U.S. patent application number 12/711774 was filed with the patent office on 2010-06-17 for mixtures of reactive dyes and their use.
This patent application is currently assigned to Huntsman International LLC. Invention is credited to Georg Roentgen, Athanassios Tzikas.
Application Number | 20100151134 12/711774 |
Document ID | / |
Family ID | 34928914 |
Filed Date | 2010-06-17 |
United States Patent
Application |
20100151134 |
Kind Code |
A1 |
Tzikas; Athanassios ; et
al. |
June 17, 2010 |
MIXTURES OF REACTIVE DYES AND THEIR USE
Abstract
Dye mixtures comprising at least one dye of formula ##STR00001##
together with at least one dye from the group of formulae
##STR00002## wherein the radicals have the definitions given in the
claims, are suitable for dyeing or printing cellulose-containing
fibre materials, while at the same time exhibiting good build-up
behaviour, and yield dyeings of deep shade having good fastness
properties.
Inventors: |
Tzikas; Athanassios;
(Pratteln, CH) ; Roentgen; Georg; (Freiburg,
DE) |
Correspondence
Address: |
HUNTSMAN INTERNATIONAL LLC
LEGAL DEPARTMENT, 10003 WOODLOCH FOREST DRIVE
THE WOODLANDS
TX
77380
US
|
Assignee: |
Huntsman International LLC
The Woodlands
TX
|
Family ID: |
34928914 |
Appl. No.: |
12/711774 |
Filed: |
February 24, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10592888 |
Sep 15, 2006 |
|
|
|
PCT/EP2005/051037 |
Mar 9, 2005 |
|
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|
12711774 |
|
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Current U.S.
Class: |
427/288 ;
106/31.44; 106/31.48; 427/256; 8/549 |
Current CPC
Class: |
D06P 1/38 20130101; C09B
67/0057 20130101; C09B 62/09 20130101; C09B 67/0058 20130101; C09B
67/0044 20130101; C09B 67/0042 20130101; D06P 3/148 20130101; C09D
11/328 20130101; D06P 3/666 20130101; D06P 5/30 20130101 |
Class at
Publication: |
427/288 ;
106/31.44; 106/31.48; 427/256; 8/549 |
International
Class: |
C09B 62/006 20060101
C09B062/006; C09D 11/02 20060101 C09D011/02; B05D 5/00 20060101
B05D005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 19, 2004 |
EP |
04101142.0 |
Claims
1. A dye mixture comprising at least one dye of formula
##STR00020## and at least one dye from the group of formulae
##STR00021## wherein (R.sub.1).sub.b denotes b identical or
different substituents from the group C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, sulfo and halogen, R.sub.2, R.sub.3,
R.sub.4 and R.sub.5 are each independently of the others hydrogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, sulfo or halogen, G
is a phenylene radical that is unsubstituted or substituted by
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, halogen, carboxy or
by sulfo, or is a cyclohexylene, phenylenemethylene or
C.sub.2-C.sub.6 alkylene radical, one of the radicals Q.sub.1 and
Q.sub.2 is amino and the other of the radicals Q.sub.1 and Q.sub.2
is hydroxy, X.sub.1 is halogen, Y.sub.1, Y.sub.2 and Y.sub.3 are
each independently of the others a fibre-reactive radical of
formula ##STR00022## wherein X.sub.2 is halogen, T.sub.2
independently has the definition of X.sub.2, is a
non-fibre-reactive substituent or is a fibre-reactive radical of
formula ##STR00023## (R.sub.6).sub.0-2 denotes from 0 to 2
identical or different substituents from the group halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4alkoxy and sulfo, Z is vinyl
or a --CH.sub.2--CH.sub.2-U radical and U is a group that is
removable under alkaline conditions, Q is a --CH(Hal)-CH.sub.2-Hal
or --C(Hal)=CH.sub.2 group, m and n are each independently of the
other the number 2, 3 or 4 and Hal is halogen, T.sub.1 is a
fibre-reactive radical of the above formula (6b), (6c), (6d) or
(6e) and b and k are each independently of the other the number 0,
1 or 2.
2. A dye mixture according to claim 1, wherein T.sub.1 is a radical
of formula (6b), (6c) or (6d).
3. A dye mixture according to claim 1, wherein the dye of formula
(1) is a dye of formula ##STR00024## wherein T.sub.1, X.sub.1,
Y.sub.1 and k each have the definitions according to claim 1.
4. A dye mixture according to claim 1, wherein the dye of formula
(2) is a dye of formula ##STR00025## wherein R.sub.2 is hydrogen or
C.sub.1-C.sub.4 alkoxy, R.sub.3 is hydrogen, C.sub.1-C.sub.4 alkyl
or C.sub.1-C.sub.4 alkoxy, and each Z, independently, has the
definition according to claim 1.
5. A dye mixture according to claim 1, wherein the dye of formula
(3) is a dye of formula ##STR00026## wherein (R.sub.7).sub.0-4
denotes from 0 to 4 identical or different substituents from the
group C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, halogen,
carboxy and sulfa and Y.sub.2 has the definition according to claim
1.
6. A dye mixture according to claim 1, wherein the dye of formula
(4) is a dye of formula ##STR00027## wherein Y.sub.3 has the
definition according to claim 1.
7. An aqueous ink comprising a dye mixture according to claim
1.
8. A process for the printing of a substrate comprising spraying
individual droplets of an aqueous ink onto the substrate from a
nozzle in a controlled manner wherein the aqueous ink comprises a
dye mixture comprising at least one dye of formula ##STR00028## and
at least one dye from the group of formulae ##STR00029## wherein
(R.sub.1).sub.b denotes b identical or different substituents from
the group C.sub.1-C.sub.4a alkyl, C.sub.1-C.sub.4a alkoxy, sulfo
and halogen, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each
independently of the others hydrogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, sulfo or halogen, G is a phenylene radical
that is unsubstituted or substituted by C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, halogen, carboxy or by sulfo, or is a
cyclohexylene, phenylenemethylene or C.sub.2-C.sub.6 alkylene
radical, one of the radicals Q.sub.1 and Q.sub.2 is amino and the
other of the radicals Q.sub.1 and Q.sub.2 is hydroxy, X.sub.1 is
halogen, Y.sub.1, Y.sub.2 and Y.sub.3 are each independently of the
others a fibre-reactive radical of formula ##STR00030## wherein
X.sub.2 is halogen, T.sub.2 independently has the definition of
X.sub.2, is a non-fibre-reactive substituent or is a fibre-reactive
radical of formula ##STR00031## (R.sub.6).sub.0-2 denotes from 0 to
2 identical or different substituents from the group halogen,
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4alkoxy and sulfa, Z is vinyl
or a --CH.sub.2--CH.sub.2-U radical and U is a group that is
removable under alkaline conditions, Q is a --CH(Hal)-CH.sub.2-Hal
or --C(Hal)=CH.sub.2 group, m and n are each independently of the
other the number 2, 3 or 4 and Hal is halogen, T.sub.1 is a
fibre-reactive radical of the above formula (6b), (6c), (6d) or
(6e) and b and k are each independently of the other the number 0,
1 or 2.
9. The process of claim 8 wherein the substrate is a textile fibre
material.
10. A method for dyeing fibre material which comprises applying a
dye mixture according to claim 1 to the fibre material and fixing
the dye to the fibre material.
11. The method according to claim 10 wherein the fibre material is
a hydroxyl-group-containing fibre material or a
nitrogen-group-containing fibre material.
12. The method of claim 10 wherein the fibre material is a
cellulosic fibre material.
13. The method of claim 12 wherein the cellulosic fibre material is
a cotton-containing fibre material.
Description
[0001] This application is a continuation application of U.S.
patent application Ser. No. 10/592,888, currently pending, which
was the National Phase of International Application
PCT/EP2005/051037 filed Mar. 9, 2005 which designated the U.S. and
which claims priority to European Pat. App. No. 04101142.0 filed
Mar. 19, 2004. The noted applications are incorporated herein by
reference.
FIELD OF INVENTION
[0002] The present invention relates to mixtures of reactive dyes,
which mixtures are suitable for dyeing or printing
nitrogen-containing or hydroxy-group-containing fibre materials and
yield dyeings or prints having good all-round fastness
properties.
BACKGROUND OF THE INVENTION
[0003] The practice of dyeing has recently led to higher demands
being made on the quality of the dyeings and the economic
efficiency of the dyeing process. As a result, there continues to
be a need for novel, readily obtainable dyeing compositions having
good properties, especially in respect of their application.
[0004] Dyeing today requires reactive dyes that, for example, have
sufficient substantivity and at the same time exhibit good ease of
washing-off of unfixed dye. In addition, they should exhibit a good
colour yield and a high reactivity, the objective being especially
to obtain dyeings having high degrees of fixing. In many cases the
build-up behaviour of reactive dyes is not sufficient to meet the
demands made, especially when dyeing in very deep shades.
[0005] The problem underlying the present invention is therefore to
provide novel mixtures of reactive dyes, which mixtures are
especially suitable for dyeing and printing fibre materials and
possess the above-described qualities to a high degree. They should
also yield dyeings having good all-round fastness properties, for
example fastness to light and to wetting.
SUMMARY OF THE INVENTION
[0006] The present invention accordingly relates to dye mixtures
comprising at least one dye, for example one, two or three dyes,
preferably one dye, of formula
##STR00003##
[0007] and at least one dye, for example one, two or three dyes,
from the group of formulae
##STR00004##
[0008] wherein
[0009] (R.sub.1).sub.b denotes b identical or different
substituents from the group C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
alkoxy, sulfo and halogen,
[0010] R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently
of the others hydrogen, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
alkoxy, sulfo or halogen,
[0011] G is a phenylene radical that is unsubstituted or
substituted by C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy,
halogen, carboxy or by sulfo, or is a cyclohexylene,
phenylenemethylene or C.sub.2-C.sub.6 alkylene radical,
[0012] one of the radicals Q.sub.1 and Q.sub.2 is amino and the
other of the radicals Q.sub.1 and Q.sub.2 is hydroxy,
[0013] X.sub.1 is halogen,
[0014] Y.sub.1, Y.sub.2 and Y.sub.3 are each independently of the
others a fibre-reactive radical of formula
##STR00005##
[0015] wherein
[0016] X.sub.2 is halogen,
[0017] T.sub.2 independently has the definition of X.sub.2, is a
non-fibre-reactive substituent or is a fibre-reactive radical of
formula
##STR00006##
[0018] (R.sub.6).sub.0-2 denotes from 0 to 2 identical or different
substituents from the group halogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy and sulfo,
[0019] Z is vinyl or a --CH.sub.2--CH.sub.2-U radical and U is a
group that is removable under alkaline conditions,
[0020] Q is a --CH(Hal)-CH.sub.2-Hal or --C(Hal)=CH.sub.2
group,
[0021] m and n are each independently of the other the number 2, 3
or 4, and Hal is halogen,
[0022] T.sub.1 is a fibre-reactive radical of the above-mentioned
formula (6b), (6c), (6d) or (6e), and b and k are each
independently of the other the number 0, 1 or 2.
DETAILED DESCRIPTION OF THE INVENTION
[0023] A suitable combination of at least one, two or three dyes
from the group of formulae (2), (3) and (4) is, for example, one or
two dyes of formula (2); one or two dyes of formula (3); or one or
two dyes of formula (4); one dye of formula (2) and one dye of
formula (3); one dye of formula (2) and one dye of formula (4); or
one dye of formula (3) and one dye of formula (4); or one dye of
formula (2), one dye of formula (3) and one dye of formula (4);
preferably one dye of formula (2), one dye of formula (3), or one
dye of formula (4).
[0024] As C.sub.1-C.sub.4 alkyl there come into consideration for
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and the
corresponding radicals in the bridging member G, each independently
of the others, for example, methyl, ethyl, propyl, isopropyl,
butyl, sec-butyl, tert-butyl and isobutyl, preferably methyl and
ethyl and especially methyl.
[0025] As C.sub.1-C.sub.4 alkoxy there come into consideration for
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.8 and the
corresponding radicals in the bridging member G, each independently
of the others, for example, methoxy, ethoxy, n-propoxy, isopropoxy,
n-butoxy and isobutoxy, preferably methoxy and ethoxy and
especially methoxy.
[0026] As halogen there come into consideration for R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and the corresponding
radicals in the bridging member G, each independently of the
others, for example, fluorine, chlorine and bromine, preferably
chlorine and bromine and especially chlorine.
[0027] As a C.sub.2-C.sub.6 alkylene radical for the bridging
member G there come into consideration a branched or unbranched
radical, such as, for example, 1,2-ethylene, 1,3-propylene,
1,2-propylene, 1,4-butylene, 1,3-butylene, 1,5-pentylene,
3,5-pentylene, 1,6-hexylene, 2,5-hexylene, 4,6-hexylene and the
radicals of formulae
##STR00007##
and
##STR00008##
[0028] For X.sub.i and X.sub.2, each independently of the other,
there come into consideration, for example, fluorine, chlorine and
bromine, preferably fluorine and chlorine. X.sub.1 is especially
chlorine.
[0029] As the leaving group U there come into consideration, 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.4 alkyl and
--OSO.sub.2--N(C.sub.1-C.sub.4 alkyl).sub.2. Preferably, U is a
group of formula --Cl, --OSO.sub.3H, --SSO.sub.3H, --OCO--CH.sub.3,
--OCO--C.sub.6H.sub.5 or --OPO.sub.3H.sub.2, especially --Cl or
--OSO.sub.3H and more especially --OSO.sub.3H.
[0030] Examples of suitable radicals Z are accordingly vinyl,
.beta.-bromo- or .beta.-chloroethyl, .beta.-acetoxyethyl,
.beta.-benzoyloxyethyl, .beta.-phosphatoethyl, .beta.-sulfatoethyl
and .beta.-thiosulfatoethyl.
[0031] Preferably, Z is independently vinyl, .beta.-chloroethyl or
.beta.-sulfatoethyl, especially vinyl or .beta.-sulfatoethyl.
[0032] Preferably, (R.sub.1).sub.b denotes b identical or different
substituents from the group C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
alkoxy and sulfo, especially b sulfo substituents.
[0033] Preferably, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each
independently of the others hydrogen, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy or sulfo, especially hydrogen, methyl,
methoxy or sulfo.
[0034] R.sub.4 and R.sub.5 are especially preferably hydrogen.
[0035] (R.sub.6).sub.0-2 denotes preferably from 0 to 2 identical
or different substituents from the group C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy and sulfo, especially methyl, methoxy and
sulfo.
[0036] R.sub.6 is especially preferably hydrogen.
[0037] G is preferably an unsubstituted phenylene radical or a
phenylene radical substituted by C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.4 alkoxy, halogen, carboxy or by sulfo.
[0038] Preferably, T.sub.1 is a radical of formula (6b), (6c) or
(6d), especially of formula (6c), the definitions and preferred
meanings given hereinbefore applying to the variables.
[0039] In an embodiment of interest, T.sub.1 is a radical of
formula
##STR00009##
[0040] wherein
[0041] (R.sub.6).sub.0-2 and Z each have the definitions and
preferred meanings given hereinbefore.
[0042] T.sub.2 is preferably a non-fibre-reactive substituent or a
fibre-reactive radical of formula (6a), (6b), (6c), (6d) or
(6e).
[0043] As a fibre-reactive radical, T.sub.2 is preferably a radical
of formula (6b), (6c), (6d) or (6e), especially of formula (6b),
(6c) or (6d), and more especially of formula (6c), the definitions
and preferred meanings given hereinbefore applying to the
variables.
[0044] When T.sub.2 is a non-fibre-reactive substituent it may be,
for example, hydroxy; C.sub.1-C.sub.4 alkoxy; C.sub.1-C.sub.4
alkylthio unsubstituted or substituted, for example, by hydroxy,
carboxy or by sulfo; amino; amino mono- or di-substituted by
C.sub.1-C.sub.8 alkyl, wherein the alkyl is unsubstituted or is
further substituted, for example, by sulfo, sulfato, hydroxy,
carboxy or by phenyl, especially by sulfo or by hydroxy, and may be
interrupted one or more times by the radical --O--;
cyclo-hexylamino; morpholino; N--C.sub.1-C.sub.4
alkyl-N-phenylamino or phenylamino or naphthylamino, wherein the
phenyl or naphthyl is unsubstituted or substituted, for example, by
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy, C.sub.2-C.sub.4
alkanoylamino, carboxy, sulfo or by halogen and the alkyl is
unsubstituted or substituted, for example, by hydroxy, sulfo or by
sulfato.
[0045] Examples of suitable non-fibre-reactive substituents T.sub.2
are amino, methylamino, ethylamino, .beta.-hydroxyethylamino,
N-methyl-N-.beta.-hydroxyethylamino,
N-ethyl-N-.beta.-hydroxyethylamino,
N,N-di-.beta.-hydroxyethylamino, .beta.-sulfoethylamino,
cyclohexylamino, morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3-
or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or
4-sulfophenylamino, 2,5-disulfophenylamino, 2-, 3- or
4-carboxyphenylamino, 1- or 2-naphthylamino,
1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino,
N-ethyl-N-phenylamino, N-methyl-N-phenylamino, methoxy, ethoxy, n-
or iso-propoxy and hydroxy.
[0046] As a non-fibre-reactive substituent, T.sub.2 preferably has
the definition C.sub.1-C.sub.4 alkoxy; C.sub.1-C.sub.4 alkylthio
that is unsubstituted or substituted by hydroxy, carboxy or by
sulfo; hydroxy; amino; N-mono- or N,N-di-C.sub.1-C.sub.4 alkylamino
that is unsubstituted or substituted in the alkyl moiety/moieties
by hydroxy, sulfato or by sulfo; morpholino; phenylamino that is
unsubstituted or substituted in the phenyl ring by sulfo, carboxy,
acetylamino, chlorine, methyl or by methoxy; or N--C.sub.1-C.sub.4
alkyl-N-phenylamino that is unsubstituted or substituted in the
same way on the phenyl ring, wherein the alkyl is unsubstituted or
substituted by hydroxy, sulfo or by sulfato; or naphthylamino that
is unsubstituted or substituted by from 1 to 3 sulfo groups.
[0047] Non-fibre-reactive substituents T.sub.2 to which special
preference is given are amino, N-methylamino, N-ethylamino,
N-.beta.-hydroxyethylamino, N-methyl-N-.beta.-hydroxyethylamino,
N-ethyl-N-.beta.-hydroxyethylamino,
N,N-di-.beta.-hydroxyethylamino, .beta.-sulfoethylamino,
morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or
4-sulfophenylamino, 2,5-disulfophenylamino and
N--C.sub.1-C.sub.4alkyl-N-phenylamino.
[0048] In the case of the fibre-reactive radicals T.sub.2 of
formulae (6a) and (6b), Z is preferably vinyl or
.beta.-chloroethyl. In the case of the fibre-reactive radicals
T.sub.2 of formulae (6c) and (6d), Z is preferably vinyl or
.beta.-sulfatoethyl.
[0049] In an embodiment of interest, T.sub.2 is one of the
above-mentioned fibre-reactive radicals.
[0050] Hal in the fibre-reactive radicals of formulae (5d), (5e)
and (6e) is preferably chlorine or bromine, especially bromine.
[0051] Preferably, Y.sub.1 is a radical of formula (5a), (5b),
(5c), (5d) or (5e), especially of formula (5a), (5b) or (5c) and
more especially of formula (5a), the definitions and preferred
meanings given above applying to the variables.
[0052] Preferably, Y.sub.2 is a radical of formula (5a) or (5f),
especially of formula (5a), the definitions and preferred meanings
given above applying to the variables.
[0053] Preferably, Y.sub.3 is a radical of formula (5a) or (5f),
especially of formula (5a), the definitions and preferred meanings
given above applying to the variables. When Y.sub.3 is a radical of
formula (5f), T.sub.2 denoting a radical of formula (6b) or (6c),
especially (6b), is of interest.
[0054] b is preferably the number 1 or 2 and especially the number
1.
[0055] k is preferably the number 1 or 2 and especially the number
1.
[0056] m and n are preferably each independently of the other the
number 2 or 3.
[0057] m is especially preferably the number 3.
[0058] n is especially preferably the number 2.
[0059] The dye of formula (1) is preferably a dye of formula
##STR00010##
[0060] wherein
[0061] T.sub.1, X.sub.1, Y.sub.1 and k each have the definitions
and preferred meanings given above.
[0062] The dye of formula (2) is preferably a dye of formula
##STR00011##
[0063] wherein
[0064] R.sub.2 is hydrogen or C.sub.1-C.sub.4 alkoxy, preferably
C.sub.1-C.sub.4 alkoxy,
[0065] R.sub.3 is hydrogen, C.sub.1-C.sub.4 alkyl or
C.sub.1-C.sub.4 alkoxy, and
[0066] each Z, independently, has the definition and preferred
meanings given above.
[0067] R.sub.2 is especially preferably methoxy.
[0068] R.sub.3 is especially preferably hydrogen, methyl or
methoxy, especially hydrogen.
[0069] The dye of formula (3) is preferably a dye of formula
##STR00012##
[0070] wherein
[0071] (R.sub.7).sub.0-4 denotes from 0 to 4 identical or different
substituents from the group C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4
alkoxy, halogen, carboxy and sulfo, preferably from the group
C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4 alkoxy and sulfa and
[0072] Y.sub.2 has the definition and preferred meanings given
above.
[0073] The dye of formula (4) is preferably a dye of formula
##STR00013##
[0074] wherein
[0075] Y.sub.3 has the definition and preferred meanings given
above.
[0076] A dye of formula (1) to which special preference is given is
a dye of formula
##STR00014##
[0077] wherein
[0078] X.sub.1 is halogen, especially chlorine, and
[0079] each Z independently has the definition and preferred
meanings given above and is preferably vinyl or
.beta.-sulfatoethyl.
[0080] The dye of formula (1) is, for example, a dye of formula
##STR00015##
[0081] preferably of formula (1.1).
[0082] The dye of formula (2) is, for example, a dye of formula
##STR00016##
[0083] preferably of formula (2.1).
[0084] The dye of formula (3) is, for example, a dye of formula
##STR00017## ##STR00018##
[0085] preferably of formula (3A).
[0086] The dye of formula (4) is, for example, a dye of formula
##STR00019##
[0087] preferably of formula (4.1) or (4.2), especially of formula
(4.1).
[0088] The reactive dyes of formulae (1) to (4) in the dye mixtures
according to the invention contain sulfo groups, each of which is
either in the form of the free sulfonic acid or, preferably, in the
form of a salt thereof, for example in the form of the sodium,
lithium, potassium or ammonium salt, or in the form of a salt of an
organic amine, for example in the form of the triethanolammonium
salt.
[0089] The reactive dyes of formulae (1) to (4), and therefore also
the dye mixtures, may comprise further additives, for example
sodium chloride or dextrin.
[0090] The dyes of formula (1) and the total amount of the dyes of
formulae (2), (3) and (4) are present in the dye mixture according
to the invention in a weight ratio of, for example, from 1:99 to
99:1, preferably from 5:95 to 95:5 and especially from 10:90 to
90:10.
[0091] The dyes of formulae (1), (2), (3) and (4) are known or can
be prepared according to methods known per se. Dyes of formula (1)
are described, for example, in U.S. Pat. No. 4,622,390. Dyes of
formula (2) are disclosed, for example, in DE 960 534, DE 31 13 989
A1, EP 0 063 276 A2 and EP 0 122 600 A1. Dyes of formula (3) are
known, for example, from U.S. Pat. No. 3,558,621, U.S. Pat. No.
4,631,341, U.S. Pat. No. 4,754,023, GB 2 034 731 A and EP 0 064 250
A1. Dyes of formula (4) are described, for example, in U.S. Pat.
No. 4,336,190 and U.S. Pat. No. 4,754,023.
[0092] The dye mixtures according to the invention can be prepared,
for example, by mixing the individual dyes. Such a mixing process
is carried out, for example, in suitable mills, for example ball
mills or pin mills, and also in kneaders or mixers.
[0093] The dye mixtures according to the invention may, where
appropriate, comprise further auxiliaries that, for example,
improve handling or increase storage stability, such as, for
example, buffers, dispersants or anti-dusts. Such auxiliaries are
known to the person skilled in the art.
[0094] The dye mixtures according to the invention are suitable for
dyeing and printing an extremely wide variety of materials,
especially hydroxyl-group-containing or nitrogen-containing fibre
materials. Examples are paper, silk, leather, wool, polyamide
fibres and polyurethanes and also especially cellulosic fibre
materials of all kinds. Such fibre materials are, for example, the
natural cellulosic fibres, such as cotton, linen and hemp, and also
cellulose and regenerated cellulose. The dye mixtures according to
the invention are also suitable for dyeing or printing
hydroxyl-group-containing fibres present in blend fabrics, e.g.
mixtures of cotton with polyester fibres or polyamide fibres.
[0095] The present invention accordingly relates also to the use of
the dye mixtures according to the invention in the dyeing or
printing of hydroxyl-group-containing or nitrogen-containing,
especially cellulose-containing, fibre materials.
[0096] The dye mixtures according to the invention can be applied
to the fibre material and fixed to the fibre in a variety of ways,
especially in the form of aqueous dye solutions and dye print
pastes. They are suitable both for the exhaust method and for
dyeing in accordance with the pad-dyeing method; they can be used
at low dyeing temperatures and require only short steaming times in
the pad-steam process. The build-up behaviour is very good, the
degrees of fixing are high and unfixed dye can be washed off
easily, the difference between the degree of exhaust and the degree
of fixing being remarkably small, that is to say the soaping loss
is very low. The dye mixtures according to the invention are also
suitable for printing, especially on cotton, but are equally
suitable also for printing nitrogen-containing fibres, for example
wool or silk or blend fabrics that contain wool.
[0097] The dyeings and prints produced using the dye mixtures
according to the invention can be reproduced very well, have a high
tinctorial strength and a high fibre-to-dye binding stability in
both the acidic and the alkaline range, and furthermore have good
fastness to light and very good wet-fastness properties, such as
fastness to washing, to water, to sea water, to cross-dyeing and to
perspiration. The dyeings obtained exhibit fibre levelness and
surface levelness.
[0098] The dye mixtures according to the invention are also
suitable as colorants for use in recording systems. Such recording
systems are, for example, commercially available inkjet printers
for paper or textile printing, or writing instruments, such as
fountain pens or ballpoint pens and especially inkjet printers. For
that purpose the dye mixture according to the invention is first
brought into a form suitable for use in recording systems. A
suitable form is, for example, an aqueous ink that comprises the
dye mixture according to the invention as colorant. The inks can be
prepared in customary manner by mixing together the individual
constituents in the desired amount of water.
[0099] Substrates that come into consideration include the
above-mentioned hydroxyl-group-containing or nitrogen-containing
fibre materials, especially cellulose-containing fibre
materials.
[0100] The dyes used in the aqueous inks should preferably have a
low salt content, that is to say they should have a total content
of salts of less than 0.5% by weight, based on the weight of the
dyes. Dyes that have relatively high salt contents as a result of
their preparation and/or as a result of the subsequent addition of
diluents can be salted out, for example, by membrane separation
procedures, such as ultrafiltration, reverse osmosis or
dialysis.
[0101] The inks preferably have a total content of dyes of from 1
to 35% by weight, especially from 1 to 30% by weight and preferably
from 1 to 20% by weight, based on the total weight of the ink. The
preferred lower limit in this case is a limit of 1.5% by weight,
preferably 2% by weight and especially 3% by weight.
[0102] The inks may comprise water-miscible organic solvents, for
example C.sub.1-C.sub.4alcohols, e.g. methanol, ethanol,
n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or
iso-butanol; amides, e.g. dimethylformamide or dimethylacetamide;
ketones or ketone alcohols, e.g. acetone, diacetone alcohol;
ethers, e.g. tetrahydrofuran or dioxane; nitrogen-containing
heterocyclic compounds, e.g. N-methyl-2-pyrrolidone or
1,3-dimethyl-2-imidazolidone, poly-alkylene glycols, e.g.
polyethylene glycol or polypropylene glycol; C.sub.2-C.sub.6
alkylene glycols and thioglycols, e.g. ethylene glycol, propylene
glycol, butylene glycol, triethylene glycol, thio-diglycol,
hexylene glycol and diethylene glycol; other polyols, e.g. glycerol
or 1,2,6-hexanetriol; and C.sub.1-C.sub.4 alkyl ethers of
polyhydric alcohols, e.g. 2-methoxyethanol,
2-(2-methoxy-ethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,
2-[2-(2-methoxyethoxy)ethoxy]ethanol or
2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably
N-methyl-2-pyrrolidone, diethylene glycol, glycerol or especially
1,2-propylene glycol, usually in an amount of from 2 to 30% by
weight, especially from 5 to 30% by weight and preferably from 10
to 25% by weight, based on the total weight of the ink.
[0103] In addition, the inks may also comprise solubilisers, e.g.
.epsilon.-caprolactam.
[0104] The inks may comprise thickeners of natural or synthetic
origin inter alia for the purpose of adjusting the viscosity.
[0105] Examples of thickeners that may be mentioned include
commercially available alginate thickeners, starch ethers or locust
bean flour ethers, especially sodium alginate on its own or in
admixture with modified cellulose, e.g. methyl cellulose, ethyl
cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl
hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl
methyl cellulose, especially with preferably from 20 to 25% by
weight carboxymethyl cellulose. Synthetic thickeners that may be
mentioned are, for example, those based on poly(meth)acrylic acids
or poly(meth)acrylamides and also polyalkylene glycols having a
molecular weight of e.g. from 2000 to 20 000, for example
polyethylene glycol or poly-propylene glycol or the mixed
polyalkylene glycols of ethylene oxide and propylene oxide.
[0106] The inks comprise such thickeners, for example, in an amount
of from 0.01 to 2% by weight, especially from 0.01 to 1% by weight
and preferably from 0.01 to 0.5% by weight, based on the total
weight of the ink.
[0107] The inks may also comprise buffer substances, e.g. borax,
borates, phosphates, polyphosphates or citrates. Examples that may
be mentioned include borax, sodium borate, sodium tetraborate,
sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium
tripolyphosphate, sodium pentapolyphosphate and sodium citrate.
They are used especially in amounts of from 0.1 to 3% by weight,
preferably from 0.1 to 1% by weight, based on the total weight of
the ink, in order to establish a pH value of, for example, from 4
to 9, especially from 5 to 8.5.
[0108] As further additives, the inks may comprise surfactants or
humectants.
[0109] Suitable surfactants include commercially available anionic
or non-ionic surfactants. As humectants in the inks according to
the invention there come into consideration, for example, urea or a
mixture of sodium lactate (advantageously in the form of a 50% to
60% aqueous solution) and glycerol and/or propylene glycol in
amounts of preferably from 0.1 to 30% by weight, especially from 2
to 30% by weight.
[0110] Preference is given to inks having a viscosity of from 1 to
40 mPas, especially from 1 to 20 mPas and more especially from 1 to
10 mPas.
[0111] Furthermore, the inks may in addition comprise customary
additives, e.g. anti-foams or especially preservatives that inhibit
fungal and/or bacterial growth. Such additives are usually used in
amounts of from 0.01 to 1% by weight, based on the total weight of
the ink.
[0112] Preservatives that come into consideration include
formaldehyde-yielding agents, e.g. paraformaldehyde and trioxane,
especially aqueous, approximately 30 to 40% by weight formaldehyde
solutions, imidazole compounds, e.g. 2-(4-thiazolyl)benzimidazole,
thiazole compounds, e.g. 1,2-benzisothiazolin-3-one or
2-n-octyl-isothiazolin-3-one, iodine compounds, nitriles, phenols,
haloalkylthio compounds and pyridine derivatives, especially
1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one. A
suitable preservative is e.g. a 20% by weight solution of
1,2-benzisothiazolin-3-one in dipropylene glycol (Proxel.RTM.
GXL).
[0113] The inks may also comprise further additives, such as
fluorinated polymers or telomers, e.g. polyethoxyperfluoroalcohols
(Forafac.RTM. or Zonyl.RTM. products) in an amount of e.g. from
0.01 to 1% by weight, based on the total weight of the ink.
[0114] In inkjet printing, individual droplets of the ink are
sprayed onto a substrate in a controlled manner from a nozzle. For
that purpose, predominantly the continuous inkjet method and the
drop-on-demand method are used. In the continuous inkjet method,
the droplets are produced continuously and any droplets not
required for the printing are conveyed to a collecting vessel and
recycled, whereas in the drop-on-demand method droplets are
produced and printed as required, that is to say droplets are
produced only when required for the printing. The production of the
droplets can be effected, for example, by means of a piezo-inkjet
head or by means of thermal energy (bubble jet). Printing by means
of a piezo-inkjet head and printing in accordance with the
continuous inkjet method are preferred.
[0115] The present invention accordingly relates also to aqueous
inks comprising the dye mixtures according to the invention and to
the use of such inks in an inkjet printing method for the printing
of various substrates, especially textile fibre materials, the
definitions and preferred meanings given above applying to the dye
mixtures, the inks and the substrates.
[0116] The following Examples serve to illustrate the invention.
Unless otherwise indicated, the temperatures are given in degrees
Celsius, parts are parts by weight and percentages relate to % by
weight. Parts by weight relate to parts by volume in a ratio of
kilograms to litres.
Example 1
[0117] 100 parts of a cotton fabric are introduced at a temperature
of 60.degree. C. into a dye bath containing 3.0 parts of the dye of
formula (1.1), 3.0 parts of the dye of formula (2.1) and 60 parts
of sodium chloride in 1000 parts of water. After 45 minutes at a
temperature of 60.degree. C., 20 parts of calcined soda are added.
The temperature of the dye bath is maintained at 60.degree. C. for
a further 45 minutes. The dyed fabric is then rinsed and dried in
the usual manner. A navy-blue dyeing having good fastness
properties is obtained.
Examples 2 to 4
[0118] By proceeding as indicated in Example 1 but, instead of
using 3.0 parts of the dye of formula (2.1), using 3.0 parts of the
dye of formula (2.2), 3.0 parts of the dye of formula (2.3) or 3.0
parts of the dye of formula (2.4), there is likewise obtained a
navy-blue dyeing having good fastness properties.
[0119] In a manner analogous to that described in Example 1,
instead of 3.0 parts of the dye of formula (1.1), the same amount
of one of the dyes of formulae (1.2), (1.3), (1.4), (1.5) and (1.6)
may be used.
Example 5
[0120] 100 parts of a cotton fabric are introduced at a temperature
of 60.degree. C. into a dye bath containing 3.0 parts of the dye of
formula (1.1), 3.0 parts of the dye of formula (3.1) and 60 parts
of sodium chloride in 1000 parts of water. After 45 minutes at a
temperature of 60.degree. C., 20 parts of calcined soda are added.
The temperature of the dye bath is maintained at 60.degree. C. for
a further 45 minutes. The dyed fabric is then rinsed and dried in
the usual manner. A navy-blue dyeing having good fastness
properties is obtained.
Examples 6 to 11
[0121] By proceeding as indicated in Example 1 but, instead of
using 3.0 parts of the dye of formula (3.1), using 3.0 parts of the
dye of formula (3.2), 3.0 parts of the dye of formula (3.4), 3.0
parts of the dye of formula (3.5), 3.0 parts of the dye of formula
(3.6), 3.0 parts of the dye of formula (3.7) or 3.0 parts of the
dye of formula (3.8), there is likewise obtained a navy-blue dyeing
having good fastness properties.
[0122] In a manner analogous to that described in Example 5,
instead of 3.0 parts of the dye of formula (1.1), the same amount
of one of the dyes of formulae (1.2), (1.3), (1.4), (1.5) and (1.6)
may be used.
Example 12
[0123] 100 parts of a cotton fabric are introduced at a temperature
of 60.degree. C. into a dye bath containing 3.0 parts of the dye of
formula (1.1), 3.0 parts of the dye of formula (4.1) and 60 parts
of sodium chloride in 1000 parts of water. After 45 minutes at a
temperature of 60.degree. C., 20 parts of calcined soda are added.
The temperature of the dye bath is maintained at 60.degree. C. for
a further 45 minutes. The dyed fabric is then rinsed and dried in
the usual manner. A navy-blue dyeing having good fastness
properties is obtained.
Examples 13 to 15
[0124] By proceeding as indicated in Example 12 but, instead of
using 3.0 parts of the dye of formula (4.1), using 3.0 parts of the
dye of formula (4.2), 3.0 parts of the dye of formula (4.3) or 3.0
parts of the dye of formula (4.4), there is likewise obtained a
navy-blue dyeing having good fastness properties.
[0125] In a manner analogous to that described in Example 12,
instead of 3.0 parts of the dye of formula (1.1), the same amount
of one of the dyes of formulae (1.2), (1.3), (1.4), (1.5) and (1.6)
may be used.
Example 16
[0126] 10 parts of a woolen fabric are dyed in a laboratory dyeing
apparatus using the following liquor:
[0127] 0.2 part of sodium acetate,
[0128] 0.5 part of 80% acetic acid,
[0129] 0.2 part of a commercially available levelling agent
(Albegal B.RTM.),
[0130] 0.30 part of the dye of formula (1.3),
[0131] 0.30 part of the dye of formula (3.3), and
[0132] 200 parts of water.
[0133] The pH of the liquor is 4.5. The textile is treated in the
dye liquor for 5 min. at 40.degree. C. and is then heated at a
heating rate of 1.degree./min to boiling temperature (98.degree.
C.) and dyed at that temperature for 90 minutes. After cooling the
liquor to 80.degree. C., a solution of 0.8 part of sodium carbonate
in 8 parts of water is added and the textile material is treated
for 20 min. at 80.degree. C. and a pH of 8.5. The dyeing is then
rinsed and finished in the usual manner. A navy-blue dyeing
exhibiting fibre levelness and surface levelness and having good
fastness properties is obtained.
Example 17
[0134] By proceeding as indicated in Example 16 but, instead of
using 0.30 part of the dye of formula (1.3), using 0.30 part of the
dye of formula (1.4), there are likewise obtained navy-blue dyeings
exhibiting fibre levelness and surface levelness and having good
fastness properties.
Example 18
[0135] Mercerised cotton satin is pad-dyed using a liquor
containing 30 g/l of sodium carbonate and 50 g/l of urea (70%
liquor pick-up) and dried.
[0136] Using a drop-on-demand inkjet head (bubble jet), the cotton
satin pretreated according to step (a) is printed with an aqueous
ink containing
[0137] -10% by weight of a mixture of 3.0 parts of the reactive dye
of formula (1.1) and 3.0 parts of the reactive dye of formula
(2.1),
[0138] -20% by weight of 1,2-propylene glycol and
[0139] -70% by weight of water.
[0140] The print is fully dried and is fixed in saturated steam at
102.degree. C. for 8 minutes, cold-rinsed, washed-off at boiling
temperature, rinsed again and dried.
[0141] A navy-blue print having good fastness properties is
obtained.
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