U.S. patent application number 09/773292 was filed with the patent office on 2001-08-16 for process for dyeing or printing and novel reactive dyes.
Invention is credited to Aeschlimann, Peter, Frick, Marcel, Lehmann, Urs, Scheibli, Peter.
Application Number | 20010013149 09/773292 |
Document ID | / |
Family ID | 8230518 |
Filed Date | 2001-08-16 |
United States Patent
Application |
20010013149 |
Kind Code |
A1 |
Scheibli, Peter ; et
al. |
August 16, 2001 |
Process for dyeing or printing and novel reactive dyes
Abstract
Process for dyeing or printing paper, films of plastic or fiber
material containing hydroxyl groups or containing nitrogen with
reactive dyes, which comprises using at least one reactive dye of
the formula (1) from the following group a) and at least one
reactive dye from the following groups b), c) and d): a) green- or
blue-dyeing reactive dyes of the formula (1) 1 b) blue-dyeing
reactive dyes of the formula (2) or (3) 2 c) red-dyeing reactive
dyes of the formula (4) 3 d) yellow- or orange-dyeing reactive dyes
of the formula (5) 4
Inventors: |
Scheibli, Peter;
(Bottmingen, CH) ; Aeschlimann, Peter; (Allschwil,
CH) ; Lehmann, Urs; (Basel, CH) ; Frick,
Marcel; (Reinach, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8230518 |
Appl. No.: |
09/773292 |
Filed: |
January 31, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09773292 |
Jan 31, 2001 |
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09541763 |
Apr 3, 2000 |
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09541763 |
Apr 3, 2000 |
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09207539 |
Dec 8, 1998 |
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6063137 |
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Current U.S.
Class: |
8/543 ; 8/506;
8/536; 8/636 |
Current CPC
Class: |
C09B 67/004 20130101;
C09B 67/0042 20130101; C09B 67/0044 20130101; C09D 11/328 20130101;
Y10S 8/918 20130101; Y10S 8/92 20130101; Y10S 8/924 20130101; C09B
67/0041 20130101; Y10S 8/919 20130101; C09B 67/0052 20130101; D06P
1/38 20130101 |
Class at
Publication: |
8/543 ; 8/636;
8/506; 8/536 |
International
Class: |
D06P 001/00; C09B
001/00; C09B 062/00; D06P 005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 11, 1997 |
EP |
97810975.9 |
Claims
What is claimed is:
1. A process for dyeing or printing paper, films of plastic or
fibre material containing hydroxyl groups or containing nitrogen
with reactive dyes, which comprises using at least one reactive dye
of the formula (1) from the following group a) and at least one
reactive dye from the following groups b), c) and d): a) green- or
blue-dyeing reactive dyes of the formula (1) 77in which NiPhC is
the radical of a nickel phthalocyanine, R.sub.1 is hydrogen or
substituted or unsubstituted C.sub.1-C.sub.4alkyl, V.sub.1 is
hydrogen or substituted or unsubstituted C.sub.1-C.sub.8alkyl,
phenyl or naphthyl and x is 2 to 4 and y is 1 to 2, the reactive
dye of the formula (1) containing at least one fibre-reactive
group; b) blue-dyeing reactive dyes of the formula (2) or (3) 78in
which (R.sub.2).sub.0-3 is 0 to 3 C.sub.1-C.sub.4alkyl radicals
which are identical or different from one another and
(R.sub.3).sub.0-3 is 0 to 3 substituents, which are identical or
different from another, from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl and
sulfo, X.sub.1 is chlorine or fluorine and R.sub.4 is hydrogen or
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by
hydroxyl, sulfo or sulfato, 79in which R.sub.5 is hydrogen or
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by
hydroxyl, sulfo or sulfato, X.sub.2 is chlorine or fluorine,
Y.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl which is unsubstituted or
substituted by hydroxyl, sulfo or sulfato and uninterrupted or
interrupted by oxygen, or phenyl or naphthyl which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, and the benzene
nuclei I, II and III contain no further substituents or are further
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen
or carboxyl; c) red-dyeing reactive dyes of the formula (4) 80in
which R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato, R.sub.7
and R.sub.8 independently of one another are hydrogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl or
sulfo, X.sub.3 is chlorine or fluorine and Y.sub.2 is hydrogen,
C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by
hydroxyl, sulfo, sulfato or a radical of the formula --SO.sub.2--Z
and is uninterrupted or interrupted by oxygen, or phenyl or
naphthyl which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl,
sulfo or a radical of the formula --SO.sub.2--Z or
--CO--NH--(CH.sub.2).sub.2-3--SO.sub.2--Z, or the radical
--N(R.sub.6)--Y.sub.2 is morpholino, in which Z is a radical of the
formula --CH.dbd.CH.sub.2 or --CH.sub.2--CH.sub.2--U.sub.1 and
U.sub.1 is a leaving group; d) yellow- or orange-dyeing reactive
dyes of the formula (5) 81in which R.sub.9 is hydrogen or
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by
hydroxyl, sulfo or sulfato, R.sub.10 and R.sub.11 independently of
one another are hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, X.sub.4 is
chlorine or fluorine and Y.sub.3 is hydrogen, C.sub.1-C.sub.8alkyl
which is unsubstituted or substituted by hydroxyl, sulfo or sulfato
and is uninterrupted or interrupted by oxygen, or phenyl or
naphthyl which are unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl,
sulfo or a halogenotriazinylamino radical which is unsubstituted or
further substituted, or the radical --N(R.sub.9)--Y.sub.3 is
morpholino, and K.sub.1 is a radical of the formula 82in which
R.sub.12 is hydroxyl or amino, R.sub.13 is methyl or carboxyl,
(R.sub.14).sub.0-3 is 0 to 3 identical or different substituents
from the group consisting of C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl and sulfo, R.sub.15 and
R.sub.17 are C.sub.1-C.sub.4alkyl and R.sub.16 is cyano, carbamoyl
or sulfomethyl.
2. A process according to claim 1, wherein R.sub.1 is hydrogen or
C.sub.1-C.sub.4alkyl and V.sub.1 is a radical of the formula 83in
which R' is hydrogen or C.sub.1-C.sub.4alkyl, X.sub.5 is fluorine
or chlorine, Y.sub.4 is hydrogen or phenyl which is unsubstituted
or substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
halogen, carboxyl or sulfo, alkylene is C.sub.1-C.sub.6alkylene and
Z is as defined in claim 1.
3. A process according to claim 1, wherein the reactive dye of the
formula (1) used is a reactive dye of the formula 84in which NiPhC,
x and y are as defined in claim 1.
4. A process according to claim 1, wherein R.sub.3 is sulfo,
R.sub.4 is hydrogen or C.sub.1-C.sub.4alkyl and X.sub.1 is
chlorine.
5. A process according to claim 1, wherein the reactive dye of the
formula (2) used is a reactive dye of the formula 85
6. A process according to claim 1, wherein the reactive dye of the
formula (3) used is a reactive dye of the formula 86in which
R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl and X.sub.2 and Y.sub.1
are as defined in claim 1.
7. A process according to claim 1, wherein R.sub.5 is hydrogen or
C.sub.1-C.sub.4alkyl, X.sub.2 is chlorine and Y.sub.1 is
hydrogen.
8. A process according to claim 1, wherein R.sub.6 is hydrogen or
C.sub.1-C.sub.4alkyl, R.sub.7 is sulfo, R.sub.8 is hydrogen or
sulfo and Y.sub.2 is hydrogen, C.sub.1-C.sub.8alkyl, which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and is
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, or the radical
--N(R.sub.6)--Y.sub.2 is morpholino.
9. A process according to claim 1, wherein the reactive dye of the
formula (4) used is a reactive dye of the formula 87in which
R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl, R.sub.7 is sulfo,
R.sub.8 is hydrogen or sulfo and Y.sub.2 is C.sub.1-C.sub.4alkyl
which is substituted by hydroxyl, sulfo or sulfato and is
uninterrupted or interrupted by oxygen, or is phenyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo.
10. A process according to claim 1, wherein R.sub.9 is hydrogen or
C.sub.1-C.sub.4alkyl, R.sub.10 is sulfo, R.sub.11 is hydrogen or
sulfo, R.sub.12 is hydroxyl, R.sub.13 is methyl, R.sub.16 is
carbamoyl and X.sub.4 is chlorine.
11. A process according to claim 1, wherein the reactive dye of the
formula (5) used is a reactive dye of the formula 88
12. A process according to claim 1, wherein at least one reactive
dye of the formula (1) from group a) and at least one reactive dye
of the formula (4) from group c) are used.
13. A process according to claim 1, wherein at least one reactive
dye of the formula (1) from group a) and at least one reactive dye
of the formula (5) from group d) are used.
14. A process according to claim 1, wherein at least one reactive
dye of the formula (1) from group a), at least one reactive dye of
the formula (4) from group c) and at least one reactive dye of the
formula (5) from group d) are used.
15. A process according to claim 1, wherein at least one reactive
dye of the formula (1) from group a), at least one reactive dye of
the formula (2) or (3) from group b), at least one reactive dye of
the formula (4) from group c) and at least one reactive dye of the
formula (5) from group d) are used.
16. A process according to claim 1, wherein fibre material
containing hydroxyl groups or containing nitrogen is printed.
17. A process according to claim 16, wherein fibre material
containing hydroxyl groups or containing nitrogen is printed by the
ink jet printing process.
18. A process according to claim 17, wherein the fibre material is
printed with aqueous inks which comprise 5 to 35% by weight of the
reactive dye.
19. A process according to claim 18, wherein the aqueous inks
comprise 5 to 30% by weight of 1,2-propylene glycol.
20. A process according to claim 1, wherein fibre material
containing hydroxyl groups or containing nitrogen is dyed by the
exhaust method or the pad-dyeing method.
21. A process according to claim 1, wherein the fibre material is
fibre material containing hydroxyl groups.
22. A process according to claim 21, wherein the fibre material is
cellulosic fibre material.
23. A process according to claim 1, wherein paper or films of
plastic are printed.
24. A reactive dye of the formula 89in which R.sub.6 is hydrogen or
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by
hydroxyl, sulfo or sulfato, R.sub.7 and R.sub.8 independently of
one another are hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, X.sub.3 is
fluorine and Y.sub.2 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and is
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, or the radical
--N(R.sub.6)--Y.sub.2 is morpholino.
25. A dye mixture which comprises at least one reactive dye of the
formula (2) 90in which (R.sub.2).sub.0-3 is 0 to 3
C.sub.1-C.sub.4alkyl radicals which are identical or different from
one another and (R.sub.3).sub.0-3 is 0 to 3 substituents, which are
identical or different from another, from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl and
sulfo, X.sub.1 is chlorine or fluorine and R.sub.4 is hydrogen or
C.sub.1-C.sub.4alkyl which is unsubstituted or substituted by
hydroxyl, sulfo or sulfato, and at least one reactive dye of the
formula (3) 91in which R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl
which is unsubstituted or substituted by hydroxyl, sulfo or
sulfato, X.sub.2 is chlorine or fluorine, Y.sub.1 is hydrogen,
C.sub.1-C.sub.8alkyl which is unsubstituted or substituted by
hydroxyl, sulfo or sulfato and uninterrupted or interrupted by
oxygen, or phenyl or naphthyl which are unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
halogen, carboxyl or sulfo, and the benzene nuclei I, II and III
contain no further substituents or are further substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen or carboxyl.
Description
[0001] The present invention relates to a process for dyeing or
printing fibre materials containing hydroxyl groups or containing
nitrogen with reactive dyes, and to novel reactive dyes. The
process on which the present invention is based is also suitable
for dyeing or printing paper or films of plastic.
[0002] The practice of dyeing and printing with reactive dyes has
recently led to increased demands on the quality of the dyeings and
prints and on the profitability of the dyeing or printing process.
Consequently, there continues to be a need for novel processes
which have improved properties in respect of application and in
respect of the dyeings or prints obtained.
[0003] Processes wherein the reactive dyes have an adequate
substantivity and at the same time a good ease of wash off of the
non-fixed portions are now required for dyeing and printing. The
dyeings and prints furthermore should have a good dyeing yield,
high degrees of fixing and good allround properties, such as wet
fastness properties and, in particular, light fastness properties.
When a combination of reactive dyes is used, the effect of
so-called catalytic fading should therefore largely be avoided. By
this effect, one of the reactive dyes in combination with other
reactive dyes fades significantly more than is the case when it is
used by itself, i.e. in an individual shade.
[0004] The process should furthermore be suitable for ink jet
printing processes get and ink jet processes).
[0005] Ink jet printing processes have already been used in the
textile industry for some years. These processes enable the
otherwise customary production of a printing screen to be omitted,
so that considerable savings in cost and time can be achieved. In
the production of pattern samples in particular, changed
requirements can be reacted to within a significantly shorter
time.
[0006] Appropriate ink jet printing processes should have, in
particular, optimum use properties. In this connection there may be
mentioned properties such as the viscosity, stability, surface
tension and conductivity of the inks used. Increased demands are
furthermore made on the quality of the resulting prints, for
example in respect of colour strength, fibre-dye bond stability and
in respect of the wet fastness properties and, in particular, the
light fastness properties.
[0007] Furthermore, the reactive dyes to be used for the
abovementioned processes should be easy to combine and should allow
as far as possible all shades of the colour space to be established
by combination.
[0008] These requirements are not met in all the properties by the
known processes.
[0009] The present invention is therefore based on the object of
discovering novel, improved processes for dyeing and printing fibre
materials which have the qualities characterized above to a high
degree.
[0010] It has been found that the object described is largely
achieved by the process defined below.
[0011] The present invention relates to a process for dyeing or
printing paper, films of plastic or fibre material containing
hydroxyl groups or containing nitrogen with reactive dyes, which
comprises using at least one reactive dye of the formula (1) from
the following group a) and at least one reactive dye from the
following groups b), c) and d):
[0012] a) green- or blue-dyeing reactive dyes of the formula (1)
5
[0013] in which
[0014] NiPhC is the radical of a nickel phthalocyanine,
[0015] R.sub.1 is hydrogen or substituted or unsubstituted
C.sub.1-C.sub.4alkyl,
[0016] V.sub.1 is hydrogen or substituted or unsubstituted
C.sub.1-C.sub.8alkyl, phenyl or naphthyl and
[0017] x is 2 to 4 and y is 1 to 2,
[0018] the reactive dye of the formula (1) containing at least one
fibre-reactive group;
[0019] b) blue-dyeing reactive dyes of the formula (2) or (3) 6
[0020] in which
[0021] (R.sub.2).sub.0-3 is 0 to 3 C.sub.1-C.sub.4alkyl radicals
which are identical or different from one another and
[0022] (R.sub.3).sub.0-3 is 0 to 3 substituents, which are
identical or different from another, from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl and
sulfo,
[0023] X.sub.1 is chlorine or fluorine and
[0024] R.sub.4 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato, 7
[0025] in which
[0026] R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato,
[0027] X.sub.2 is chlorine or fluorine,
[0028] Y.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, and the benzene
nuclei I, II and III contain no further substituents or are further
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen
or carboxyl;
[0029] c) red-dyeing reactive dyes of the formula (4) 8
[0030] in which
[0031] R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroyl, sulfo or sulfato,
[0032] R.sub.7 and R.sub.8 independently of one another are
hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen,
carboxyl or sulfo,
[0033] X.sub.3 is chlorine or fluorine and
[0034] Y.sub.2 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo, sulfato or a
radical of the formula --SO.sub.2--Z and is uninterrupted or
interrupted by oxygen, or phenyl or naphthyl which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl, sulfo or a radical of the
formula --SO.sub.2--Z or --CO--NH--(CH.sub.2).sub.2-3--SO.sub.2--Z,
or the radical --N(R.sub.6)--Y.sub.2 is morpholino, in which
[0035] Z is a radical of the formula --CH.dbd.CH.sub.2 or
--CH.sub.2--CH.sub.2--U.sub.1 and U.sub.1 is a leaving group;
[0036] d) yellow- or orange-dyeing reactive dyes of the formula (5)
9
[0037] in which
[0038] R.sub.9 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato,
[0039] R.sub.10 and R.sub.11 independently of one another are
hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen,
carboxyl or sulfo,
[0040] X.sub.4 is chlorine or fluorine and
[0041] Y.sub.3 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and is
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl, sulfo or a
halogenotriazinylamino radical which is unsubstituted or further
substituted, or the radical --N(R.sub.9)--Y.sub.3 is morpholino,
and
[0042] K.sub.1 is a radical of the formula 10
[0043] in which
[0044] R.sub.12 is hydroxyl or amino,
[0045] R.sub.13 is methyl or carboxyl,
[0046] (R.sub.14).sub.0-3 is 0 to 3 identical or different
substituents from the group consisting of C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl and sulfo,
[0047] R.sub.15 and R.sub.17 are C.sub.1-C.sub.4alkyl and
[0048] R.sub.16 is cyano, carbamoyl or sulfomethyl.
[0049] Sulfo groups present in the above reactive dyes can in
general be present both as the free acid (--SO.sub.3H) and in any
salt form, for example as an alkali metal, alkaline earth metal or
ammonium salt or as a salt of an organic amine, for example the
sodium, potassium, lithium or ammonium salt, the salt of
triethanolamine or the mixed salt of two or more different cations,
for example as the Na/Li--, Na/NH.sub.4-- or Na/Li/NH.sub.4 mixed
salt.
[0050] C.sub.1-C.sub.4Alkyl R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11,
R.sub.14, R.sub.15 and R.sub.17 and the other C.sub.1-C.sub.4alkyl
radicals mentioned above as substituents are, for example, methyl,
ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl,
in particular methyl or ethyl. The methyl radicals are of
particular importance here. Substituents of the alkyl radical
R.sub.1 are, for example, hydroxyl, sulfo or sulfato. The alkyl
radicals R.sub.4, R.sub.5, R.sub.6 and R.sub.9 can be substituted
as mentioned above. Preferably, the alkyl radicals mentioned are
unsubstituted.
[0051] C.sub.1-C.sub.4Alkoxy R.sub.3, R.sub.7, R.sub.8, R.sub.10,
R.sub.11 and R.sub.14 and the other C.sub.1-C.sub.4alkoxy radicals
mentioned above as substituents are, for example, methoxy, ethoxy,
propoxy, isopropoxy, bultoxy or isobutoxy, in particular
methoxy.
[0052] Halogen R.sub.3, R.sub.7, R.sub.8, R.sub.10, R.sub.11 and
R.sub.14 and the other halogen radicals mentioned above as
substituents are, for example, fluorine or, in particular,
chlorine.
[0053] The leaving group U.sub.1 is, for example, --Cl, --Br, --F,
--OSO.sub.3H, --SSO.sub.3H, --OCO--CH.sub.3, --OPO.sub.3H.sub.2,
--OCO--C.sub.6H.sub.5, --OSO.sub.2--C.sub.1-C.sub.4alkyl or
--OSO.sub.2--N(C.sub.1-C.sub.4alkyl).sub.2. Preferably, U.sub.1 is
a group of the formula --Cl, --OSO.sub.3H, --SSO.sub.3H,
--OCO--CH.sub.3, --OCO--C.sub.6H.sub.5 or --OPO.sub.3H.sub.2, in
particular --Cl or --OSO.sub.3H and particularly preferably
--OSO.sub.3H.
[0054] Z is preferably vinyl or a radical of the formula
--CH.sub.2--CH.sub.2--OSO.sub.3H.
[0055] Substituted or unsubstituted C.sub.1-C.sub.8alkyl V.sub.1
is, in particular, C.sub.1-C.sub.4alkyl, and preferably ethyl, the
alkyl radicals being unsubstituted or preferably substituted by a
fibre-reactive group.
[0056] Unsubstituted or substituted phenyl or naphthyl V.sub.1 are
the unsubstituted radicals and, preferably, the radicals
substituted by, for example, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl, sulfo or a fibre-reactive
group. Those phenyl or naphthyl radicals which are substituted by a
fibre-reactive group and furthermore may be substituted by sulfo
are of particular interest. The corresponding phenyl radicals are
of very particular interest here for V.sub.1.
[0057] Fibre-reactive groups which are contained in the reactive
dye of the formula (1) are, for example, those of the formula
11
[0058] in which
[0059] R' is hydrogen or C.sub.1-C.sub.4alkyl, in particular
hydrogen,
[0060] X.sub.5 is fluorine or, in particular, chlorine,
[0061] Y.sub.4 is as defined above for Y.sub.1, and is preferably
hydrogen or phenyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl or
sulfo, and
[0062] Z is as defined and preferred above.
[0063] Preferably, V.sub.1 is a radical of the formula 12
[0064] in which
[0065] R' is hydrogen or C.sub.1-C.sub.4alkyl, in particular
hydrogen,
[0066] X.sub.5 is fluorine or, in particular, chlorine,
[0067] Y.sub.4 is hydrogen or phenyl which is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
halogen, carboxyl or sulfo, in particular hydrogen or phenyl which
is substituted by sulfo, alkylene is C.sub.2-C.sub.6alkylene, in
particular C.sub.2-C.sub.4alkylene, and preferably ethylene, and Z
is as defined and preferred above.
[0068] V.sub.1 is particularly preferably a radical of the formula
(9a) or (9b), in particular a radical of the formula (9a).
[0069] Preferred reactive dyes of the formula (1) are those in
which
[0070] R.sub.1 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
hydrogen, and V.sub.1 is as defined and preferred above.
[0071] Particularly preferred reactive dyes of the formula (1) are
those of the formula 13
[0072] in which NiPhC, x and y are as defined above.
[0073] R.sub.2 is preferably methyl.
[0074] R.sub.3 is preferably C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy or sulfo, in particular sulfo.
[0075] X.sub.1 is preferably chlorine.
[0076] R.sub.4 is preferably hydrogen or C.sub.1-C.sub.4alkyl, in
particular hydrogen.
[0077] Preferred reactive dyes of the formula (2) are those in
which
[0078] R.sub.3 is sulfo,
[0079] R.sub.4 is hydrogen or C.sub.1-C.sub.4alkyl and
[0080] X.sub.1 is chlorine. Preferably, the reactive dyes of the
formula (2) contain three radicals R.sub.2.
[0081] Particularly preferred reactive dyes of the formula (2) are
those of the formula 14
[0082] R.sub.5 is preferably hydrogen or C.sub.1-C.sub.4alkyl, in
particular hydrogen.
[0083] X.sub.2 is preferably chlorine.
[0084] Y.sub.1 is preferably hydrogen or C.sub.1-C.sub.8alkyl which
is unsubstituted or substituted by hydroxyl, sulfo or sulfato and
is uninterrupted or interrupted by oxygen, and in particular is
hydrogen.
[0085] The benzene nuclei I, II and III of the reactive dye of the
formula (3) preferably contain no further substituents.
[0086] Preferred reactive dyes of the formula (3) are those in
which
[0087] R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
hydrogen,
[0088] X.sub.2 is chlorine and
[0089] Y.sub.1 is hydrogen.
[0090] Particularly preferred reactive dyes of the formula (3) are
those of the formula 15
[0091] in which
[0092] R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
hydrogen, and
[0093] X.sub.2 and Y.sub.1 are as defined and preferred above.
[0094] Especially preferred reactive dyes of the formula (3) are
those of the formula 16
[0095] R.sub.6 is preferably hydrogen or C.sub.1-C.sub.4alkyl, in
particular C.sub.1-C.sub.4alkyl and preferably methyl.
[0096] R.sub.7 is preferably sulfo.
[0097] R.sub.8 is preferably hydrogen or sulfo, in particular
hydrogen.
[0098] X.sub.3 is preferably chlorine.
[0099] Y.sub.2 is preferably hydrogen, C.sub.1-C.sub.8alkyl, in
particular C.sub.1-C.sub.4alkyl which is unsubstituted or
substituted by hydroxyl, sulfo or sulfato and is uninterrupted or
interrupted by oxygen, or phenyl or naphthyl which are
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, or the radical
--N(R.sub.6)--Y.sub.2 is morpholino.
[0100] Y.sub.2 is particularly preferably C.sub.1-C.sub.4alkyl
which is unsubstituted or substituted by hydroxyl, sulfo or
sulfato, in particular by sulfo, and is uninterrupted or
interrupted by oxygen, or phenyl which is unsubstituted or
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy,
halogen, carboxyl or sulfo, in particular by sulfo.
[0101] Y.sub.2 is especially preferably C.sub.1-C.sub.4alkyl which
is unsubstituted or substituted by hydroxyl, sulfo or sulfato, in
particular by sulfo.
[0102] Preferred reactive dyes of the formula (4) are those in
which
[0103] R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
C.sub.1-C.sub.4alkyl, and preferably methyl,
[0104] R.sub.7 is sulfo,
[0105] R.sub.8 is hydrogen or sulfo, in particular hydrogen,
[0106] X.sub.3 is fluorine or, in particular, chlorine, and
[0107] Y.sub.2 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and is
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, or the radical
--N(R.sub.6)--Y.sub.2 is morpholino. In this case, Y.sub.2 is as
preferred above.
[0108] Particularly preferred reactive dyes of the formula (4) are
those of the formula 17
[0109] in which
[0110] R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
C.sub.1-C.sub.4alkyl, and preferably methyl,
[0111] R.sub.7 is sulfo,
[0112] R.sub.8 is hydrogen or sulfo, in particular hydrogen,
and
[0113] Y.sub.2 is C.sub.1-C.sub.4alkyl which is substituted by
hydroxyl, sulfo or sulfato, in particular by sulfo, and is
uninterrupted or interrupted by oxygen, or is phenyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo. Y.sub.2 here is
as preferred above.
[0114] Especially preferred reactive dyes of the formula (4) are
those of the formula 18
[0115] in which
[0116] R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
C.sub.1-C.sub.4alkyl, and preferably methyl, and
[0117] Y.sub.2 is C.sub.1-C.sub.4alkyl which is substituted by
hydroxyl, sulfo or sulfato, in particular by sulfo.
[0118] R.sub.9 is preferably hydrogen or C.sub.1-C.sub.4alkyl, in
particular hydrogen.
[0119] R.sub.10 is preferably sulfo.
[0120] R.sub.11 is preferably hydrogen or sulfo, in particular
hydrogen.
[0121] X.sub.4 is preferably chlorine.
[0122] R.sub.12 is preferably hydroxyl.
[0123] R.sub.13 is preferably methyl.
[0124] R.sub.14 is preferably halogen or sulfo.
[0125] R.sub.15 is preferably methyl and
[0126] R.sub.17 is preferably ethyl.
[0127] R.sub.16 is, in particular, carbamoyl or sulfomethyl,
preferably carbamoyl.
[0128] The radical K.sub.1 is preferably a radical of the formula
(6).
[0129] Y.sub.3 is preferably naphthyl or, in particular, phenyl
which are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl, sulfo or a
halogenotriazinylamino radical which is unsubstituted or further
substituted. A halogenotriazinylamino radical which is
unsubstituted or further substituted is, for example, such a
radical of the formula (8a), in which the substituents are as
defined and preferred under formula (8a) and Y.sub.4 is, in
particular, hydrogen.
[0130] Y.sub.3 is particularly preferably phenyl which is
substituted by sulfo or a radical of the formula (8a), in
particular phenyl which is substituted by sulfo.
[0131] Preferred reactive dyes of the formula (5) are those in
which
[0132] R.sub.9 is hydrogen or C.sub.1-C.sub.4alkyl, in particular
hydrogen,
[0133] R.sub.10 is sulfo,
[0134] R.sub.11 is hydrogen or sulfo, in particular hydrogen,
[0135] R.sub.12 is hydroxyl,
[0136] R.sub.13 is methyl,
[0137] R.sub.16 is carbamoyl and
[0138] X.sub.4 is chlorine.
[0139] Particularly preferred reactive dyes of the formula (5) are
those of the formula 19
[0140] in particular those of the formula (16).
[0141] Preferably, reactive dyes of group a) which are used are
those of the formula (10), reactive dyes of group b) which are used
are those of the formula (11) or (12), in particular those of the
formula (11) or (13), reactive dyes of group c) which are used are
those of the formula (14), in particular of the formula (15), and
reactive dyes of group d) which are used are those of the formula
(16) or (17), in particular of the formula (16).
[0142] Reactive dyes of group b) which are used are, in particular,
a mixture of reactive dyes of the formulae (2) and (3), the
reactive dyes of the formulae (2) and (3) being as defined and
preferred above.
[0143] Preferably, at least one reactive dye of the formula (1)
from group a) and at least one reactive dye of the formula (4) from
group c) are used.
[0144] Preferably, furthermore, at least one reactive dye of the
formula (1) from group a) and at least one reactive dye of the
formula (5) from group d) are used.
[0145] Particularly preferably, at least one reactive dye of the
formula (1) from group a), at least one reactive dye of the formula
(4) from group c) and at least one reactive dye of the formula (5)
from group d) are used.
[0146] According to an especially preferred embodiment of the
process according to the invention,
[0147] at least one reactive dye of the formula (1) from group
a),
[0148] at least one reactive dye of the formula (2) or (3) from
group b),
[0149] at least one reactive dye of the formula (4) from group c)
and
[0150] at least one reactive dye of the formula (5) from group d)
are used.
[0151] The process according to the invention is suitable for
dyeing or printing fibre materials containing hydroxyl groups or
containing nitrogen.
[0152] The process according to the invention is furthermore
suitable for dyeing or printing paper or films of plastic.
[0153] Examples of nitrogen-containing fibre materials are natural
polyamide materials, for example wool, or synthetic polyamide
materials, for example polyamide 6 or polyamide 6.6.
[0154] Fibre materials containing hydroxyl groups, in particular
cellulosic fibre materials made entirely or partly of cellulose,
are preferred for the process according to the invention. Examples
are natural fibre materials, such as cotton, linen or hemp, and
pulp and regenerated fibre materials, for example viscose and
lyocell. Viscose or, preferably, cotton are particularly preferred
here.
[0155] The fibre materials mentioned are preferably in the form of
textile fibre materials, in particular as flat textile woven
fabric, knitted fabric or webs.
[0156] Examples of paper which can be dyed or printed by the
process according to the invention are commercially available ink
jet paper, photo paper, glossy paper, paper coated with plastic,
for example Epson Ink Jet Paper, Epson Photo Paper, Epson Glossy
Film, HP Special InkJet Paper, Encad Photo Gloss Paper and Ilford
Photo Paper. Films of plastic which can be dyed or printed by the
process according to the invention are, for example, transparent or
milky/opaque. Suitable films of plastic are, for example, 3M
Transparency Film.
[0157] According to one embodiment of the process according to the
invention, the dyeing or printing can be carried out by the
customary dyeing or printing processes. The dye liquors or printing
pastes here can comprise, in addition to water and the dyes,
further additives, for example wetting agents, antifoams, levelling
agents or agents which affect the nature of the substrate, for
example of the textile material, for example softening agents,
additives for flameproofing or dirt-, water- and oil-repellant
agents, as well as water-softening agents and natural or synthetic
thickeners, for example alginates and cellulose ethers.
[0158] Dyeing by the exhaust method or the pad-dyeing method are
preferred for the process according to the invention. The methods
mentioned are preferably suitable for dyeing fibre materials
containing hydroxyl groups or containing nitrogen.
[0159] According to the exhaust method, dyeing is as a rule carried
out in an aqueous medium at a liquor ratio of, for example, 1:2 to
1:60, in particular a liquor ratio of 1:5 to 1:20, and a
temperature of 20 to 105.degree. C., in particular 30 to 90.degree.
C., and preferably 30 to 70.degree. C.
[0160] The amounts in which the reactive dyes are used here in the
dyebaths can vary according to the desired depth of shade, and in
general amounts of 0.01 to 10% by weight, in particular 0.01 to 6%
by weight, based on the goods to be dyed, have proved
advantageous.
[0161] According to the pad-dyeing method, the goods are as a rule
impregnated with aqueous dye solutions, which may contain salts.
The liquor pick-up here is, for example, 20 to 150%, in particular
40 to 120%, and preferably 50 to 100%, based on the weight of the
fibre material to be dyed. If appropriate, the liquor already
comprises fixing alkali, or the fibre material is treated with
fixing alkali after the impregnation. Alkalis are, for example,
sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium
phosphate, trisodium phosphate, borax, aqueous ammonia, sodium
trichloroacetate, sodium formate or a mixture of water-glass and an
aqueous sodium carbonate solution. Alkali metal hydroxide and/or
alkali metal carbonate, in particular sodium hydroxide and/or
sodium carbonate, are preferred here.
[0162] Fixing can be carried out, for example, by the action of
heat, such as by steaming the impregnated fibre material at a
temperature of, for example, 100 to 120.degree. C., preferably in
saturated steam. According to the so-called cold pad-batch process,
the dye is applied on the padder together with the alkali and
thereafter is fixed at room temperature by storage for several
hours, for example 3 to 40 hours. After the fixing, the dyeings or
prints are rinsed thoroughly, if appropriate with the addition of a
dispersing agent.
[0163] Printing is particularly preferred for the process according
to the invention. Examples of corresponding printing processes are
conventional printing, screen printing and ink jet printing
processes.
[0164] Ink jet printing processes are especially preferred for the
process according to the invention.
[0165] For printing fibre materials, inks which comprise a total
content of reactive dyes of, for example, 3 to 35% by weight, in
particular 5 to 35% by weight, and preferably 10 to 30% by weight,
based on the total weight of the ink, are as a rule used.
[0166] For printing paper or films of plastic, inks which comprise
a total content of reactive dyes of, for example, 1 to 30% by
weight, in particular 1.5 to 25% by weight, and preferably 2 to 20%
by weight, based on the total weight of the ink, are as a rule
used.
[0167] The reactive dyes used in the inks should preferably have a
low salt content, i.e. comprise a total content of salts of less
than, for example, 0.5% by weight, based on the weight of the dyes.
Reactive dyes which, because of their preparation and/or the
subsequent addition of diluents, comprise higher salt contents can
be desalinated, for example, by membrane separation processes, such
as ultrafiltration, reverse osmosis or dialysis.
[0168] The inks can furthermore also comprise water-soluble,
nonionic cellulose ethers, for example methyl-, ethyl-,
hydroxyethyl-, methylhydroxyethyl-, hydroxypropyl- or
hydroxypropylmethylcellulose. Methylcellulose or, in particular,
hydroxyethylcellulose are preferred. The cellulose ethers can
usually be used in the ink in an amount of 0.01 to 2% by weight, in
particular 0.01 to 1% by weight, and preferably 0.01 to 0.5% by
weight, based on the total weight of the ink.
[0169] The inks can furthermore comprise alginates, in particular
alkali metal alginates, and preferably sodium alginate. These can
usually be used in the ink in an amount of 0.01 to 2% by weight, in
particular 0.01 to 1% by weight, and preferably 0.01 to 0.5% by
weight, based on the total weight of the ink.
[0170] The inks preferably have a viscosity of 1 to 40 mpa.s.
[0171] The inks can furthermore comprise buffer substances, for
example borax, borate or citrate. Examples are sodium borate,
sodium tetraborate and sodium citrate. They can be used, in
particular, in amounts of 0.1 to 3% by weight, preferably 0.1 to 1%
by weight, based on the total weight of the ink, in order to
establish a pH of, for example, 5 to 9, in particular 6 to 8.
[0172] The inks can comprise, as further additives, for example,
N-methyl-2-pyrrolidone or, in particular, 1,2-propylene glycol.
These can usually be used in the ink in an amount of 5 to 30% by
weight, in particular 5 to 20% by weight, and preferably 10 to 20%
by weight, based on the total weight of the ink.
[0173] If desired, the inks can furthermore also comprise customary
additives, for example foam-suppressing agents or, in particular,
substances which inhibit the growth of fungi and/or bacteria. These
are usually used in amounts of 0.01 to 1% by weight, based on the
total weight of the ink.
[0174] The process according to the invention for printing by the
ink jet printing process can be carried out with ink jet printers
which are suitable for textile printing and are known per se.
[0175] In the case of the ink jet printing process, individual
drops of the ink are sprayed in a controlled manner onto a
substrate from a nozzle. The continuous ink jet method and the drop
on demand method are usually used for this. In the case of the
continuous ink jet method, the drops are generated continuously,
drops which are not required for printing being diverted to a
collecting container and recycled. In the case of the drop on
demand method, on the other hand, drops are generated and printed
as required, i.e. drops are only generated when required for
printing. The drops can be generated, for example, by means of a
piezo ink jet head or by means of thermal energy (bubble jet).
Printing by the drop on demand method, in particular by means of a
piezo ink jet head, is preferred for the process according to the
invention.
[0176] According to a preferred embodiment of the process according
to the invention for printing by the ink jet printing process, the
fibre material is pretreated before the printing, during which the
fibre material to be printed is first treated with an aqueous
alkaline liquor and, if appropriate, the treated fibre material is
dried.
[0177] The aqueous alkaline liquor comprises at least one of the
customary bases employed for fixing reactive dyes in conventional
reactor printing processes. The base is employed, for example, in
an amount of 10 to 100 g/l of liquor, preferably 10 to 50 g/l of
liquor. Bases are, for example, sodium carbonate, sodium hydroxide,
disodium phosphate, trisodium phosphate, sodium acetate, sodium
propionate, sodium bicarbonate, aqueous ammonia or alkali donors,
for example sodium chloroacetate or sodium formate. Sodium
bicarbonate, sodium carbonate or a mixture of water-glass and
sodium carbonate is preferably used. The pH of the alkaline liquor
is as a rule 7.5 to 13.5, preferably 8.5 to 12.5. In addition to
the bases, the aqueous alkaline liquor can comprise further
additives, for example hydrotropic agents. Urea is preferably used
as the hydrotropic agent, and is employed, for example, in an
amount of 25 to 200 g/l of liquor, preferably 50 to 150 g/l of
liquor. The fibre material is preferably dried after the other
pretreatment.
[0178] After the printing by the ink jet printing process, the
fibre material is advantageously dried, preferably at temperature
of up to 150.degree. C., in particular 80 to 1 20.degree. C., and
is then subjected to a heat treatment process in order to complete
the printing or to fix the dye.
[0179] The heat treatment can be carried out, for example, by a hot
pad-batch process, a thermosol process or, preferably, by a
steaming process.
[0180] In the steaming process, the printed fibre material is
subjected, for example, to a treatment in a steamer with steam,
which may be superheated, advantageously at a temperature of 95 to
180.degree. C., advantageously in saturated steam.
[0181] Thereafter, the printed fibre material is as a rule washed
out with water in the customary manner in order to remove non-fixed
dye.
[0182] The dyeings and prints obtainable by the process according
to the invention have good all-round properties; they have, for
example, a high fibre-dye bond stability both in the acid and in
the alkaline range, good wet fastness properties, such as fastness
to washing, water, saltwater, crossdyeing and perspiration, a good
fastness to chlorine, fastness to rubbing, fastness to ironing and
fastness to pleating, as well as sharp contours and a high colour
strength. The very good fastness to light is furthermore to be
emphasized.
[0183] The present invention furthermore relates to reactive dyes
of the formula 20
[0184] in which
[0185] R.sub.6 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato,
[0186] R.sub.7 and R.sub.8 independently of one another are
hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen,
carboxyl or sulfo,
[0187] X.sub.3 is fluorine and
[0188] Y.sub.2 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and is
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, or the radical
--N(R.sub.6)--Y.sub.2 is morpholino.
[0189] The individual substituents and the reactive dyes of the
formula (4a) are as preferred above.
[0190] The present invention furthermore relates to a process for
the preparation of the reactive dyes of the formula (4a), which
comprises subjecting a compound of the formula 21
[0191] to a condensation reaction with a compound of the formula
22
[0192] or subjecting a compound of the formula (18) to a
condensation reaction with cyanuric chloride or cyanuric fluoride
and then subjecting the resulting product to a condensation
reaction with a compound of the formula 23
[0193] in which
[0194] R.sub.6, R.sub.7, R.sub.8, Y.sub.2 and X.sub.3 are as
defined under formula (4a) and
[0195] X.sub.3' is as defined for X.sub.3 under formula (4a).
[0196] The individual condensation reactions are carried out, for
example, by processes which are known per se, as a rule in aqueous
solution, at a temperature of, for example, 0 to 50.degree. C., in
particular 0 to 30.degree. C., and a pH of, for example, 3 to 10,
in particular 3 to 8.
[0197] The further reactive dyes used for the process according to
the invention are known or can be prepared analogously to known
dyes.
[0198] Thus, for example, reactive dyes of the formula (1) can be
obtained by subjecting a compound of the formula 24
[0199] to a condensation reaction with a compound of the formula
25
[0200] in which
[0201] NiPhC, R.sub.1 and V.sub.1 are as defined under formula
(1).
[0202] The condensation reaction is carried out, for example,
according to processes which are known per se, as a rule in aqueous
solution, at a temperature of, for example, 0 to 50.degree. C., in
particular 0 to 30.degree. C., and a pH of, for example 3 to 10, in
particular 3 to 8.
[0203] If appropriate, further condensation reactions can follow.
Thus, for example, if the radical V.sub.1 of the compound of the
formula (22) contains a further amino group, this amino group can
be subjected to a condensation reaction with cyanuric chloride or
cyanuric fluoride. Thereafter, an amino radical can be introduced
by condensation into the cyanuric chloride or cyanuric fluoride
radical of the intermediate thus obtained. The individual
condensation reactions can be carried out, for example, as
described above.
[0204] The present invention furthermore relates to dye mixtures
which comprise at least one reactive dye of the formula (2) 26
[0205] in which
[0206] (R.sub.2).sub.0-3 is 0 to 3 C.sub.1-C.sub.4alkyl radicals
which are identical or different from one another and
[0207] (R.sub.3).sub.0-3 is 0 to 3 substituents, which are
identical or different from another, from the group consisting of
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen, carboxyl and
sulfo,
[0208] X.sub.1 is chlorine or fluorine and
[0209] R.sub.4is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato,
[0210] and at least one reactive dye of the formula (3) 27
[0211] in which
[0212] R.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato,
[0213] X.sub.2 is chlorine or fluorine,
[0214] Y.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl which is
unsubstituted or substituted by hydroxyl, sulfo or sulfato and
uninterrupted or interrupted by oxygen, or phenyl or naphthyl which
are unsubstituted or substituted by C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.4alkoxy, halogen, carboxyl or sulfo, and the benzene
nuclei I, II and III contain no further substituents or are further
substituted by C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, halogen
or carboxyl.
[0215] The reactive dyes of the formulae (2) and (3) here are as
preferred above.
[0216] The dye mixtures according to the invention preferably
comprise reactive dyes of the formula (11) as those of the formula
(2).
[0217] The dye mixtures according to the invention preferably
comprise reactive dyes of the formula (12), in particular of the
formula (13), as those of the formula (3).
[0218] Dye mixtures which comprise a reactive dye of the formula
(11) and a reactive dye of the formula (12), in particular a
reactive dye of the formula (13), are of particular interest.
[0219] The reactive dyes of the formulae (2) and (3) are present in
the dye mixture, for example, in a weight ratio of 1:99 to 99:1,
preferably 10:90 to 90:10, and particularly preferably 20:80 to
80:20.
[0220] The dye mixtures according to the invention can be prepared,
for example, by mixing the individual dyes. This mixing process is
carried out, for example, in suitable mills, for example bead or
pinned disk mills, and in kneaders or mixers.
[0221] The reactive dyes of the formula (4a) according to the
invention and the dye mixtures according to the invention of the
reactive dyes of the formulae (2) and (3) give dyeings and prints
with good allround properties; they have, for example, a high
fibre-dye bond stability both in the acid and in the alkaline
range, a good fastness to light and good wet fastness properties,
such as fastness to washing, water, saltwater, crossdyeing and
perspiration, a good fastness to chlorine, fastness to rubbing,
fastness to ironing and fastness to pleating, and sharp contours
and a high colour strength. The reactive dyes of the formula (4a)
and the dye mixtures of the reactive dyes of the formulae (2) and
(3) are particularly suitable in the process according to the
invention.
[0222] In the following examples, parts are by weight. The
temperatures are degrees Celsius. Parts by weight bear the same
relation to parts by volume as the gram to the cubic
centimetre.
PREPARATION EXAMPLE 1
[0223] a) 21.8 parts of 4-nitroaniline-2-sulfonic acid are stirred
into 350 parts of hot water and the mixture is rendered neutral
with an aqueous sodium hydroxide solution (30%). 6.9 parts of
sodium nitrite are added to this solution and the mixture is
stirred until solution is complete. This solution is added dropwise
at a temperature of 0.degree. C. to a mixture of 100 parts of ice
and 25 parts of hydrochloric acid (30%). When a nitrite excess is
visible on potassium iodide paper, the mixture is subsequently
stirred at a temperature of 0 to 2.degree. C. for half an hour and
the excess nitrite is destroyed by addition of sulfamic acid
solution.
[0224] b) In a separate operation, 31.9 parts of sulfo-gamma acid
in 125 parts of water are rendered neutral with 4 parts of sodium
hydroxide and dissolved to give a clear solution. This sulfo-gamma
acid solution is slowly metered into the solution prepared as
described above under a). Formation of the dyestuff takes place
immediately, and is brought to completion by increasing the pH to a
value of 2.0 by addition of an aqueous sodium acetate solution. A
solution which comprises the compound, shown in the form of the
free acid, of the formula 28
[0225] is obtained.
[0226] c) The solution prepared as described under b) of the
compound of the formula (101) is heated to a temperature of
40.degree. C. and brought to a pH of 9 with sodium hydroxide. The
following solution is now added dropwise at a temperature of about
40.degree. C. in the course of one hour:
[0227] 40.9 parts of sodium sulfide and 7.1 parts of elemental
sulfur, dissolved in 250 parts of hot water at 80.degree. C.
[0228] The pH is kept at a value of 9.0 by metering in hydrochloric
acid solution. The end point is determined by means of thin layer
chromatography.
[0229] The resulting compound is precipitated out by addition of
140 parts of sodium chloride, filtered off and washed with a 10%
aqueous sodium chloride solution. A compound which, in the form of
the free acid, has the formula 29
[0230] is obtained.
[0231] d) 1.84 parts of cyanuric chloride are stirred intensively
in 50 parts of ice-water together with 0.1 part of a surface-active
auxiliary and 0.2 part of disodium hydrogen phosphate. 2.53 parts
of aniline-2,5-disulfonic acid are added. The temperature is kept
constantly at 0.degree. C. The pH is increased to 4.0 with aqueous
sodium hydroxide solution and kept constant until a test
chromatogram no longer indicates uncondensed aniline-2,5-disulfonic
acid. 5.18 parts of the compound of the formula (102) obtained
according to c) are now added, the pH is brought to 7.0 and the
reaction mixture is heated to 30.degree. C. and kept constant under
these conditions until a chromatogram no longer indicates
non-condensed compound of the formula (102). A chromatographically
uniform solution of the reactive dye of the formula (103) shown
below is obtained. After addition of sodium chloride, the dye is
precipitated out, filtered off and dried. A reactive dye which, in
the form of the free acid, is tie compound of the formula 30
[0232] is obtained. The reactive dye of the formula (103) dyes
cotton in red colour shades.
PREPARATION EXAMPLES 2 to 24
[0233] The reactive dyes shown in colume 2 in the following Table
1, which dye cotton in red colour shades, can be obtained in a
manner analogous to that described in Preparation Example 1.
1TABLE 1 Preparation Example Reactive dye 2 31 3 32 4 33 5 34 6 35
7 36 8 37 9 38 10 39 11 40 12 41 13 42 14 43 15 44 16 45 17 46 18
47 19 48 20 49 21 50 22 51 23 52 24 53
PREPARATION EXAMPLE 25
[0234] 28.7 parts of aniline-2,5-disulfonic acid are stirred into
150 parts of water and dissolved under neutral conditions with 2.0
parts of sodium hydroxide. After addition of the customary amount
of buffer and wetting agent, the mixture is cooled to 0.degree. C.
and a little finely crushed ice is additionally added. 4.7 parts by
volume of cyanuric fluoride are then metered in, while stirring
rapidly, and the pH is kept at 6.0 by addition of 15% sodium
hydroxide solution. The mixture is then subsequently stirred for a
short time. A solution of 24.6 parts of the compound of the formula
(102), which has first been dissolved under neutral conditions in
300 parts of water at 30.degree. C., is added dropwise to this
reaction mass and the pH is kept at 6.0 with 15% sodium hydroxide
solution. After the addition, the temperature is kept at 25.degree.
C. for one hour. The reaction solution is dialysed and
freeze-dried. A reactive dye which, in the form of the free acid,
is the compound of the formula (104) 54
[0235] is obtained. The reactive dye of the formula (104) dyes
cotton in red colour shades.
PREPARATION EXAMPLE 26
[0236] The following reactive dye of the formula (105) 55
[0237] which dyes cotton in red colour shades, can be obtained in a
manner analogous to that described in Preparation Example 25.
PREPARATION EXAMPLE 27
[0238] a) 345 parts of chlorosulfonic acid are initially introduced
into a sulfonating flask and 85.7 parts of nickel phthalocyanine
are introduced at a temperature of 20 to 25.degree. C. in the
course of one hour. The mixture is then subsequently stirred for
half an hour.
[0239] The temperature is now increased to 110.degree. C. in the
course of two hours and this temperature is maintained for a
further 30 minutes. The temperature is then increased to
130.degree. C. in the course of one hour and kept at about
133.degree. C. for a further six hours. The temperature is lowered
to 80.degree. C., 59 parts of thionyl chloride are added dropwise
at a temperature of 77 to 80.degree. C. in the course of two hours
and the temperature is maintained for a further four hours. The
reaction mass is cooled. The mass comprises 500 parts. The mass can
be kept in stock. As required, an aliquot portion is discharged
onto ice-water, filtered off and washed, the nickel phthalocyanine
compound, shown in the form of the free acid, of the formula 56
[0240] being obtained.
[0241] b) 66.6 parts of the reaction mass obtained as described
under a) are discharged onto 500 parts of ice and 100 parts of
water and the nickel phthalocyanine trisulfochloride-monosulfonic
acid is washed free from the adherring acid with a 5% sodium
chloride solution.
[0242] 5.64 parts of 1,3-phenylenediamine-4-sulfonic acid are
dissolved in 100 parts of water under neutral conditions with 0.8
parts of sodium hydroxide. 50 parts of fine ice are added to the
solution and the nickel phthalocyanine
trisulfochloride-monosulfonic acid, which has been washed free from
the adherring acid as described above, is introduced. The pH is
kept at 5.0 and the temperature is kept at 0.degree. C. for 12
hours. The temperature is then increased to 50.degree. C. and
maintained for two hours. A content assay shows that 1.0 equivalent
of the amine has undergone condensation with the sulfochloride. 20
parts of sodium chloride are added to the reaction solution and the
precipitate is filtered off and washed free from the non-condensed
phenylenediaminesulfonic acid with a 10% aqueous sodium chloride
solution. An intermediate which, in the form of the free acid, is
the compound of the formula 57
[0243] is obtained.
[0244] c) 3.7 parts of cyanuric chloride are stirred intensively in
70 parts of ice and 30 parts of water, with the addition of a
surface-active agent and 0.2 parts of disodium hydrogen phosphate,
for 10 minutes. The paste of the intermediate obtained as described
under b) is then introduced and the condensation reaction is
carried out at a temperature of 0.degree. C. and a pH of 6.0 for
six hours. 1.3 parts of ammonium chloride are then introduced, the
temperature is increased to 30 to 35.degree. C. and the mixture is
stirred at a pH of 8.0 to 8.5 for a further twelve hours. The
resulting solution is desalinated by means of dialysis and
evaporated to dryness. 27 parts of a reactive dye which, in the
form of the free acid, is the compound of the formula 58
[0245] are obtained. The reactive dye of the formula (106) dyes
cotton in turquoise blue colour shades.
PREPARATION EXAMPLES 28 to 34
[0246] Reactive dyes of the formula 59
[0247] in which
[0248] V.sub.1, x and y are as defined in columns 2 to 4 in the
following Table 2, can be obtained in a manner analogous to that
described in Preparation Example 27. The reactive dyes shown in the
following Table 2 dye cotton in turquoise blue colour shades.
2TABLE 2 Prearation Example V.sub.1 x y 28 60 3 1 29 61 3 1 30 62 3
1 31 63 3 1 32 64 2.75 1.25 33 65 2.5 1.5 34 66 2.2 1.8
PREPARATION EXAMPLE 35
[0249] 28.7 parts of aniline-2,5-disulfonic acid are stirred into
150 parts of water and dissolved under neutral conditions with 2.0
parts of sodium hydroxide. After addition of the customary amount
of buffer and wetting agent, the mixture is cooled to 0.degree. C.
and a little finely crushed ice is additionally added. 4.7 parts by
volume of cyanuric fluoride are then metered in, while stirring
rapidly, and the pH is kept at 6.0 by addition of 15% sodium
hydroxide solution. The mixture is then subsequently stirred for a
short time. A hot, neutral 10% solution of 49.0 parts of the
compound of the formula 67
[0250] (x=1.5; preparation analogous to Preparation Example 27a)
and b)) is added dropwise to this reaction mass at 10 to 15.degree.
C., the pH being kept at 7.0 with 15% sodium hydroxide solution.
After the addition, the temperature is allowed to rise to about
25.degree. C., until the uptake of alkali has ended. The reaction
solution is dialysed and freeze-dried. A reactive dye which, in the
form of the free acid, is the compound of the formula (107) 68
[0251] is obtained. The reactive dye of the formula (107) dyes
cotton in turquoise blue colour shades.
APPLICATION EXAMPLE 1
[0252] a) Mercerized cotton-satin is padded with a liquor
comprising 40 g/l of sodium carbonate and 100 g/l of urea (liquor
pick-up 70%) and dried.
[0253] b) On the cotton-satin pretreated according to step a), on
the same substrate area, an ink A comprising 15% by weight of the
reactive dye of the formula 69
[0254] 20% by weight of 1,2-propylene glycol and 65% by weight of
water,
[0255] and
[0256] an ink B comprising 15% by weight of the reactive dye of the
formula 70
[0257] 20% by weight of 1,2-propylene glycol and 65% by weight of
water, are printed with two different drop on demand piezo ink jet
heads. The print is dried completely and fixed in saturated steam
at 102.degree. C. for 8 minutes, rinsed cold, washed out at the
boil,, rinsed again and dried. A green print which is fast to
washing and has a very high fastness to light is obtained. If the
procedure is as described in Application Example 1, but an ink A
which comprises 15% by weight of one of the reactive dyes according
to Preparation Examples 27 and 29 to 35 instead of 15% by weight of
the reactive dye of the formula (108) is used, analogous prints are
obtained.
[0258] If the procedure is as described in Application Example 1,
but an ink B which comprises 11% by weight of the reactive dye of
the formula (109) and 4% by weight of the reactive dye of the
formula (112) instead of 15% by weight of the reactive dye of the
formula (109) is used, analogous prints are obtained.
APPLICATION EXAMPLE 2
[0259] a) Causticized viscose fabric is padded with a liqour
comprising 40 g/l of sodium carbonate and 150 g/l of urea (liquor
pick-up 70%) and dried.
[0260] b) On the viscose fabric pretreated according to step a), on
the same area of substrate, an ink A comprising 15% by weight of
the reactive dye of the formula (108), 20% by weight of
1,2-propylene glycol and 65% by weight of water,
[0261] and
[0262] an ink B comprising 15% by weight of the reactive dye of the
formula 71
[0263] 20% by weight of 1,2-propylene glycol and 65% by weight of
water, are printed with two different drop on demand piezo ink jet
heads. The print is dried completely and fixed in saturated steam
at 102.degree. C. for 8 minutes, rinsed cold, washed out at the
boil, rinsed again and dried. A green print which is fast to
washing and has a very high fastness to light is obtained.
[0264] If the procedure is as in Application Example 2 but an ink A
which comprises 15% by weight of one of the reactive dyes according
to Preparation Examples 27 and 29 to 35 instead of 15% by weight of
the reactive dye of the formula (108) is used, analogous prints are
obtained.
APPLICATION EXAMPLE 3
[0265] a) Mercerized cotton-satin is padded with a liquor
comprising 40 g/l of sodium carbonate and 100 g/l of urea (liquor
pick-up 70%) and dried.
[0266] b) On the cotton-satin pretreated according to step a), on
the same area of substrate, an ink A comprising 15% by weight of
the reactive dye of the formula (108), 20% by weight of
1,2-propylene glycol and 65% by weight of water,
[0267] and
[0268] an ink B comprising 15% by weight of the reactive dye of the
formula 72
[0269] 20% by weight of 1,2-propylene glycol and 65% by weight of
water, are printed with two different drop on demand piezo ink jet
heads. The print is dried completely and fixed in saturated steam
at 102.degree. C. for 8 minutes, rinsed cold, washed out at the
boil, rinsed again and dried. A violet print which is fast to
washing and has a very high fastness to light is obtained.
[0270] If the procedure is as described in Application Example 3,
but an ink A which comprises 15% by weight of one of the reactive
dyes according to Preparation Examples 27 and 29 to 35 instead of
15% by weight of the reactive dye of the formula (108) is used,
analogous prints are obtained.
[0271] If the procedure is as described in Application Example 3,
but an ink B which comprises 15% by weight of one of the reactive
dyes according to Preparation Examples 11 and 3 to 26 instead of
15% by weight of the reactive dye of the formula (111) is used,
analogous prints are obtained.
APPLICATION EXAMPLE 4
[0272] a) Mercerized cotton-satin is padded with a liquor
comprising 40 g/l of sodium carbonate and 100 g/l of urea (liquor
pick-up 70%) and dried.
[0273] b) On the cotton-satin pretreated according to step a), on
the same area of substrate, an ink A comprising 15% by weight of
the reactive dye of the formula (108), 20% by weight of
1,2-propylene glycol and 65% by weight of water, an ink B
comprising 15% by weight of the reactive dye of the formula 73
[0274] 20% by weight of 1,2-propylene glycol and 65% by weight of
water, and an ink C comprising 5% by weight of the reactive dye of
the formula 74
[0275] and 10% by weight of the reactive dye of the formula 75
[0276] 20% by weight of 1,2-propylene glycol and 60% by weight of
water, are printed with three different drop on demand piezo ink
jet heads. The print is dried completely and fixed in saturated
steam at 102.degree. C. for 8 minutes, rinsed cold, washed out at
the boil, rinsed again and dried. A green print which is fast to
washing and has a very high fastness to light is obtained.
[0277] If the procedure is as described in Application Example 4,
but an ink which comprises 15% by weight of one of the reactive
dyes according to Preparation Examples 27 and 29 to 35 instead of
15% by weight of the reactive dye of the formula (108) is used,
analogous prints are obtained.
[0278] If the procedure is as described in Application Example 4,
but an ink B which comprises 11% by weight of the reactive dye of
the formula (109) and 4% by weight of the reactive dye of the
formula (112) instead of 15% by weight of the reactive dye of the
formula (112) is used, analogous prints are obtained.
APPLICATION EXAMPLE 5
[0279] 1.8 parts of a mixture of the reactive dyes of the formulae
(109) and (112) in a ratio of 4:1 and
[0280] 3 parts of the reactive dye of the formula (108) are
stirred, with rapid stirring, into 100 parts of a stock thickener
comprising 50 parts of 5% sodium alginate thickener, 10 parts of
urea, 1 part of sodium m-nitrobenzenesulfonate, 1.5 parts of
calcined sodium carbonate and 32.7 parts of water. Mercerized
cotton-satin is printed with the printing paste thus obtained and
dried and the resulting printed material is fixed in saturated
steam at 102.degree. C. for 8 minutes. The material is rinsed cold,
washed out at the boil, rinsed again and dried. A green print which
is fast to washing and has a very high fastness to light is
obtained.
[0281] If the procedure is as described in Application Example 5,
but 3 parts of one of the reactive dyes according to Preparation
Examples 27 and 29 to 35 are used instead of 3 parts of the
reactive dye of the formula (108), analogous prints are
obtained.
APPLICATION EXAMPLE 6
[0282] 0.8 part of the reactive dye of the formula (110) and
[0283] 3 parts of the reactive dye of the formula (108) are
stirred, with rapid stirring, into 100 parts of a stock thickener
comprising 50 parts of 5% sodium alginate thickener, 15 parts of
urea, 1 part of sodium m-nitrobenzenesulfonate, 1.5 parts of
calcined sodium carbonate and 28.7 parts of water. Causticized
viscose fabric is printed with the printing paste thus obtained and
dried and the resulting printed material is fixed in saturated
steam at 102.degree. C. for 8 minutes. The material is rinsed cold,
washed out at the boil, rinsed again and dried. A green print which
is fast to washing and has a very high fastness to light is
obtained.
[0284] If the procedure is as described in Application Example 6,
but 3 parts of one of the reactive dyes according to Preparation
Examples 27 and 29 to 35 are used instead of 3 parts of the
reactive dye of the formula (108), analogous prints are
obtained.
APPLICATION EXAMPLE 7
[0285] 0.8 part of the reactive dye of the formula (111) and
[0286] 3 parts of the reactive dye of the formula (108) are
stirred, with rapid stirring, into 100 parts of a stock thickener
comprising 50 parts of 5% sodium alginate thickener, 10 parts of
urea, 1 part of sodium m-nitrobenzenesulfonate, 1.5 parts of
calcined sodium carbonate and 33.7 parts of water. Mercerized
cotton-satin is printed with the printing paste thus obtained and
dried and the resulting printed material is fixed in saturated
steam at 102.degree. C. for 8 minutes. The material is rinsed cold,
washed out at the boil, rinsed again and dried. A violet print
which is fast to washing and has a very high fastness to light is
obtained.
[0287] If the procedure is as described in Application Example 7,
but 3 parts of one of the reactive dyes according to Preparation
Examples 27 and 29 to 35 are used instead of 3 parts of the
reactive dye of the formula (108), analogous prints are
obtained.
[0288] If the procedure is as described in Application Example 7,
but 0.8 part of one of the reactive dyes according to Preparation
Examples 1 and 3 to 26 is used instead of 0.8 part of the reactive
dye of the formula (111), analogous prints are obtained.
APPLICATION EXAMPLE 8
[0289] 1.8 parts of a mixture of the reactive dyes of the formulae
(109) and (112) in a ratio of 4:1
[0290] and
[0291] 3 parts of the reactive dye of the formula (108) are
dissolved in 50 parts of water. 50 parts of a solution which
comprises, per litre, 5 g of sodium hydroxide and 20 g of calcined
sodium carbonate are added. A bleached cotton fabric is padded with
the solution thus obtained such that it increases by 70% of its
weight, and is wound up onto a roll. The cotton fabric is stored at
room temperature in this manner for 6 hours. Thereafter, the dyed
goods are rinsed, washed out at the boil, rinsed again and dried. A
green dyeing which is fast to washing and has a very high fastness
to light is obtained.
[0292] If the procedure is as described in Application Example 8
but 3 parts of one of the reactive dyes according to Preparation
Examples 27 and 29 to 35 are used instead of 3 parts of the
reactive dye of the formula (108), analogous dyeings are
obtained.
APPLICATION EXAMPLE 9
[0293] 1.8 parts of the reactive dye of the formula (109) and
[0294] 3 parts of the reactive dye of the formula (108) are
dissolved in 100 parts of water. A bleached cotton fabric is padded
with the solution thus obtained such that it increases by 70% of
its weight, and is dried. The fabric is then padded with a solution
which comprises, per litre, 4 g of sodium hydroxide and 300 g of
sodium chloride and the dyeing is steamed in saturated steam at
102.degree. C. for 30 seconds. Thereafter, the dyed goods are
rinsed, washed out at the boil, rinsed again and dried. A green
dyeing which is fast to washing and has a very high fastness to
light is obtained.
[0295] If the procedure is as described in Application Example 9,
but 3 parts of one of the reactive dyes according to Preparation
Examples 27 and 29 to 35 are used instead of 3 parts of the
reactive dye of the formula (108), analogous dyeings are
obtained.
APPLICATION EXAMPLE 10
[0296] 1.0 part of the reactive dye of the formula 76
[0297] and 3 parts of the reactive dye according to Preparation
Example 18 are dissolved in 200 parts of water. 800 parts of a
solution which comprises, per litre, 50 g of Glauber's salt are
added. 100 parts of a bleached cotton knitted fabric are introduced
into this dyebath at 40.degree. C. After 45 minutes, 50 parts of a
solution which comprises, per litre, 16 g of sodium hydroxide and
20 g of calcined sodium carbonate are added. The temperature of the
dyebath is kept at 40.degree. C. for a further 45 minutes.
Thereafter, the dyed goods are rinsed, washed out at the boil,
rinsed again and dried. A green dyeing which is fast to washing and
has a very high fastness to light is obtained.
[0298] If the procedure is as described in Application Example 10
but 3 parts of one of the reactive dyes according to Preparation
Examples 33 or 34 are used instead of 3 parts of the reactive dye
according to Preparation Example 32, analogous dyeings are
obtained.
APPLICATION EXAMPLE 11
[0299] 2.54 parts of the reactive dye according to Preparation
Example 11 are dissolved in 100 parts of distilled water and the
solution is filtered. The ink thus obtained is printed by means of
a drop on demand ink jet printer onto a commercially available ink
jet paper or photo paper or a glossy film (for example Epson Glossy
Film). The resulting print in a brilliant red shade has a very good
fastness to light.
[0300] If the procedure is as described in Application Example 11
but 2.54 parts of one of the reactive dyes according to Preparation
Examples 12 or 16 are used instead of 2.54 parts of the reactive
dye according to Preparation Example 11, prints with a very good
fastness to light are likewise obtained.
* * * * *