M, 11.78 g) was dissolved
in water/acetone (100 ml, 1:1) at 50.degree. C. A solution of
1,5-difluoro-2,4-dinitrobenzene (0.023M, 4.7 g taken as 100%
strength) in acetone (20 ml) was added over 0.25 hr and the mixture
heated at 55.degree. C. for 3 hrs. The pH was maintained at 7
throughout the reaction by the addition of 2N sodium carbonate
solution.
[0376] The reaction mixture was cooled to 20.degree. C. and acetone
(150 ml) added to precipitate the dye. The product was collected by
filtration and washed with acetone (50 ml) and dried at 40.degree.
C. to give a greenish-navy dye (11.12 g; 0.0075M;
strength=74.8%)(.lambda..sub.Max=607 nm;
.epsilon..sub.Max=57,036).
Example 2
[0377] The method of Example 1 was followed except that the
diaminodisazo was reacted with 1,5-dichloro-2,4-dinitrobenzene in
place of 1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy
dye (.lambda..sub.Max=607 nm; .epsilon..sub.Max=48,212).
Example 3
[0378] The method of Example 1 was followed except that the
diaminodisazo was reacted with 1,5-difluoro-2-cyan-4-nitrobenzene
in place of 1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy
dye (.lambda..sub.Max=607 nm; .epsilon..sub.Max=56,416).
Example 4
[0379] The method of Example 1 was followed except that the
diaminodisazo was reacted with 1,5-difluoro-2-nitrobenzene in place
of 1,5-difluoro-2,4-dinitrobenzene to give a greenish-navy dye
(.lambda..sub.aMax=608 nm; .epsilon..sub.Max=54,660).
Example 5
[0380] 4-Amino benzene sulphatoethylsulphone (0.1M, 30 g) was
stirred in ice/water (400 ml) and hydrochloric acid 35% (0.58M, 52
ml, SG=1.18) and the temperature maintained at below 5.degree. C.
2M Sodium nitrite solution (0.104M, 52 ml) was added dropwise at
below 5.degree. C. and the mixture stirred for a further 2 hours. A
solution of sulphamic acid was added (10%) to remove excess nitrous
acid and provide a diazo suspension for coupling.
[0381] H-Acid (0.103M, 42.6 g) was dissolved in water (300 ml) at
pH 6 and the solution cooled to 5.degree. C. This solution was
added dropwise to the above diazo suspension with good agitation,
while maintaining the temperature below 5.degree. C. The mixture
was then stirred for 18 hours, allowing the temperature to rise to
20.degree. C. Sodium chloride (10% w/v) was added and the mixture
stirred for 1 hour. The precipitated monoazo dye was collected by
filtration and reslurried in ethanol (600 ml) for 1 hour at
20.degree. C. The product was collected by filtration and dried at
40.degree. C. (70 g; 0.0825M; strength =72%).
[0382] 3-Amino-5'-fluoro-2',4'-dinitrodiphenylamine-4-sulphonic
acid (0.0068M, 3.2 g) was dissolved in water (100 ml) at
50-60.degree. C. and the solution cooled to 20.degree. C. 2M Sodium
nitrite solution (0.008M, 4 ml) was added and the mixture cooled to
0-2.degree. C. and added dropwise to ice (50 g) and hydrochloric
acid 35% (0.09M, 8 ml), while maintaining the temperature at
0-2.degree. C. The resulting yellow suspension was stirred at
0-2.degree. C. for 0.5 hour and a solution of sulphamic acid (10%)
added to remove excess nitrous acid and provide a diazo suspension
for coupling.
[0383] The diazo suspension was then added dropwise to a solution
of the above monoazo dye (0.006M, 5.1 g) in water (150 ml) at pH 5
and 0-2.degree. C. The pH of the coupling mixture was maintained at
pH 5 by the addition of 2M sodium carbonate solution and stirred at
this pH for 18 hours, allowing the temperature to rise to
20.degree. C. Sodium chloride was added (20% w/v) and the product
collected by filtration. The solid was reslurried in ethanol (100
ml) for 1 hour at 20.degree. C., collected by filtration and dried
at 40.degree. C. to obtain a greenish-navy dye (4.4 g; 0.003M;
strength =67%) (.lambda..sub.Max=603 nm; .epsilon..sub.Max=54,279)
of the structure given below: 41
Examples 6-61
[0384] Other disazo naphthalene structures embodying the invention
are shown as Examples 6 to 61 in Table 1. They can be prepared by
methods analogous to those outlined in Examples 1 to 5.
Examples 62-67
[0385] Still further disazo naphthalene dyes embodying the
invention, in which the chromophore has been doubled up via a
linking group, are shown in Examples 62 to 67 in Table 2.
Example 68
[0386] This Example describes how a dye may be synthesised where
the fibre-reactive halobenzene group is attached via a linking
diamine to a second fibre-reactive group, and thereby to a
chromophore. 42
[0387] The N-dichlorotriazinyl derivative of the azo dye resulting
from azo-coupling 7-aminonaphthalene-1,3,6-trisulphonic acid with
m-ureidoaniline was prepared by conventional means. A solution of
this dye (35 mmol in 450 ml) was added at room temperature with
stirring to N-(4-aminophenyl)piperazine (7.5 g, 42 mmol) dissolved
in 50/50 acetone/water (400 ml) maintained at pH 6-6.5 by addition
of sodium carbonate solution. After completion of the reaction the
solution was concentrated, and the product was precipitated by
addition of methylated spirit. To a solution of this intermediate
(8.4 mmol) in 50/50 acetone/water (200 ml) was added a solution of
1,5-difluoro-2,4-dinitrobe- nzene (8.5 mmol) in acetone (20 ml),
maintaining the pH at 8.5 by addition of sodium carbonate solution.
On completion of the reaction, the pH was adjusted to 6.5 and the
solution was concentrated to ca 100 ml. Methylated spirit was
added, and the product dye was filtered, washed with meths and
dried. .lambda..sub.max(water)=379 nm, .epsilon..sub.max=33000 l
mol.sup.-1 cm.sup.-1, half band width >150 nm. This material
dyed cotton a bright golden yellow shade with very good fastness
properties.
Examples 69-77
[0388] By following the principles described in Example 68, dyes of
a similar nature may be prepared as further exemplified by dyes
69-77 listed in Table 3.
Examples 78-97
[0389] Disazo naphthalene dyes containing two reactive groups
attached to the chromophore as described in Example 68 are
exemplified by Examples 78 to 97 listed in Table 4.
Examples 98-127
[0390] Further yellow dyes may be prepared by the methods described
in Examples 1-6 and 68, and are listed in Tables 5 to 9.
Examples 128-160
[0391] Monoazo naphthalene dyes embodying the invention are listed
in Tables 10 to 12.
Examples 161-189
[0392] A variety of dyes embodying the invention, containing blue
and green chromophores, are listed in Tables 13 to 16.
APPLICATION EXAMPLES
Examples 190-192
[0393] Each of the dyes (0.2 parts) of respective Examples 1, 3 and
5 was dissolved in respective amounts of water (50 parts) at
25.degree. C. and pH 9. Cotton fabric (5 parts) and Glaubers salt
(2.5 parts) were added. The dyes were fixed to the cotton by
raising the temperature to between 50.degree. C.-60.degree. C.,
basifying to pH 11.0 and maintaining this for 1 hr. The cotton was
removed and washed in soapy water to give a dark greenish-navy
cotton having high general fastness properties.
Examples 193 and 194
[0394] Each of the dyes (0.2 parts) of respective Examples 2 and 4
was dissolved in water (50 parts) at 25.degree. C. and pH 9. Cotton
fabric (5 parts) and salt (4 parts) were added. The dyes were fixed
to cotton by raising the temperature to 80-100.degree. C. and
maintaining this for 1 hr. The cotton was removed and washed in
soapy water to give a deep greenish-navy cotton having good
fastness properties.
Examples 195-198
[0395] Methodology for applying dyes embodying the present
invention to cotton may be further exemplified by means of the
following pad-batch dyeing protocol.
Example 195-198
[0396] Example 195.-Dye from Example 5 (0.5 parts) was dissolved in
water (30 parts) at 25.degree. C. and the following agents were
added: Primasol NF (1 part of 20% solution) and sodium silicate Q70
(9.5 parts of 50% solution), sodium hydroxide (5.1 parts of 10%
solution). The solution was made up to 50 parts by addition of
water, and then padded onto woven cotton fabric (70% pick-up) The
cloth was wrapped in cling film and batched at room temperature for
24 hours. The cling film was removed and the dyed cloth was rinsed
successively with cold water and hot water, then washed with a soap
solution, rinsed with water, and dried to give cotton coloured a
dull greenish blue shade.
Example 196
[0397] If the amount of dye used in Example 193 is doubled and the
procedure repeated, a greenish-navy shade is obtained.
Example 197
[0398] If the amount of dye used in Example 193 is trebled and the
procedure repeated, a dark navy shade is obtained.
Example 198
[0399] If six times the amount of dye in Example 193 is used and
the procedure repeated, an almost black shade is obtained.
[0400] Other dyes from the above Examples, particularly those
containing the 2,4-dinitrofluorobenzene unit and/or a vinyl
sulphone group or its sulphate half-ester precursor, can be applied
to cotton by the same method.
Example 199
[0401] Dyes embodying the present Invention may be applied to
textile substrates, especially cotton, by conventional printing
technology, as the following exemplifies.
[0402] A dye from Example 5 (30 parts) was dissolved in a solution
containing Manutex F 700 (500 parts of a 10% solution) and Vitexol
D (20 parts). The solution was made up to 1000 parts by the
addition of water and printed by means of a Zimmer screen printer.
The printed cloth was dried and padded through a solution
containing sodium silicate (48degBe, 700 parts) made up to 1000
parts by the addition of water (80% pickup). Immediately after
padding, the printed cotton was steamed in a Roaches Elash-ager
steam chamber at 120 deg C. for 45 seconds. The printed cloth was
rinsed in cold water, washed with a soap solution at the boil,
rinsed again in cold water and dried to give a dull greenish navy
print on the cotton.
Example 200
[0403] Dyes embodying the present invention may be used in the
preparation of inks specially formulated for application by ink-jet
technology. As an Example, the dye from Example 5 (6 parts) was
dissolved in a solution of propylene glycol (15 parts) and water
(79 parts). When this solution was applied to cotton which had
previously been pretreated (for example, with a pretreatment agent
described in EP-A-0534660) by means of commercial ink-jet printing
equipment, deep navy shades were obtained.
[0404] Other dyes from the above examples as well as others
described by the Invention may be used to prepare inks suitable for
ink-jet printing.
Example 201
[0405] Reactive dyes, including those of Examples 1-189, are
usually isolated as their sodium salts, and are contaminated with
inorganic impurities resulting from the method of preparation. Dyes
free of impurities suitable for ink jet printing, and/or with
increased solubility, may be prepared by conventional ion exchange
techniques, where for example sodium is replaced by lithium and
inorganic impurities are simultaneously removed.
[0406] Dye from Example 1 (10 parts) was dissolved in water (100
parts) and treated on a reverse osmosis rig until the permeate
conductivity was 10 micro reciprocal ohms. A solution of lithium
chloride was added to the dye solution and treatment on the r.o.
rig was continued until the permeate conductivity had decreased to
1 micro reciprocal ohm. The sample was concentrated to a volume of
about 80 parts, after which the solution was buffered and other
formulating agents were added. The dye solution was then diluted to
90 parts by addition of water, at which stage it was suitable for
storage. Dye solution prepared in this way could be diluted and
applied to cotton by the methods described in any of the Examples
190, 195-198, or formulated into an ink by addition of suitable
humectants and/or cosolvents, and applied by ink-jet methodology to
cotton, for example by the method described in Example 200. In all
these cases, dull blue, greenish navy or black shades were imparted
to the substrate, depending on the amount of dye applied.
Example 202
[0407] Dye from Example 1 was ion exchanged to the lithium form as
in Example 201, and formulated into an ink with the composition:
dye (5 parts), propylene glycol (12 parts), diethanolamine
(sufficient to buffer the final pH to 7-8.5), and water (to bring
the total to 100 parts). The ink was added to the ink reservoir of
an ink jet printer (e.g. HP Desk Jet 500) and printed onto paper
(Logic 300), to give a black print of generally good fastness
properties.
1TABLE 1 43 .lambda.max nm (W.sub.1/2 nm) Colour on Example A B
cotton 6 44 45 606 (121) greenish- navy 7 46 47 607 (105) greenish-
navy 8 48 49 623 (121) dark bluish- green 9 50 51 618 (121)
greenish- navy 10 52 53 603 (105) greenish- navy 11 54 55 618 (130)
greenish- navy 12 56 57 614 (110) dark bluish- green 13 58 59 594
(112) greenish- navy 14 60 61 595 (108) greenish- navy 15 62 63 604
(110) dark bluish green 16 64 65 645 (137) very dull dark green 17
66 67 604 (119) greenish- navy 18 68 69 603 (127) greenish- navy 19
70 71 600 (134) greenish- navy 20 72 73 596 120) greenish- navy 21
74 75 609 (111) greenish- navy 22 76 77 604 (120) greenish- navy 23
78 79 625 (104) greenish- navy 24 80 81 620 (112) dark bluish-
green 25 82 83 632 (114) dark bluish- green 26 84 85 609 (141) dark
bluish- green 27 86 87 602 (125) greenish- navy 28 88 89 605 (143)
dark bluish- green 29 90 91 596 (129) greenish- navy 30 92 93 607
(109) greenish- navy 31 94 95 595 (107) greenish- navy 32 96 97 622
(123) greenish- navy 33 98 99 619 (114) dark bluish- green 34 100
101 606 (114) dark bluish- green 35 102 103 618 (113) dark bluish-
green 36 104 105 616 (110) dark bluish- green 37 106 107 616 (106)
greenish- navy 38 108 109 616 (111) dark bluish- green 39 110 111
608 (111) greenish- navy 40 112 113 608 (116) greenish- navy 41 114
115 608 (116) greenish- navy 42 116 117 616 (111) dark bluish-
green 43 118 119 615 (120) dark bluish- green 44 120 121 615 (118)
dark bluish- green 45 122 123 greenish- navy 46 124 125 dark
bluish- green 47 126 127 greenish- navy 48 128 129 dark bluish-
green 49 130 131 greenish- navy 50 132 133 dark bluish- green 51
134 135 greenish- navy 52 136 137 dark bluish- green 53 138 139
dark bluish- green 54 140 141 greenish- navy 55 142 143 dark
bluish- green 56 144 145 dark bluish- green 57 146 147 greenish-
navy 58 148 149 greenish- navy 59 150 151 dark bluish- green 60 152
153 dark bluish- green 61 154 155 greenish- navy
[0408]
2TABLE 1 156 .lambda.max nm (W.sub.1/2 Ex- nm) Co- am- lour on ple
A B cotton 62 157 158 609 (116) dull dark green 63 159 160 608
(112) dull dark green 64 161 162 620 (130) daull dark green 65 163
164 Green- ish- navy 66 165 166 Green- ish- navy 67 167 168 Green-
ish- navy
[0409]
3TABLE 3 169 Colour on Example L .lambda.max nm W.sub.1/2 nm cotton
69 170 415 139 Golden yellow 70 171 367 140 Golden yellow 71 172
403 200 Golden yellow 72 173 419 200 Golden yellow 73 174 366 119
Golden yellow 74 NHC.sub.2H.sub.4NH 410 170 Golden yellow 75 175
378 155 Golden yellow 76 176 389 150 Golden yellow 77 177 360 160
Golden yellow
[0410]
4TABLE 4 178 Ex- Colour am- on ple A B X Y cotton 78 179 180
NH.sub.2 OH Green ish navy 79 181 182 OH NH.sub.2 Green ish navy 80
183 184 NH.sub.2 OH Green ish navy 81 185 186 OH NH.sub.2 Green ish
navy 82 187 188 NH.sub.2 OH Green ish navy 83 189 190 OH NH.sub.2
Green ish navy 84 191 192 NH.sub.2 OH Green ish navy 85 193 194 OH
NH.sub.2 Green ish navy 86 195 196 NH.sub.2 OH Green ish navy 87
197 198 OH NH.sub.2 Green ish navy 88 199 200 NH.sub.2 OH Green ish
navy 89 201 202 OH NH.sub.2 Navy 90 203 204 NH.sub.2 OH Navy 91 205
206 OH NH.sub.2 Green ish navy 92 207 208 NH.sub.2 OH Green ish
navy 93 209 210 OH NH.sub.2 Green ish navy 94 211 212 OH NH.sub.2
Green ish navy 95 213 214 NH.sub.2 OH Green ish navy 96 215 216 OH
NH.sub.2 Green ish navy 97 217 218 OH NH.sub.2 Green ish navy
[0411]
5TABLE 5 219 Example Structure .lambda.max nm W.sub.1/2 nm Colour
on cotton 98 Dye-SC.sub.2H.sub.4OH 407 148 Golden yellow 99
Dye-N(CH.sub.3)Ph 403 138 Golden yellow 100
Dye-NHC.sub.2H.sub.4SO.sub.3H 407 129 Golden yellow 101
Dye-NHC.sub.2H.sub.4OC.sub.2H.sub.4OH 412 134 Golden yellow 102
Dye-C.sub.6H.sub.3-m-SO.sub.3H 409 143 Golden yellow 103
Dye-NHC.sub.2H.sub.4NH-Dye Golden yellow 104 220 412 130 Golden
yellow
[0412]
6TABLE 6 221 Colour on Example Structure .lambda.max nm w.sub.1/2
nm cotton 105 Dye-SC.sub.2H.sub.4OH 437 151 Mid yellow 106 222 430
135 Mid yellow 107 Dye-NHC.sub.2H.sub.4OC.sub- .2H.sub.4OH 436 141
Mid yellow 108 223 435 132 Mid yellow 109 224 439 143 Mid yellow
110 225 438 149 Mid yellow 111 226 437 131 Mid yellow 112
Dye-NHC.sub.2H.sub.4NH-Dye Mid yellow 113
Dye-NHC.sub.3H.sub.6NH-Dye Mid yellow
[0413]
7TABLE 7 .lambda.max nm Ex- (w.sub.1/2 nm) am- Colour on ple
Structure cotton 114 227 435 (172) mid yellow 115 228 422 (148)
golden yellow 116 229 406 (124) golden yellow
[0414]
8TABLE 6 Example 230 Other substituents Colour on cotton 117
4-1,3-(SO.sub.3H).sub.2 3'-SO.sub.2C.sub.2H.sub.4OSO.sub.3H Yellow
118 3-1,4-(SO.sub.3H).sub.2 2'-SO.sub.2C.sub.2H.sub.4OSO.sub.3H
Yellow 119 4-1,1'-(SO.sub.3H).sub.2 231 Yellow 120
4-1,1'-(SO.sub.3H).sub.2 232 Yellow 121 4'-1,1',4-(SO.sub.3H).sub.3
233 Yellow
[0415]
9TABLE 9 234 Ex- Colour am- on ple A B X Y cotton 122 235 236 H H
Green- ish yellow 123 237 238 H CN Green- ish yellow 124 239 240 H
CONH.sub.2 Green- ish yellow 125 241 242 C.sub.2H.sub.4OH H Green-
ish yellow 126 243 244 C.sub.2H.sub.4OH CONH.sub.2 Green- ish
yellow 127 245 246 H H Green- ish yellow
[0416]
10TABLE 10 247 Ex- Colour am- on ple A B X Y cotton 128 248 249
SO.sub.3H H Blueish red 129 250 251 SO.sub.3H H Blueish red 130 252
253 H SO.sub.3H Blueish red 131 254 255 SO.sub.3H H Blueish red 132
256 257 SO.sub.3H H Blueish red 133 258 259 H SO.sub.3H Blueish red
134 260 261 SO.sub.3H H Blueish red 135 262 263 SO.sub.3H H Blueish
red 136 264 265 SO.sub.3H H Blueish red 137 266 267 H SO.sub.3H
Blueish red 138 268 269 SO.sub.3H H Blueish red
[0417]
11TABLE 11 270 Colour Exam- on ple A B X cotton 139 271 272 H Red
140 273 274 SO.sub.3H Red 141 275 276 H Red 142 277 278 SO.sub.3H
Red 143 279 280 H Red 144 281 282 SO.sub.3H Red 145 283 284
SO.sub.3H Red 146 285 286 SO.sub.3H Red 147 287 288 H Red 148 289
290 H Red 149 291 292 SO.sub.3H Red
[0418]
12TABLE 12 293 Ex- Colour am- on ple A B X Y cotton 150 294 295 H H
Reddish yellow 151 296 297 H SO.sub.3H Reddish yellow 152 298 299
Me H Reddish yellow 153 300 301 H H Reddish yellow 154 302 303 H H
Orange 155 304 305 H SO.sub.3H Orange 156 306 307 Me H Orange 157
308 309 H H Orange 158 310 311 H H Orange 159 312 313 H SO.sub.3H
Orange 160 314 315 Me H Orange
[0419]
13TABLE 13 316 Colour on Example A cotton 161 317 Greenish blue 162
318 Greenish blue 163 319 Greenish blue 164 320 Greenish blue
[0420]
14TABLE 14 321 Colour on Example R R' R" x y z cotton 165 322 H H 2
0 2 Green 166 323 H H 1.5 0.5 2 Green 167 C.sub.2H.sub.4 H H 2 0 2
Bluish-green 168 C.sub.3H.sub.6 CH.sub.3 CH.sub.3 1.7 0.3 2
Bluish-green 169 324 H C.sub.2H.sub.4OSO.sub.3H 2.5 0.5 1 Green 170
325 H H 1.5 1.5 1 Green 171 326 H C.sub.2H.sub.4SO.sub.3H 2.5 0 1.5
Green 172 327 H H 3 0 1 Green
[0421]
15 328 Example A B X Y Colour on cotton 173 329 330 Cl Cl Blue 174
331 332 Cl Cl Blue 175 333 334 Cl Et Blue 176 335 336 Cl Cl
Greenish blue 177 337 338 Cl Et Greenish blue 178 339 340 Cl Cl
Greenish blue 179 H 341 Cl Cl Greenish blue 180 342 343 Cl Me Blue
181 344 345 Cl Cl Greenish blue
[0422]
16TABLE 16 346 Colour on Example A X cotton 182 347 H Dull greenish
blue 183 348 H Dull greenish blue 184 349 H Dull greenish blue 185
350 H Dull greenish blue 186 351 H Dull blue 187 352 H Dull
greenish blue 188 353 3-SO.sub.3H Dull greenish blue 189 354
4-SO.sub.2C.sub.2H.sub.4OSO.sub.3H Dull greenish blue
* * * * *