Title of Invention

REACTIVE DYE MIXTURES AND A PROCESS FOR THE PREPARATION THEREOF

Abstract Reactive dye mixture consisting of one or more dyes of the herein below indicated and defined general formula (1) in an amount of 10 to 90% by weight and one or more monoazo dyes of the general formulae (15) to (16) each in an amount of 0-10% by weight, and one or more dyes of the herein below indicated and defined general formulae (Ga)-(Gf), independently in each case in an amount of 10 to 90% by weight where D1, D2, D3, D4, D5, D6, D7, R*, R**, R31, R32, R33, R34, R35, R36, R37, R38, R39, Z, Z3m, n and M are each as defined in claim 1, the dyes of the general formulae (1) and (Ga)-(Gf) containing at least one fiber-reactive group of the formula -SO2-Z or -Z2, their preparation and their use for dyeing hydroxyl- and/or carboxamido-containing the fiber material.
Full Text

REACTIVE DYE MIXTURES AMD THE PROCESS FOR THE PREPARATION
THEREOF
The invention relates to the technical field of fiber-reactive azo dyes.
Fiber-reactive azo dye mixtures and their use for dyeing hydroxyl- and/or
carboxamido-containing material in orange to red hues are known for example from
EP 1090962 and EP 0979848. However, these have certain performance defects, for
example an excessive dependence of the color yield on changing dyeing parameters
in the dyeing operation, or an insufficient or unlevel color buildup on cotton (good
color buildup follows from the ability of a dye to produce the correspondingly stronger
dyeing from an increased concentration of dye in the dyebath). Possible
consequences of these defects are for example poor reproducibilities for the dyeings
which are obtainable, which ultimately compromises the economics of the dyeing
operation.
Consequently, there continues to be a demand for novel reactive dyes or reactive
dye mixtures having improved properties, such as high substantivity combined with
good washoff for unfixed portions. They shall moreover also provide good dyeing
yields and possess high reactivity and they shall more particularly provide dyeings
having high degrees of fixation.
The present invention, then, provides dye mixtures which possess these above-
described properties to a high degree. The novel dye mixtures are notable in
particular for high yields of fixation and ready washoff for portions not fixed on the
fiber. In addition, the dyeings exhibit good general fastnesses, such as for example
high lightfastness and very good wetfastnesses, and also have a low tendency to
stain polyamide in the case of cotton-polyamide blend fabrics.
The invention accordingly provides dye mixtures consisting of one or more, such as
two or three, preferably 1 or 2, dyes of the hereinbelow indicated and defined general
formula (I)


and one or more monoazo dyes of the general formulae (15) to (16), each in
an amount of 0-10% by weight,

and one or more, such as two or three, preferably 1 or 2, dyes of the hereinbelow
indicated and defined general formulae (Ga)-(Gf)



where
D1 to D7 are independently a group of the general formula (1)

where
R1 and R2 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl,
sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and

X1 is hydrogen or a group of the formula -SO2-Z,
where
Z is -CH=CH2, -CH2CH2Z1 or hydroxyl,
where
Z1 is hydroxyl or an alkali-detachable group,
or
D1 to D7 are independently a naphthyl group of the general formula (2)

where
R3 and R4 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl,
sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and
X2 has one of the meanings of X1; or
D1 to D7 are independently a group of the general formula (3)

where
R5 and R6 independently have one of the meanings of R1 and R2;
R7 is hydrogen, (C1-C4)-alkyl, unsubstituted or (C1-C4)-alkyl-,
(C1-C4)-alkoxy-, sulfo-, halogen-or carboxyl- substituted phenyl; and
Z2 is a group of the general formula (4) or (5) or (6)


where
V is fluorine or chlorine;
U1, U2 are independently fluorine, chlorine or hydrogen;
and
Q1, Q2 are independently chlorine, fluorine, cyanamido, hydroxyl,
(C1-C6)-alkoxy, phenoxy, sulfophenoxy, mercapto, (C1-C6)-alkyl-
mercapto, pyridino, carboxypyridino, carbamoylpyridino or a
group of the general formula (7) or (8)

where
R8 is hydrogen or (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl or phenyl
which is unsubstituted or substituted by (C1-C4)-alkyl,
(C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido,
ureido;
R9and R10 independently have one of the meanings of R8 or
combine to form a cyclic ring system of the formula
-(CH2)j-, wherein j is 4 or 5, or alternatively
-(CH2)2-E-(CH2)2-, wherein E is oxygen, sulfur, sulfonyl,
-NR11 where R11 = (C1-C6)-alkyl;
W is phenylene, which is unsubstituted or substituted by 1 or
2 substituents, such as (C1-C4)-alkyl, (C1-C4)-alkoxy,
carboxyl, sulfo, chlorine, bromine, or is (C1-C4)-alkylene-
arylene or (C2-C6)-alkylene, which may be interrupted by

oxygen, sulfur, sulfonyl, amino, carbonyl, carboxamido, or
is phenylene-CONH-phenylene which is unsubstituted or
substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl,
sulfo, carboxyl, amido, ureido or halogen, or is
naphthylene which is unsubstituted or substituted by one
or two sulfo groups; and
Z is as defined above; or
D1 to D7 are independently a group of the general formula (9)

where
R12 is hydrogen, (C1-C4)-alkyl, aryl or a substituted aryl radical;
R13 and R14 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and
A is a phenylene group of the general formula (10)

where
R15 and R16 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, sulfo, carboxyl, cyano, nitro, amido, ureido or halogen;
or
A is a naphthylene group of the general formula (11)


where
R17 and R18 are independently hydrogen, (C1-C4)-alkyl,
(C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, cyano, nitro, amido,
ureido or halogen; or
A is a polymethylene group of the general formula (12)

where
k is an integer greater than 1 and
R19and R20 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy,
hydroxyl, cyano, amido, halogen or aryl; and
X3 has one of the meanings of X1; and
R*, R** are independently hydrogen, (C1-C4)-alkyl or a group of the formula (14)
-CH2-SO3M (14);
R31 is hydrogen, acetyl, carbamoyl or a group of the general formula (4) or (5) or
(14),
R32 is hydrogen or a group of the general formula (14),
R33 is methyl, carboxyl or carboxyalkyl with C1- to C4-alkyl,
R34 is hydrogen or methyl,
R35 is hydrogen, cyano, carbamoyl, carboxyl or a group of the general
formula (14),
R35 is methyl, ethyl or ß-sulfoethyl,
R37 is methyl, carboxyl or carboxyalkyl with C1- to C4-alkyl,

R38 is acetamido, ureido, methyl or methoxy,
R39 is hydrogen, methyl or methoxy,
m is 0 or 1,
n is 1, 2 or 3,
Z3 has one of the meanings of Z2, and
M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal
wherein
the dyes of the general formulae (I) and (Ga)-(Gf) contain at least one fiber-reactive
group of the formula -SO2-Z or -Z2.
The individual symbols in the general formulae above and below can have identical
or different meanings under their definition, irrespective of whether the symbols bear
the same or a different designation.
(C1-C4)-Alkyl R may be straight-chain or branched and is in particular methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are
preferred. The same logic applies to (C1-C4)-alkoxy groups.-
Aryl R is in particular phenyl. Substituted aryl R8 to R10, R12 or R21 is in particular
phenyl substituted by one, two or three independent groups selected from the group
consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxyl, sulfo, carboxyl, amido and
halogen.
Halogen R is in particular fluorine, chlorine or bromine, and fluorine and chlorine are
preferred.
Alkali-eliminable Z1 in the Imposition of the ethyl group of Z include for example
halogen atoms, such as chlorine and bromine, ester groups of organic carboxylic and
sulfonic acids, such as alkylcarboxylic acids, substituted or unsubstituted
benzenecarboxylic acids and substituted or unsubstituted benzenesulfonic acids,
such as alkanoyloxy of 2 to 5 carbon atoms, especially acetyloxy, benzoyloxy,
sulfobenzoyloxy, phenylsulfonyloxy and toluylsulfonyloxy, also acidic ester groups of
inorganic acids, such as phosphoric acid, sulfuric acid and thiosulfuric acid

(phosphato, sulfato and thiosulfato groups), similarly dialkylamino groups having alkyl
groups of 1 to 4 carbon atoms in each case, such as dimethylamino and
diethylamino.
Z is preferably vinyl, ß-chloroethyl and particularly preferably ß-sulfatoethyl.
The groups "sulfo", "carboxyl", "thiosulfato", "phosphato" and "sulfato" include not
only their acid form but also their salt form. Accordingly, sulfo groups are groups
conforming to the general formula -SO3M, thiosulfato groups are groups conforming
to the general formula -S-SO3M, carboxyl groups are groups conforming to the
general formula -COOM, phosphato groups are groups conforming to the general
formula -OPO3M2 and sulfato groups are groups conforming to the general formula
-OSO3M, in each of which M is as defined above.
The dyes of the general formula (I) and (Ga)-(Gf) may possess different fiber-reactive
groups -SO2Z within the meaning of Z. More particularly, the fiber-reactive groups
-SO2Z may be on the one hand vinylsulfonyl groups and on the other -CH2CH2Z1
groups, preferably p-sulfatoethylsulfonyl groups. If the dyes of the general formula (I)
and (Ga)-(Gf) contain vinylsulfonyl groups in some instances, then the fraction of the
respective dye with the vinylsulfonyl group is up to about 30 mol%, based on the
respective amount of total dye.
Alkali M is in particular lithium, sodium or potassium. M is preferably hydrogen or
sodium.
The radicals R* and R** in the general formula (I) are independently preferably
hydrogen, methyl or a group of the formula (14), with hydrogen or a group of the
formula (14) being particularly preferred.
R1 and R2 are preferably hydrogen, (C1-C4)-alkyl groups, (C1-C4)-alkoxy groups, sulfo
or carboxyl and more preferably hydrogen, methyl, methoxy or sulfo.
R3 to R6 and R12 to R20 are preferably hydrogen, R3 to R6, R17 and R18 are also
preferably sulfo.
R7 to R10 are preferably hydrogen or methyl, R7 and R8 are also preferably phenyl

and R9 and R10 are preferably 2-sulfoethyl, 2-, 3- or 4-sulfophenyl or R9 and R10
combine to form a cyclic ring system which preferably conforms to the
formula -(CH2)2-O-(CH2)2-.
Examples of groups D1 to D7 of the general formulae (1) and (2) are 2-(ß-suIfato-
ethylsulfonyl)-phenyl, 3-(ß-sulfatoethylsulfonyl)-phenyl, 4-(ß-sulfatoethylsulfonyl)-
phenyl, 2-carboxy-5-(ß-sulfatoethylsulfonyl)-phenyl, 2-chloro-4-(ß-sulfatoethyl-
sulfonyl)-phenyl, 2-chloro-5-(ß-sulfatoethylsulfonyl)-phenyl, 2-bromo-4-(ß-sulfato-
ethylsulfonyl)-phenyl, 2-sulfo-4-(ß-sulfatoethylsulfonyl)-phenyl, 2-sulfo-5-(ß-sulfato-
ethylsulfonyl)-phenyl, 2-methoxy-5-(ß-sulfatoethylsulfonyl)-phenyl, 2-ethoxy-
5-(ß-sulfatoethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(ß-sulfatoethylsulfonyl)-phenyl,
2-methoxy-5-methyl-4-(ß-sulfatoethylsulfonyl)-phenyl, 2-methyl-4-(ß-sulfatoethyl-
sulfonyl)-phenyl, 2- or 3- or 4-(ß-thiosulfatoethylsulfonyl)-phenyl, 2-methoxy-
5-(ß-thiosulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(ß-phosphatoethylsulfonyl)-phenyl,
2- or 3- or 4-vinylsulfonyl-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl, 2-chloro-4-(ß-chloro-
ethylsulfonyl)-phenyl, 2-chloro-5-(ß-chloroethylsulfonyl)-phenyl, 3- or
4-(ß-acetoxyethylsulfonyl)-phenyl, 6- or 8-(ß-sulfatoethylsulfonyl)-naphth-2-yl,
6-(ß-sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl and 8-(ß-sulfatoethylsulfonyl)-6-sulfo-
naphth-2-yl, preferably 3-(ß-sulfatoethylsulfonyl)-phenyl, 4-(ß-sulfatoethylsulfonyl)-
phenyl, 2-sulfo-4-(ß-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-(ß-sulfato-
ethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(ß-sulfatoethylsulfonyl)-phenyl, 2-methoxy-
5-methyl-4-(ß-sulfatoethylsulfonyl)-phenyl and 3- or 4-vinylsulfonyl-phenyl, or D1 to
D7 conform to a group of the general formula (3) or (9) where R5 to R7 and R12 to R14
have the above-described preferred meanings.
When D1 to D7 is a group of the general formula (1) and X1 is -SO2Z, the SO2Z group
is preferably disposed meta or para to the diazo group, and when D1 to D7 is a group
of the general formula (2), the bond which leads to the diazo group is preferably
attached to the naphthalene nucleus in the ß-position.
When A is phenylene and X3 is -SO2Z, the SO2Z group is preferably disposed meta
or para relative to the nitrogen atom. In the group of the general formula (9), the
carboxamide group is preferably disposed para or meta relative to the diazo group.
When A is naphthylene, the bond leading to the nitrogen atom is preferably attached

to the naphthalene nucleus in the ß-position.
Examples of substituents A are in particular 1,2-phenylene, 1,3-phenylene,
1,4-phenylene, 2-chloro-1,4-phenylene, 2-chloro-1,5-phenylene, 2-bromo-
1,4-phenylene, 2-sulfo-1,4-phenylene, 2-sulfo-1,5-phenylene, 2-methoxy-
1,5-phenylene, 2-ethoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-
5-methyl-1,4-phenylene, 2-methyl-1,4-phenylene, 2,6-naphthylene, 2,8-naphthylene,
1-sulfo-2,6-naphthylene, 6-sulfo-2,8-naphthylene or 1,2-ethylene and 1,3-propylene.
A is particularly preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene,
2-methoxy-1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-
1,4-phenylene or 1,2-ethylene and 1,3-propylene, and in the case of the two
last-mentioned alkylene groups R12 is preferably phenyl or 2-sulfophenyl.
k is preferably 2 or 3.
W is preferably 1,3-phenylene, 1,4-phenylene, 2-sulfo-1,4-phenylene, 2-methoxy-
1,5-phenylene, 2,5-dimethoxy-1,4-phenylene, 2-methoxy-5-methyl-1,4-phenylene,
1,2-ethylene, 1,3-propylene.
Examples of the groups Q1 and Q2 in the general formula (5) are independently
fluorine, chlorine, hydroxyl, methoxy, ethoxy, phenoxy, 3-sulfophenoxy,
4-sulfophenoxy, methyl me rcapto, cyanamido, amino, methylamino, ethylamino,
morpholino, piperidino, phenylamino, methylphenylamino, 2-sulfophenylamino,
3-sulfophenylamino, 4-sulfophenylamino, 2,4-disulfophenylamino,
2,5-disulfophenylamino, 2-sulfoethylamino, N-methyl-2-sulfoethylamino, pyridino,
3-carboxypyridino, 4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino,
2-(2-sulfatoethylsulfonyl)-phenylamino, 3-(2-sulfatoethylsulfonyl)-phenylamino,
4-(2-sulfatoethylsulfonyl)-phenylamino, N-ethyl-3-(2-sulfatoethylsulfonyl)-
phenylamino, N-ethyl-4-(2-sulfatoethylsulfonyl)-phenylamino, 2-carboxy-
5-(2-sulfatoethylsulfonyl)-phenylamino), 2-chloro-4-(2-sulfatoethylsulfonyl)-
phenylamino, 2-chloro-5-(2-sulfatoethylsulfonyl)-phenylamino, 2-bromo-
4-(2-sulfatoethylsulfonyl)-phenylamino, 2-sulfo-4-(2-sulfatoethylsulfonyl)-
phenylamino, 2-sulfo-5-(2-sulfatoethylsulfonyl)phenylamino, 2-methoxy-

5-(2-sulfatoethylsulfonyl)-phenylamino, 2,5-dimethoxy-4-(2-sulfatoethylsulfonyl)-
phenylamino, 2-methoxy-5-methyl-4-(2-sulfatoethylsulfonyl)-phenylamino, 2-methyl-
4-(2-sulfatoethylsulfonyl)-phenylamino, 2-(vinylsulfonyl)-phenylamino,
3-(vinylsulfonyl)-phenylamino, 4-(vinylsulfonyl)-phenylamino, N-ethyl-3-(vinylsulfonyl)-
phenylamino, N-ethyl-4-(vinylsulfonyl)-phenylamino, 6-(2-sulfatoethylsulfonyl)-
naphth-2-ylamino, 8-(2-sulfatoethylsulfonyl)-naphth-2-ylamino, 8-(2-sulfatoethyl-
sulfonyl)-6-sulfo-naphth-2-ylamino, 3-(2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-
phenylamino, 4-(2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-phenylamino,
3-(2-(vinylsulfonyl)-ethylcarbamoyl)-phenylamino, 4-(2-(2-vinylsulfonyl)-
ethylcarbamoyl)-phenylamino, 4-(N-methyl-2-(2-sulfatoethylsulfonyl)-ethylcarbamoyl)-
phenylamino, 4-(N-phenyl-2-(2-sulfatoethylsulfonyl)ethylcarbamoyl)phenylamino,
4-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino, 4-(4-(2-sulfatoethyl-
sulfonyl)-phenylcarbamoyl)-phenylamino, 3-(3-(2-sulfatoethylsuIfonyl)-phenyl-
carbamoyl)-phenylamino, 3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-
phenylamino, 3-(2-sulfatoethylsulfonyl)-propylamino, N-methyl-
N-(2-(2-suIfatoethylsulfonyl)-ethyl)-amino, N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-
ethyl)-amino, N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-propyl)-amino.
Preferably, the groups Q1 and Q2 in the general formula (5) are independently
fluorine, chlorine, cyanamido, morpholino, 2-suIfophenylamino, 3-sulfophenylamino,
4-sulfophenylamino, N-methyl-2-sulfoethylamino, 3-carboxypyridino,
4-carboxypyridino, 3-carbamoylpyridino, 4-carbamoylpyridino, 3-(2-sulfatoethyl-
sulfonyl)-phenylamino, 4-(2-sulfatoethylsulfonyl)-phenylamino, 3-(vinylsulfonyl)-
phenylamino, 4-(vinylsulfonyl)-phenylamino, 4-(3-(2-sulfatoethylsulfonyl)-
phenylcarbamoyl)-phenylamino, 4-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-
phenylamino, 3-(3-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino,
3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-phenylamino, N-methyl-
N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino, N-phenyl-N-(2-(2-sulfatoethylsulfonyl)-
ethyl)-amino.
More preferably, the groups Q1 and Q2 in the general formula (5) are independently
fluorine, chlorine, cyanamido, morpholino, 2-sulfophenylamino, 3-sulfophenylamino,
4-sulfophenylamino, 3-(2-sulfatoethylsulfonyl)-phenylamino,
4-(2-sulfatoethylsulfonyl)-phenylamino, 3-(vinylsulfonyl)-phenylamino, 4-(vinyl-

sulfonyl)-phenylamino, N-methyl-N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino, N-phenyl-
N-(2-(2-sulfatoethylsulfonyl)-ethyl)-amino.
Examples of the group Z2 and Z3 are 2,4-difluoro-pyrimidin-6-yl, 4,6-difluoro-
pyrimidin-2-yl, 5-chloro-2,4-difluoro-pyrimidin-6-yl, 5-chloro-4,6-difluoro-pyrimidin-2-yl,
4,5-difluoro-pyrimidin-6-yl, 5-chloro-4-fluoro-pyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-
6-yl, 4,5-dichloro-pyrimidin-6-yl, 2,4-dichloro-pyrimidin-6-yl, 4-fluoro-pyrimidin-6-yl,
4-chloro-pyrimidin-6-yl, or a group of the general formula (5) having the above-
indicated examples of Q1 and Q2 or a group of the formula (6).
Preferably, Z2 and Z3 are 2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl,
5-chloro-2,4-difluoropyrimidin-6-yl, 5-chloro-4,6-difluoropyrimidin-2-yl or a group of
the general formula (5) having the above-indicated preferred groups Q1 and Q2.
More preferably, Z2 and Z3 are 2,4-difluoropyrimidin-6-yl, 5-chloro-2,4-difluoro-
pyrimidin-6-yl or a group of the general formula (5) having the above-indicated
particularly preferred groups Q1 and Q2.
R31 in the formula (Ga) is preferably hydrogen, acetyl, 2,4-difluoropyrimidin-6-yl,
5-chloro-2,4-difluoropyrimidin-6-yl or a group of the general formula (5) with the
above-indicated particularly preferred groups Q1 und Q2;
R32 in the formula (Gb) is preferably hydrogen;
R33 and R37 in the formulae (Gc) and (Ge) are each preferably carboxyl or methyl;
preferred meanings in the formula (Gd) are R34 methyl, R35 cyano, carbamoyl or a
group of the formula (14) and R36 methyl or ethyl;
preferred meanings in the formula (Gf) are m 1 and n 1 or 2.
The dye mixtures of the present invention comprise bisazo dyes of the general
formula (I) in an amount from 1 % to 99% by weight and preferably 10% to 90% by
weight and dyes of the general formulae (Ga)-(Gf) independently each in an amount
from 1 % to 99% by weight and preferably from 10% to 90% by weight.
Preferred dye mixtures comprise one or more, such as two or three, preferably 1 or
2 dyes of the indicated and defined general formula (l-a)


and one or more dyes of the general formula (Ga), (Gb), (Ge) and (Gf),


in each of which D1 to D5, R*. R31, R32, R37, R38, R39, Z, Z3, m, n and M are each as
defined above.
Further preferred dye mixtures comprise at least one dye of the general formula (l-b)

and at least one dye of the general formulae (Ga), (Gb), (Ge) and (Gf), where D3 to
D5, R31, R32, R37, R38, R39, Z, Z3, m, n and M are each as defined above and R201 to
R204 are independently hydrogen, methyl, methoxy or sulfo.
Particularly preferred dye mixtures comprise one or more, such as two or three,
preferably 1 or 2, dyes of the indicated and defined general formula (l-c),

and one or more dyes of the general formula (Ga-a) and (Gb-a),


in which D2, D4, D5, R31, Z and M are each as defined above.
Preferred meanings in the general formulae (l-c) and (Ga-a) are R101 to R104
independently hydrogen, C1-C4-alkyl, C1-C4-alkoxy, sulfo, carboxyl or halogen and Z
vinyl or ß-sulfatoethyl and very particularly preferred meanings in the formula (l-c)
and (Ga-a) are R101 to R104 independently hydrogen, methyl, methoxy or sulfo and Z
vinyl or ß-sulfatoethyl.
The dye mixtures according to the invention can be present as a preparation in solid
or liquid (dissolved) form. In solid form, they contain, to the extent necessary, the
electrolyte salts customary in the case of water-soluble and especially fiber-reactive
dyes, such as sodium chloride, potassium chloride and sodium sulfate, and may
further contain the auxiliaries customary in commercial dyes, such as buffer
substances capable of setting a pH in aqueous solution between 3 and 7, for
example sodium acetate, sodium citrate, sodium borate, sodium bicarbonate, sodium
dihydrogenphosphate and disodium hydrogenphosphate, also dyeing auxiliaries,
dustproofing agents and small amounts of siccatives; when they are present in a
liquid, aqueous solution (including a content of thickeners of the type customary in
print pastes), they may also contain substances which ensure a long life for these
preparations, for example mold preventatives.
In solid form, the dye mixtures according to the invention are generally present as
powders or granules which contain electrolyte salt and which will hereinbelow
generally be referred to as a preparation with or without one or more of the

abovementioned auxiliaries. In the preparations, the dye mixture is present at 20 to
90% by weight, based on the preparation containing it. The buffer substances are
generally present in a total amount of up to 5% by weight, based on the preparation.
When the dye mixtures according to the invention are present in an aqueous
solution, the total dye content of these aqueous solutions is up to about 50% by
weight, for example between 5 and 50% by weight, the electrolyte salt content of
these aqueous solutions preferably being below 10% by weight, based on the
aqueous solution; the aqueous solutions (liquid preparations) can contain the
aforementioned buffer substances in an amount which is generally up to 5% by
weight and preferably up to 2% by weight.
Dyes of the general formula (I) are described in DE 196 00 765 A1 and dyes of the
general formulae (Ga) to (Gf) are described extensively in the literature and are
obtainable via standard synthesis methods. Dyes of the general formulae (15) and
(16) are in some instances formed during the synthesis of dyes of the general
formulae (I).
The dye mixtures according to the invention are preparable in a conventional
manner, as by mechanically mixing the individual dyes, whether in the form of their
dye powders or granules or their as-synthesized solutions or in the form of aqueous
solutions of the individual dyes generally, which may additionally contain customary
auxiliaries, or by conventional diazotization and coupling of suitable mixtures of diazo
and coupling components in the desired amount ratios.
For example, when the diazo components having the groups D2 and D3 and/or D5
and/or D6 and/or D7 as per the general formulae (I) and (Ga) and/or (Gb) and/or (Gc)
and/or (Gd) have the same meaning, it is possible for an amine of the general
formula (17)

where D2 is as defined above, to be diazotized in a conventional manner and the
diazonium compound obtained being subsequently reacted with an aqueous solution
or suspension of a mixture having a fixed ratio of a monoazo dye as per the general
formula (15) and of at least one coupler of the general formula (13) and/or (18)

and/or (19) and/or of a monoazo dye as per the general formula (20)

where D4, R*, R**, R31, R32, R33, R34, R35, R36, Z and M are each as defined above.
Alternatively, the dye mixture according to the present invention can be prepared
when the groups D1, D2 and D4, D5 as per the general formulae (I) and (Gb) have the
same meaning, which comprises an amine of the general formula (21)
D1-NH2 (21),
where D1 is as defined above, being diazotized in a conventional manner and
coupled onto a mixture of the coupling components (22) and (23),


where R*, R**, R32 and M are each as defined above, firstly at a pH below 3 in a first
stage and subsequently further coupled by an increase in pH to form a mixture of the
dyes of the general formulae (I) and (Gb).
The dye mixture according to the present invention is isolated in a conventional
manner by salting out for example with sodium chloride or potassium chloride or by
spray drying or evaporation.
Similarly, the solutions produced in the course of the synthesis of the dyes of the
general formula (I) and (Ga) to (Gf) can be used directly as liquid products in dyeing,
if appropriate after addition of a buffer substance and if appropriate after
concentrating.
Dye mixtures which as well as ß-chloroethylsulfonyl or ß-thiosulfatoethylsulfonyl or
ß-sulfatoethylsulfonyl groups also contain vinylsulfonyl groups as reactive radicals
can be synthesized not only starting from appropriately substituted vinylsulfonyl-
anilines or naphthylamines but also by reaction of a dye mixture where Z is
ß-chloroethyl, ß-thiosulfatoethyl or ß-sulfatoethyl with an amount of alkali required for
the desired fraction and converting the ß-substituted ethylsulfonyl groups mentioned
into vinylsulfonyl groups. This conversion is effected in a manner familiar to one
skilled in the art.
The dye mixtures according to the invention have useful application properties. They
are used for dyeing or printing hydroxyl- and/or carboxamido-containing materials, for
example in the form of sheetlike structures, such as paper and leather or of films, for
example composed of polyamide, or in bulk, such as for example polyamide and
polyurethane, but especially for dyeing and printing these materials in fiber form.
Similarly, the as-synthesized solutions of the dye mixtures according to the invention
can be used directly as a liquid preparation for dyeing, if appropriate after addition of
a buffer substance and if appropriate after concentration or dilution.
The present invention thus also provides for the use of the dye mixtures according to
the invention for dyeing or printing these materials, or rather processes for dyeing or

printing these materials in a conventional manner, by using a dye mixture according
to the invention or its individual components (dyes) individually together as a
colorant. The materials are preferably employed in the form of fiber materials,
especially in the form of textile fibers, such as woven fabrics or yarns, as in the form
of hanks or wound packages.
Hydroxyl-containing materials are those of natural or synthetic origin, for example
cellulose fiber materials or their regenerated products and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such
as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example
staple viscose and filament viscose and also chemically modified cellulose fibers,
such as aminated cellulose fibers or fibers as described for example in WO 96/37641
and WO 96/37642 and also in EP-A-0 538 785 and EP-A-0 692 559.
Carboxamido-containing materials are for example synthetic and natural polyamides
and polyurethanes, especially in the form of fibers, for example wool and other
animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The dye mixtures according to the invention can be applied to and fixed on the
substrates mentioned, especially the fiber materials mentioned, by the application
techniques known for water-soluble dyes and especially for fiber-reactive dyes. For
instance, on cellulose fibers they produce by the exhaust method from a long liquor
and also from a short liquor, for example in a liquor to goods ratio of 5 : 1 to 100 : 1,
preferably 6 : 1 to 30 : 1, using various acid-binding agents and optionally neutral
salts as far as necessary, such as sodium chloride or sodium sulfate, dyeings having
very good color yields. Application is preferably from an aqueous bath at
temperatures between 40 and 105°C, optionally at a temperature of up to 130°C
under superatmospheric pressure, but preferably at 30 to 95°C, especially 45 to
65°C, in the presence or absence of customary dyeing auxiliaries. One possible
procedure here is to introduce the material into the warm bath and to gradually heat
the bath to the desired dyeing temperature and complete the dyeing process at that
temperature. The neutral salts which accelerate the exhaustion of the dyes may also
if desired only be added to the bath after the actual dyeing temperature has been
reached.

Padding processes likewise provide excellent color yields and a very good color
buildup on cellulose fibers, the dyes being fixable in a conventional manner by
batching at room temperature or elevated temperature, for example at up to 60°C, or
in a continuous manner, for example by means of a pad-dry-pad steam process, by
steaming or using dry heat.
Similarly, the customary printing processes for cellulose fibers, which can be carried
out in one step, for example by printing with a print paste containing sodium
bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to
103°C, or in two steps, for example by printing with a neutral to weak acidic print
color and then fixing either by passing the printed material through a hot electrolyte-
containing alkaline bath or by overpadding with an alkaline electrolyte-containing
padding liquor and subsequent batching or steaming or dry heat treatment of the
alkali-overpadded material, produce strong color prints with well-defined contours
and a clear white ground. The outcome of the prints is affected little, if at all, by
variations in the fixing conditions.
When fixing by means of dry heat in accordance with the customary thermofix
processes, hot air at 120 to 200°C is used. In addition to the customary steam at 101
to 103°C, it is also possible to use superheated steam and high-pressure steam at
temperatures of up to 160°C.
The acid-binding agents which effect the fixation of the dyes of the dye mixtures
according to the invention on the cellulose fibers are for example water-soluble basic
salts of alkali metals and likewise alkaline earth metals of inorganic or organic acids
or compounds which liberate alkali in the heat, and also alkali metal silicates.
Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to
medium inorganic or organic acids, the preferred alkali metal compounds being the
sodium and potassium compounds. Such acid-binding agents are for example
sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate,
potassium carbonate, sodium formate, sodium dihydrogenphosphate, disodium
hydrogenphosphate, sodium trichloroacetate, trisodium phosphate or waterglass or
mixtures thereof, for example mixtures of aqueous sodium hydroxide solution and

waterglass.
The present invention further relates to the use of the dye mixtures of the present
invention in printing inks for digital textile printing by the inkjet process.
The printing inks of the present invention comprise the reactive dye mixtures of the
present invention, for example in amounts from 0.1% by weight to 50% by weight,
preferably in amounts from 1% by weight to 30% by weight and more preferably in
amounts from 1 % by weight to 15% by weight based on the total weight of the ink.
They may also include combinations of the aforementioned reactive dye mixtures
with other reactive dyes used in textile printing. For the inks to be used in the
continuous flow process, a conductivity of 0.5 to 25 mS/m can be set by adding an
electrolyte.
Useful electrolytes include for example lithium nitrate and potassium nitrate.
The dye inks of the present invention may include organic solvents at a total level of
1-50% and preferably 5-30% by weight.
Suitable organic solvents are for example
alcohols, for example methanol, ethanol, 1-propanol, isopropanol, 1-butanol,
tert-butanol, pentyl alcohol, polyhydric alcohols for example: 1,2-ethanediol,
1,2,3-propanetriol, butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol,
2,3-propanediol, pentanediol, 1,4-pentanediol, 1,5-pentanediol, hexanediol,
D,L-1,2-hexanediol, 1,6-hexanediol, 1,2,6-hexanetriol, 1,2-octanediol, polyalkylene
glycols, for example: polyethylene glycol, polypropylene glycol, alkylene glycols
having 2 to 8 alkylene groups, for example monoethylene glycol, diethylene glycol,
triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene
glycol, propylene glycol, dipropylene glycol, tripropylene glycol,
low alkyl ethers of polyhydric alcohols, for example: ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene
glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol
monobutyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl
ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether,
tetraethylene glycol monomethyl ether, tetraethylene glycol monobutyl ether,
tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene
glycol monoethyl ether, propylene glycol monobutyl ether, tripropylene glycol

isopropyl ether, polyalkylene glycol ethers, such as for example: polyethylene glycol
monomethyl ether, polypropylene glycol glycerol ether, polyethylene glycol tridecyl
ether, polyethylene glycol nonylphenyl ether,
amines, such as, for example: methylamine, ethylamine, triethylamine, diethylamine,
dimethylamine, trimethylamine, dibutylamine, diethanolamine, triethanolamine,
N-acetylethanolamine, N-formylethanolamine, ethylenediamine,
urea derivatives, such as for example: urea, thiourea, N-methylurea, N.N'-dimethyl-
urea, ethyleneurea, 1,1,3,3-tetramethylurea, amides, such as for example:
dimethylformamide, dimethylacetamide, acetamide,
ketones or keto alcohols, such as for example: acetone, diacetone alcohol,
cyclic ethers, such as for example; tetrahydrofuran, trimethylolethane,
trimethylolpropane, 2-butoxyethanol, benzyl alcohol, 2-butoxyethanol, gamma
butyrolactone, epsilon-caprolactam,
further sulfolane, dimethylsulfolane, methylsulfolane, 2,4-dimethylsulfolane, dimethyl
sulfone, butadiene sulfone, dimethyl sulfoxide, dibutyl sulfoxide,
N-cyclohexylpyrrolidone, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 2-pyrrolidone,
1-(2-hydroxyethyl)-2-pyrrolidone, 1-(3-hydroxypropyl)-2-pyrrolidone, 1,3-dimethyl-
2-imidazolidinone, 1,3-dimethyl-2-imidazolinone, 1,3-bismethoxymethylimidazolidine,
2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-(2-butoxyethoxy)ethanol,
2-(2-propoxyethoxy)ethanol, pyridine, piperidine, butyrolactone, trimethylpropane,
1,2-dimethoxypropane, dioxane, ethyl acetate, ethylenediaminetetraacetate, ethyl
pentyl ether.
The printing inks of the invention may further include customary additives, for
example viscosity moderators to set viscosities in the range from 1.5 to 40.0 mPas in
a temperature range from 20 to 50°C. Preferred inks have a viscosity of 1.5 to
20 mPas and particularly preferred inks have a viscosity of 1.5 to 15 mPas.
Useful viscosity moderators include rheological additives, for example:
polyvinylcaprolactam, polyvinylpyrrolidone and their copolymers polyetherpolyol,
associative thickeners, polyurea, polyurethane, sodium alginates, modified
galactomannans, polyetherurea, polyurethane, nonionic cellulose ethers.
As further additives the inks of the invention may include surface-active substances
to set surface tensions of 20 to 65 mN/m, which are adapted if necessary as a
function of the process used (thermal or piezotechnology).
Useful surface-active substances include for example: all surfactants, preferably

nonionic surfactants, butyldiglycol, 1,2-hexanediol.
The inks may further include customary additives, for example substances to inhibit
fungal and bacterial growth in amounts from 0.01 to 1% by weight based on the total
weight of the ink.
The inks may be prepared in a conventional manner by mixing the components in
water
The dye inks of the invention are useful in inkjet printing processes for printing a wide
variety of pretreated materials, such as silk, leather, wool, polyamide fibers and
polyurethanes, and especially cellulosic fiber materials of any kind. Such fiber
materials are for example the natural cellulose fibers, such as cotton, linen and
hemp, and also pulp and regenerated cellulose. The printing inks of the invention are
also useful for printing pretreated hydroxyl- or amino-containing fibers present in
blend fabrics, for example blends of cotton, silk, wool with polyester fibers or
polyamide fibers.
In contrast to conventional textile printing, where the printing ink already contains all
the fixing chemicals and thickeners for a reactive dye, in inkjet printing the auxiliaries
have to be applied to the textile substrate in a separate pretreatment step.
The pretreatment of the textile substrate, for example cellulose and regenerated
cellulose fibers and also silk and wool, is effected with an aqueous alkaline liquor
prior to printing. To fix reactive dyes there is a need for alkali, for example sodium
carbonate, sodium bicarbonate, sodium acetate, trisodium phosphate, sodium
silicate, sodium hydroxide, alkali donors such as, for example, sodium chloroacetate,
sodium formate, hydrotropic substances such as, for example, urea, reduction
inhibitors, for example sodium nitrobenzenesulfonates, and also thickeners to
prevent flowing of the motives when the printing ink is applied, for example sodium
alginates, modified polyacrylates or highly etherified galactomannans.
These pretreatment reagents are uniformly applied to the textile substrate in a
defined amount using suitable applicators, for example using a 2- or 3-roll pad,
contactless spraying technologies, by means of foam application or using
appropriately adapted inkjet technologies, and subsequently dried.
After printing, the textile fiber material is dried at 120 to 150°C and subsequently
fixed.
The fixing of the inkjet prints prepared with reactive dyes may be effected at room
temperature or with saturated steam, with superheated steam, with hot air, with

microwaves, with infrared radiation, with laser or electron beams or with other
suitable energy transfer techniques.
A distinction is made between one- and two-phase fixing processes:
In one-phase fixing, the necessary fixing chemicals are already on the textile
substrate.
In two-phase fixing, this pretreatment is unnecessary. Fixing only requires alkali,
which, following inkjet printing, is applied prior to the fixing process, without
intermediate drying. There is no need for further additives such as urea or thickener.
Fixing is followed by the print aftertreatment, which is the prerequisite for good
fastnesses, high brilliance and an impeccable white ground.
The dye mixtures according to the invention are notable for outstanding color
strength when applied to the cellulose fiber materials by dyeing or printing in the
presence of no or very small amounts of alkali or alkaline earth metal compounds. In
these special cases, for instance, no electrolyte salt is required for a shallow depth of
shade, not more than 5 g/l of electrolyte salt is required for a medium depth of shade
and not more than 10 g/l of electrolyte salt is required for deep shades.
According to the invention, a shallow depth of shade refers to the use of 2% by
weight of dye based on the substrate to be dyed, a medium-depth of shade refers to
the use of 2 to 4% by weight of dye based on the substrate to be dyed and a deep
shade refers to the use of 4 to 10% by weight of dye based on the substrate to be
dyed.
The dyeing and prints obtainable with the dye mixtures according to the invention
possess bright shades; more particularly, the dyeings and prints on cellulose fiber
materials possess good lightfastness and especially good wetfastnesses, such as
fastness to washing, milling, water, seawater, crossdyeing and acidic and alkaline
perspiration, also good fastness to pleating, hotpressing and rubbing. Furthermore,
the cellulose dyeings obtained following the customary aftertreatment of rinsing to
remove unfixed dye portions exhibit excellent wetfastnesses, in particular since
unfixed dye portions are easily washed off because of their good solubility in cold
water.

Furthermore, the dye mixtures according to the invention can also be used for the
fiber-reactive dyeing of wool. Moreover, wool which has been given a nonfelting or
low-felting finish (cf. for example H. Rath, Lehrbuch der Textilchemie, Springer-
Verlag, 3rd edition (1972), pages 295-299, especially finished by the Hercosett
process (page 298); J. Soc. Dyers and Colorists 1972, 93-99, and 1975, 33-44), can
be dyed to very good fastness properties. The process of dyeing on wool is here
carried out in a conventional manner from an acidic medium. For instance, acetic
acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium
acetate can be added to the dyebath to obtain the desired pH. To obtain a dyeing of
acceptable levelness, it is advisable to add a customary leveling agent, for example a
leveling agent based on a reaction product of cyanuric chloride with three times the
molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalene-
sulfonic acid or on the basis of a reaction product of for example stearylamine with
ethylene oxide. For instance, the dye mixture according to the invention is preferably
subjected to the exhaust process initially from an acidic dyebath having a pH of about
3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time,
shifted into the neutral and optionally weakly alkaline range up to a pH of 8.5 to bring
about, especially for very deep dyeings, the full reactive bond between the dyes of
the dye mixtures according to the invention and the fiber. At the same time, the dye
portion not reactively bound is removed.
The procedure described herein also applies to the production of dyeings on fiber
materials composed of other natural polyamides or of synthetic polyamides and
polyurethanes. In general, the material to be dyed is introduced into the bath at a
temperature of about 40°C, agitated therein for some time, the dyebath is then
adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the
actual dyeing is carried out at a temperature between 60 and 98°C. However, the
dyeings can also be carried out at the boil or in sealed dyeing apparatus at
temperatures of up to 106°C. Since the water solubility of the dye mixtures according
to the invention is very good, they can also be used with advantage in customary
continuous dyeing processes. The color strength of the dye mixtures according to the
invention is very high.
The dye mixtures according to the invention dye the materials mentioned, preferably

fiber materials, in orange to red shades having very good fastness properties.
The examples hereinbelow serve to illustrate the invention. Parts and percentages
are by weight, unless otherwise stated. Parts by weight relate to parts by volume as
the kilogram relative to the liter. The compounds described in the examples in terms
of a formula are indicated in the form of the sodium salts, since they are generally
prepared and isolated in the form of their salts, preferably sodium or potassium salts,
and used for dyeing in the form of their salts. The starting compounds described in
the examples hereinbelow, especially the table examples, can be used in the
synthesis in the form of the free acid or likewise in the form of their salts, preferably
alkali metal salts, such as sodium or potassium salts.
Example 1
50 parts of an electrolyte-containing dye powder which contains the scarlet disazo
dye of formula (1-1)

in a 70% fraction and 50 parts of an electrolyte-containing dye powder containing the
yellow azo dye of the formula (Ge-1)


in a 75% fraction, are dissolved in 500 parts of water and the resulting dye
solution is adjusted to pH 5.5-6.5. Evaporating this dye solution gives a dye
mixture which provides golden orange to neutral orange dyeings and prints on
cotton under the dyeing conditions customary for reactive dyes. Alternatively,
the dye solution obtained can also be buffered at pH 5.5-6 by addition of a
phosphate buffer and be further diluted or concentrated to provide a liquid brand
of defined strength.
Example 2
20 parts of an electrolyte-containing dye powder containing the red disazo dye of the
formula (1-2)

in a 70% fraction and 80 parts of an electrolyte-containing dye powder containing the

golden yellow azo dye of the formula (Ga-1)

in a 70% fraction are mechanically mixed with each other.
The resulting dye mixture according to the present invention provides neutral
orange to reddish orange dyeings and prints on cotton for example under the
dyeing conditions customary for reactive dyes.
Example 3
20 parts of an electrolyte-containing dye powder containing the scarlet disazo dye of
the formula (I-3)

in a 75% fraction and 80 parts of an electrolyte-containing dye powder containing the
yellow azo dye of the formula (Gf-1)


in a 65% fraction are dissolved in 500 parts of water and the resulting dye solution is
adjusted to pH 5.5-6.5. Evaporating this dye solution gives a dye mixture which
provides orange dyeings and prints on cotton under the dyeing conditions customary
for reactive dyes. Alternatively, the dye solution obtained can also be buffered at
pH 5.5-6 by addition of a phosphate buffer and be further diluted or
concentrated to provide a liquid brand of defined strength.
Example 4
180 parts of 4-(ß-sulfatoethylsulfonyl)aniIine are suspended in 440 parts of
ice-water and 116 parts of 30% hydrochloric acid and diazotized by dropwise
addition of 11 2 parts of 40% sodium nitrite solution. After excess nitrite has
been removed with sulfamic acid, 67 parts of 4-hydroxy-
7-(sulfomethylamino)naphthalene-2-sulfonic acid (prepared by reaction of
48 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid with 32 parts of
formaldehyde sodium bisulfite in an aqueous medium at pH 5.5-6 and 45°C) and
also 23 parts of 2,4-diaminobenzenesulfonic acid are added, and a first coupling
reaction is carried out at pH 1 to 2 below 20°C to form a mixtureof two
monoazo dyes as per the formulae (15-4) and (Ga-2). The stated pH range is set
and maintained during the coupling reaction by addition of solid sodium
bicarbonate.


After the first coupling has ended, pH 5.5-6.5 is set with sodium carbonate
below 25°C. The 2 :1 mixture of the two azo dyes (I-4) and (Gb-1) which has
formed after the second coupling reaction has ended is isolated by spray drying.

The resulting dye mixture according to the present invention dyes cotton in orange
shades.
Example 5
141 parts of 4-(ß-sulfatoethylsulfonyl)aniline are suspended in 360 parts of
ice-water and 91 parts of 30% hydrochloric acid and diazotized by dropwise
addition of 87 parts of 40% sodium nitrite solution. After excess nitrite has been
removed with sulfamic acid solution, the diazo suspension obtained is pumped
into an aqueous solution of a mixture of 138 parts of the scarlet monoazo dye of
the formula (15-5) and 188 parts of the orange monoazo dye of the
formula (Ga-4)


which mixture was obtained by diazotization of 180.5 parts of 2-amino-
5-(ß-sulfatoethylsulfonyl)benzenesulfonic acid with 87 parts of 40% sodium
nitrite solution in a sulfuric acid medium and subsequent coupling onto a mixture
of 50.5 parts of 4-hydroxy-7-methylaminonaphthalene-2-sulfonic acid and
56.5 parts of 2,4-diaminobenzenesulfonic acid at pH 1.5 to 2. Then pH 5-6 is
set and maintained with sodium carbonate. The 42 : 58 mixture of the two dyes
(I-7) and (Gb-2) which has formed after the coupling reaction has ended can be
isolated by evaporation under reduced pressure or by spray drying.

The resulting dye mixture according to the present invention dyes cotton in reddish
brown shades.
Example 6
156 parts of 2-methoxy-5-(ß-sulfatoethylsulfonyl)aniline are suspended in 450 parts
of ice-water and 91 parts of 30% hydrochloric acid and diazotized by dropwise
addition of 88 parts of 40% sodium nitrite solution. After excess nitrite has been
removed with sulfamic acid solution, the diazo suspension obtained is pumped into

an aqueous solution of 169 parts of the scarlet monoazo dye of the formula (15-3)

which was obtained by diazotization of 91 parts of 2-amino-5-(ß-sulfatoethyIsulfonyl)-
benzenesulfonic acid with 44 parts of 40% sodium nitrite solution in a sulfuric acid
medium and subsequent coupling onto 60 parts of 7-amino-4-hydroxy-naphthalene-
2-sulfonic acid at pH 1.5 to 2. This is followed by the addition of 71 parts of
5-hydroxy-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid and pH 5-6 is set and
maintained with sodium carbonate below 25°C. The 60 : 40 mixture of the two
dyes (I-5) and (Gc-5) which has formed after the coupling reaction has ended can be
isolated by evaporation under reduced pressure or by spray drying.

The resulting dye mixture of the present invention dyes cotton in reddish shades.
Examples 7 to 137
The table examples which follow describe further inventive mixtures of the dyes of
the general formulae (I) and (Ga)-(Gf), which are each listed in the form of the
sodium salts. The mixing ratios are reported in percent by weight. The dye mixtures

I
provide orange/scarlet to brownish red dyeings on cotton for example by the dyeing
methods customary for reactive dyes.
Dye mixtures as per examples 1 to 3






















Use example 1
2 parts of a dye mixture obtained as per example 1 -6 and 50 parts of sodium chloride
are dissolved in 999 parts of water and 5 parts of sodium carbonate, 0.7 part of
sodium hydroxide (in the form of a 32.5% aqueous solution) and, if appropriate,
1 part'of a wetting agent are added. This dyebath is entered with 100 g of a woven
cotton fabric. The temperature of the dyebath is initially maintained at 25°C for
10 minutes, then raised to the final temperature (40-80°C) over 30 minutes and
maintained at the final temperature for a further 60-90 minutes. Thereafter, the dyed
fabric is initially rinsed with tap water for 2 minutes and then with deionized water for
5 minutes. The dyed fabric is neutralized at 40°C in 1000 parts of an aqueous
solution which contains 1 part of 50% acetic acid for 10 minutes. It is rinsed again
with deionized water at 70°C and then soaped off at the boil with a laundry detergent
for 15 minutes, rinsed once more and dried to provide an orange to red dyeing
having very good fastness properties.
Use example 2
4 parts of a dye mixture obtained as per example 1-6 and 50 parts of sodium chloride
are dissolved in 998 parts of water and 5 parts of sodium carbonate, 2 parts of
sodium hydroxide (in the form of a 32.5% aqueous solution) and if appropriate 1 part
of wetting agent are added. This dyebath is entered with 100 g of a woven cotton
fabric. The rest of the processing is carried out as reported in use example 1 to
provide an orange to red dyeing of high color intensity and having very good fastness
properties.
Use example 3
A textile fabric consisting of mercerized cotton is padded with a liquor containing
35 g/l of anhydrous sodium carbonate, 100 g/l of urea and 150 g/l of a low viscosity
sodium alginate solution (6%) and then dried. The wet pickup is 70%. The thus
pretreated textile is printed with an aqueous ink containing
2% of a dye mixture as per example 1
20% of sulfolane
0.01% of Mergal K9N
77.99% of water

using a drop-on-demand (bubble jet) inkjet print head. The print is fully dried. It is
fixed by means of saturated steam at 102°C for 8 minutes.
The print is then rinsed warm, subjected to a fastness wash with hot water at 95°C,
rinsed warm and then dried. The result is an orange to red print having excellent
service fastnesses.
Use example 4
A textile fabric consisting of mercerized cotton is padded with a liquor containing
35 g/l of anhydrous sodium carbonate, 50 g/l of urea and 150 g/l of a low viscosity
sodium alginate solution (6%) and then dried. The wet pickup is 70%. The thus
pretreated textile is printed with an aqueous ink containing
8% of a dye mixture as per example 2
20% of 1,2-propanediol
0.01%of Mergal K9N and
71.99% of water
using a drop-on-demand (bubble jet) inkjet print head. The print is fully dried. It is
fixed by means of saturated steam at 102°C for 8 minutes. The print is then rinsed
warm, subjected to a fastness wash with hot water at 95°C, rinsed warm and then
dried. The result is a reddish orange print having excellent service fastnesses.
Use example 5
A textile fabric consisting of mercerized cotton is padded with a liquor containing
35 g/l of anhydrous sodium carbonate, 100 g/l of urea and 150 g/l of a low viscosity
sodium alginate solution (6%) and then dried. The wet pickup is 70%. The thus
pretreated textile is printed with an aqueous ink containing
8% of a dye mixture as per example 5
15% of N-methylpyrrolidone
0.01%of Mergal K9N and
76.99% of water
using a drop-on-demand (bubble jet) inkjet print head. The print is fully dried. It is
fixed by means of saturated steam at 102°C for 8 minutes. The print is then rinsed
warm, subjected to a fastness wash with hot water at 95°C, rinsed warm and then
dried. The result is a reddish orange print having excellent service fastnesses.

WE-CLAIM
1. Reactive dye mixture consisting of one or more dyes of the herein below
indicated and defined general formula (1) in an amount of 10 to 90% by weight.

and one or more monoazo dyes of the general formulae (15) to (16) each in an
amount of 0-10% by weight,

and one or more dyes of the herein below indicated and defined general
formulae (Ga)-(Gf), independently in each case in an amount of 10 to 90% by
weight.




where
D1 to D7 are independently a group of the general formula (1)

where
R1 and R2 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy. hydroxyl,
sulfo, earboxyl, cyano, nitro, amido, ureido or halogen; and
X1 is hydrogen or a group of the formula -SO2-Z, where
Z is -CH=CH2, -CH2CH2f1 or hydroxyl, where
Z1 is hydroxyl or an alkali-detachable group, or
D1 to D7 are independently a naphthyl group of the general formula (2)


where
R3 and R4 are independently hydrogen (C1-C4)alkyl, (C1-C4)-alkoxy, hydroxyl,
sulfo, carboxyl, cyano, nitro, amido, ureido or halogen; and
X2 has one of the meanings of X1; or
D1 to D7 are independently a group of the general formula (3)

where
R5 and R6 independently have one of the meanings of R1 and R2;
R7 is hydrogen, (C1-C4)-alkyl, unsubstituted or (C1-C4)-alkyl-, (C1-C4) - alkoxy-,
sulfo-, halogen- or carboxyl- substituted phenyl, and
Z2 is a group of the general formula (4) or (5) or (6)

where

V is fluorine or chlorine;
U1, U2 are independently fluorine, chlorine or hydrogen;
and
Q1, Q2 are independently chlorine, fluorine, cyanamido, hydroxyl, (C1-C6)-alkoxy,
phenoxy, sulfophenoxy, mercapio, (C1-C6)-aikylmercapto, pyridino,
carboxypyridino, carbamoylpyridino or a group of the general formula (7) or (8)

where
RB is hydrogen or (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl or phenyl which is
unsubstituted or substituted by (C1-C4)-alkyl, (C1-C6)-alkoxy,sulfo,halogen,
carboxyl, acetamido,ureido;
R9 and R10 independently have one of the meanings of R8 or combine to form a
cyclic ring system of the formula -(CH2)1-, wherein j is 4 or 5, or alternatively -
(CH2)2-E-(CH2)2-, wherein E is oxygen, sulfur sulfonyl, -NR11 where R11 = (C1-C6)-
alkyl;
W is phenylene which is unsubstituted or substituted by 1 or 2 substituents, such
as (C1-C4)-alkyl, (C1-C4)-alkoxy, carboxyl, sulfo, chlorine, bromine, or is (C1-C4)-
alkylenearylene or (C2-C5) alkylene, which may be interrupted by oxygen, sulfur,
sulfonyl, amino, carbonyl, carboxamido or is phenylene CONH-phenylene which
is unsubstituted or substituted by (C1-C4) -alkyl, (C1-C4) -alkoxy hydroxyl, sulfo.

carboxyl, amido, ureido or halogen, or is naphthylene which is unsubstituted or
substituted by one or two sulfo groups ;and
Z is as defined above; or
D1 to D7 are independently a group of the general formula (9)

where
R12 is hydrogen, (C1-C4)-alkyl, aryl or a substituent aryl radical;
R13 and R14 are independently hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, hydroxy!.
sulfo, carboxyl,cyano, nitro,mido, ureido or halogen;and
A is a phenylene group of the general formula (10)

where
R15 and R16 are independently hydrogen (C1-C4)-alkyI, (C1-C4) alkoxy,
hydroxyl,ulfo, carboxyl, cyano, nitro,mido, urreido or halogen; or
A is a naphthylene group of the general formula (11)


where
R17 and R18 are independently hydrogen,(C1-C4) - alkyl, (C1-C4)-alkoxy, hydroxy!,
sulfo, carboxyl, cyano, nitro,mido, ureido or halogen; or
A is a polymerylene group of the general formula (12)

where
k is an integer greater than 1 and
R19 and R20 are independently hydrogen, (C1-C4)-alkyl,(C1-C4) alkoxy,
hydroxy!, cyano, amido, halogen or aryl; and
X3 has one of the meanings of X1; and
R* is a group of the formula (14)


R** is hydrogen or (C1-C4)-alkyl;
R31 is hydrogen, acetyl, carbamoyl or a group of the general formula (4) or (5) or
(14),
R32 is hydrogen or a group of the general formula (14),
R33 is methyl, carboxyl or carboxyalkyl with C1-C4ralkyl,
R34 is hydrogen or methyl,
R35 is hydrogen, cyano, carbamoyl, carboxyl or a group of the general formula
(14),
R36 is methyl, ethyl or β-sulfoerhyl,
R37 is methyl, carboxyl or carboxyalkyl with C1-to C4 - alky I,
R38 is acetamido, ureido, methyl or methoxy,
R39 is hydrogen, methyl or methoxy,
m is Oor l,
n is 1,2 or 3,
Z3 has one of the meanings of Z2, and
M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal
wherein the dyes of the general formulae (1) and (Ga)-(Gf) contain at least one
fiber-reactive group of the formula -SO2-Z or Z2.
2. Reactive dye mixture as claimed in claim 1, wherein R** is hydrogen.
3. Reactive dye mixture as claimed in claim 1 and/or 2, wherein Z is vinyl, p-
chioroethyl or p-sulfoerhyl.

4. Reactive dye mixture as claimed in one of claims 1 to 3, wherein Q1 and Q2
in the general formula (5) are independently fluorine, chlorine, cyanamido,
morpholino, 2-sulfophenylamino,3-ulfophenylamino,4-sulfophenylamino, 3-(2-
sulfatoethylsulfonyl)phenylamino, 4-(2-sulfatoethylsulfonyl) phenylamino, 3-
(vinlsulfonyl) phenylamino, 4-(vinylsulfonyl) phenylamino, N-methyl-N-(2-(2-
sulfatoethylsulfonyl) ethyl) amino or N-phenyl-N-(2-(2-sulfatoethylsuifonyl) ethyl)
amino.
5. A process for preparing a dye mixture as claimed in one or more of claims 1
to 4, which comprises the individual dyes of the formulae (1), (15), (16) and
(Ga)-(Gf) being mixed in the mandated ratio either mechanically in solid form or
in the form of aqueous solutions.
6. A process for preparing a dye mixture as claimed in claims 1 to 4 when D2
and D3 and/or D5 and/or D5 and/or D7 as per the general formulae (1) and (Ga)
and/or (Gb) and/or (Gc) and/or (Gd) have the same meaning, which comprises
an amine of the general formula (17)

where D2 is as defined in claim 1, being diazotized in a conventional manner and
the diazonium compound obtained being subsequently reacted with an aqueous
solution or suspension of a mixture having a fixed ratio of a monoazo dye as per
the general formula (15) and of at least one coupler as per the general formula
(13) and/or (18) and/or (19) and/or a monoazo dye as per the general formula
(20)



where D4, R*, R**, R31, R32, R33, R34, R35, R36, Z and M are each as defined in
claim 1.
7. A process for preparing a dye mixture as claimed in one of claims 1 to 4
when the groups D1, D2 and D4, D5 as per the formulae (1) and (Gb) have the
same meaning, which comprises an amine of the general formula (21)

where D1 is as defined in claim 1, being diazotized in a conventional manner and
coupled onto a mixture of the coupling components (22) and (23)

where R*, R**, R32 and M are each as defined in claim 1, in a first stage and
subsequently further converted to form a mixture of the dyes of the general
formulae (1) and (Gb).
8. Aqueous liquid product comprising a dye mixture as claimed in at least one
of claims 1 to 4 having a total dye content of 5, 50% by weight.

9. Aqueous printing ink for textile printing by the inkjet process, comprising
a dye mixture as claimed in one or more of claims 1 to 4 in amounts from
0.01 % by weight to 40% by weight based on the total weight of the ink.
10. A process for dyeing, conventionally printing and also inkjet printing
textile fiber materials, which comprises utilizing a dye mixture as claimed
in one or more of claims 1 to 4.


Reactive dye mixture consisting of one or more dyes of the herein below
indicated and defined general formula (1) in an amount of 10 to 90% by weight

and one or more monoazo dyes of the general formulae (15) to (16) each in an
amount of 0-10% by weight,

and one or more dyes of the herein below indicated and defined general
formulae (Ga)-(Gf), independently in each case in an amount of 10 to 90% by
weight



where D1, D2, D3, D4, D5, D6, D7, R*, R**, R31, R32, R33, R34, R35, R36, R37, R38,
R39, Z, Z3m, n and M are each as defined in claim 1, the dyes of the general
formulae (1) and (Ga)-(Gf) containing at least one fiber-reactive group of the
formula -SO2-Z or -Z2, their preparation and their use for dyeing hydroxyl-
and/or carboxamido-containing the fiber material.

Documents:

453-kol-2003-abstract.pdf

453-kol-2003-assignment.pdf

453-kol-2003-claims.pdf

453-kol-2003-correspondence.pdf

453-kol-2003-description (complete).pdf

453-kol-2003-drawings.pdf

453-kol-2003-examination report.pdf

453-kol-2003-form 1.pdf

453-kol-2003-form 18.pdf

453-kol-2003-form 2.pdf

453-kol-2003-form 3.pdf

453-kol-2003-gpa.pdf

453-kol-2003-reply to examination report.pdf

453-kol-2003-specification.pdf

453-kol-2004-abstract 1.1.pdf

453-KOL-2004-CANCELLED DOCUMENT.pdf

453-kol-2004-claims 1.1.pdf

453-KOL-2004-CORRESPONDENCE 1.1.pdf

453-kol-2004-correspondence-1.1.pdf

453-kol-2004-description complete 1.1.pdf

453-kol-2004-examination report-1.1.pdf

453-kol-2004-form 18-1.1.pdf

453-kol-2004-form 2 1.1.pdf

453-kol-2004-form 3-1.1.pdf

453-kol-2004-form 5.pdf

453-kol-2004-gpa-1.1.pdf

453-kol-2004-granted-abstract.pdf

453-kol-2004-granted-claims.pdf

453-kol-2004-granted-description (complete).pdf

453-kol-2004-granted-form 1.pdf

453-kol-2004-granted-form 2.pdf

453-kol-2004-granted-specification.pdf

453-KOL-2004-OTHERS 1.1.pdf

453-kol-2004-others-1.1.pdf

453-KOL-2004-OTHERS.pdf

453-KOL-2004-PETITION UNDER RULE 137.pdf

453-kol-2004-priority document.pdf

453-kol-2004-reply to examination report 1.1.pdf

453-kol-2004-reply to examination report-1.2.pdf

453-kol-2004-translated copy of priority document.pdf


Patent Number 246129
Indian Patent Application Number 453/KOL/2004
PG Journal Number 07/2011
Publication Date 18-Feb-2011
Grant Date 15-Feb-2011
Date of Filing 30-Jul-2004
Name of Patentee DYSTAR TEXTILFARBEN GMBH & CO. & DEUTSCHLAND KG.
Applicant Address D-65926 FRANKFURT AM MAIN
Inventors:
# Inventor's Name Inventor's Address
1 JOACHIM EICHHORN HORTENSIENRING 17, 65929 FRANKFURT AM MAIN
2 STEFAN MEIER GEISENHEIMER STRASSE 88, 60529 FRANKFURT
3 WERNER RUSS BAD-WEIBACH-STRASSE 9, 65439 FLORSHEIM-WICKER
PCT International Classification Number C09B 62/04
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10337637.2 2003-08-16 Germany