Title of Invention

DYE MIXTURES OF FIBER-REACTIVE AZO DYES, THEIR PREPARATION AND THEIR USE.

Abstract Reactive dye mixtures which comprise one or more dyes of the indicated general formula (I) and one or more dyes of the hereinbelow indicated and defined general formula (II) where D1, D2, D3, R°, R*. R**,T, b, f, v and M are each as defined in claim 1, the dyes of the general formulae (I) and (II) containing at least one fiber-reactive group of the formula -SO2-Z or -Z2, their preparation and their use for dyeing and printing hydroxyl- and/or carboxamido-containing fiber material.
Full Text DYE MIXTURES OF FIBER-REACTIVE AZO DYES, THEIR PREPARATION AND
THEIR USE
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 the documents EP 0 681 007, EP 1 013 729, EP 0 957 137 and
EP 0 719 841. 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 which comprise 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, such as two or three, preferably 1 or 2, dyes of the hereinbelow
indicated and defined general formula (II)
and also optionally one or more, such as two or three, preferably 1 or 2, dyes of the
hereinbelow indicated and defined general formulae (Ga) to (Gf)
where
D1 to D3 and D5 to D9 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 D3 and D5 to D9 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 D3 and D5 to D9 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)-
alkylmercapto, 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;
R9 and R10 independently have one of the meanings of R8 or
combine to form a cyclic ring system of the formula
-(CH2)-, 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-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 D3 and D5 to D9 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, carboxyi, 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, carboxyi, 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° is hydrogen or a group of the general formula (4) or (5) or
R° is a group of the general formula (13)

where
R21 is (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, carboxy-(C1-C6)-alkyl or phenyl
which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy,
sulfo, halogen, carboxyl, acetamido, ureido;
or
R° is a group of the general formula (100)
where
D4 has one of the meanings of D1 to D3 or D5 to D9,
X is halogen or hydroxyl,
d is 0 or 1; and
R*, R** are independently hydrogen, (C1-C4)-alkyl or a group of the formula (14)
-CH2-SO3M (14);
b, f, v are independently 0 or 1; and
T is hydroxyl or NH2 wherein v is 0 when T is NH2;
R 31 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),
R 33 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),
R36 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 isOor1,
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), (II) 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)-aIkyl, (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 ß-position 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), (II) and (Gg)-(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 b-sulfatoethylsulfonyl groups. If the dyes of the general
formula (I), (II) and (Gg)-(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 D9 of the general formulae (1) and (2) are 2-b-sulfato-
ethylsulfonyl)-phenyl, 3-(b-sulfatoethylsulfonyl)-phenyl,4-(b-sulfatoethylsulfonyl)-
phenyl, 2-carboxy-5-(b-sulfatoethylsulfonyl)-phenyl, 2-chloro-4-(b-sulfatoethyl-
sulfonyl)-phenyl, 2-chloro-5-(b-sulfatoethylsulfonyl)-phenyl, 2-bromo-4-(b-sulfato-
ethylsulfonyl)-phenyl, 2-sulfo-4-(b-sulfatoethylsulfonyl)-phenyl, 2-sulfo-5-(b-sulfato-
ethyls"ulfonyl)-phenyl, 2-methoxy-5-(b-sulfatoethylsulfonyl)-phenyl, 2-ethoxy-
5-(b-suifatoethylsuIfonyl)-phenyl, 2,5-dimethoxy-4-(b-sulfatoethylsulfonyl)-phenyl,
2-methoxy-5-methyl-4-(b-sulfatoethylsulfonyl)-phenyl,2-methyl-4-(b-sulfatoethyl-
sulfonyl)-phenyl, 2- or 3- or4-(b-thiosulfatoethylsulfonyl)-phenyl, 2-methoxy-
5-(b-thiosulfatoethylsulfonyl)-phenyl, 2-sulfo-4-(b-phosphatoethylsulfonyl)-phenyl, 2-
or 3- or 4-vinylsulfonyl-phenyl, 2-sulfo-4-vinylsulfonyl-phenyl, 2-chloro-4-(b-chloro-
ethylsulfonyl)-phenyl, 2-chloro-5-(b-chloroethylsulfonyl)-phenyl, 3- or
4-(b-acetoxyethylsulfonyl)-phenyl, 6- or 8-(b-sulfatoethylsulfonyl)-naphth-2-yl,
6-(b-sulfatoethylsulfonyl)-1 -sulfo-naphth-2-yl and 8-(b-sulfatoethylsulfonyl)-6-sulfo-
naphth-2-yl, preferably 3-(b-sulfatoethylsulfonyl)-phenyl, 4-(b-sulfatoethylsulfonyl)-
phenyl, 2-sulfo-4-(b-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-(b-sulfato-
ethylsulfonyl)-phenyl, 2,5-dimethoxy-4-(b-sulfatoethylsulfonyl)-phenyl, 2-methoxy-
5-methyl-4-(b-sulfatoethylsulfonyl)-phenyl and 3- or 4-vinylsulfonyl-phenyl, or D1 to
D9 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 D9 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 D9 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 b-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 b-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, methylmercapto, 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-suIfatoethylsulfonyl)-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-sulfatoethylsulfony!)-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-sulfatoethylsulfonyl)-phenyl-
carbamoyl)-phenylamino, 3-(4-(2-sulfatoethylsulfonyl)-phenylcarbamoyl)-
phenylamino, 3-(2-sulfatoethylsulfonyl)-propylamino, N-methyl-
N-(2-(2-sulfatoethylsulfonyl)-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-sulfophenylamino, 3-sulfophenyl-
amino, 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-suIfatoethylsulfonyl)-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.
T in the general formula (II) is preferably hydroxyl or amino attached to the
naphthalene nucleus in the a position, with hydroxyl being particularly preferred.
More preferably, b is 1, v is 1 and f is 0 or 1.
R° is more 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 and Q2 or is a group of the general
formula (100), in which case the group X is preferably fluorine, chlorine or
hydroxyl and more preferably chlorine;
d is more preferably 1.
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 formula (II) and also optionally (Ga) - (Gf)
independently each in an amount from 1% to 99% by weight and preferably from
10% to 90% by weight.
In addition, the dye mixtures according to the present invention may further comprise
one or more monoazo dyes of the general formulae (15) and (16) in an amount of up
to 10% by weight and preferably up to 5% by weight
where D1, M, R* and R** are each as defined above.
Preferably, D1 is 3-(b-sulfatoethylsulfonyl)-phenyl, 4-(b-sulfatoethylsulfonyl)-phenyl,
2-sulfo-4-(b-sulfatoethylsulfonyl)-phenyl, 2-methoxy-5-(b-sulfatoethylsulfonyl)-phenyl,
2,5-dimethoxy-4-(b-suIfatoethylsulfonyl)-phenyl, 2-methoxy-5-methyl-4-(b-
sulfatoethylsulfonyl)-phenyl, 3- or 4-vinylsulfonyl-phenyl, 2-sulfo-4-(vinylsulfonyl)-
phenyl, 2-methoxy-5-(vinylsulfonyl)-phenyl, 2,5-dimethoxy-4-(vinylsulfonyl)-phenyl or
2-methoxy-5-methyl-4-(vinylsulfonyl)-phenyl.
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)
one or more dyes of the hereinbelow indicated and defined genera! formula (ll-a)
and/or one or more dyes of the hereinbelow indicated and defined general
formula (ll-b)
and optionally one or more dyes of the general formula (Ga), (Gb), (Ge) and (Gf),
in each of which D1 to D7, FT, R°, f, R31, R32, R37, R38, R39, Z, Z3, m, n and M are ei
as defined above and D31 has one of the meanings of D1 to D7.
Further preferred dye mixtures comprise at least one dye of the general
formula (l-b)
and at least one dye of the general formula (ll-c)
and optionally at least one dye of the general formulae (Ga), (Gb), (Ge) and (Gf),
where D5 to D7, T, f, R31, R32, R37, R38, R39, Z, Z3, m, n and M are each as defined
above and R201 to R206 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),
one or more dyes of the hereinbelow indicated and defined general formula (ll-d)
and/or one or more dyes of the hereinbelow indicated and defined general
formula (ll-e)
and optionally one or more dyes of the general formula (Ga-a), (Gb-a) and (Ge-a)
in which D2, D3, D6, D7, R°, f, R31, Z and M are each as defined above.
Preferred meanings in the general formulae (l-c), (ll-e) and (Ga-a) are R101 to R108
independently hydrogen, C1-C4-alkyl, C1-C4-alkoxy, sulfo, carboxyl or halogen and
Z vinyl or b-sulfatoethyl and very particularly preferred meanings in the
formula (l-c), (ll-e) and (Ga-a) are R101 to R108 independently hydrogen, methyl,
methoxy or sulfo and Z vinyl or b-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 formula (II) are described in DE 2748965 and also 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, if
appropriate, D4 and optionally D7 as per the general formulae (I) and (II) and, if
appropriate, (100) and (Gb) have the same meaning, it is possible for an amine of the
general formula (17)
D2-NH2 (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 as per the general formula (18) and
optionally of a monoazo dye as per the general formula (19)
where D1, D6, R*, R**, R°, R32, T, b, f, v 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 D3 and, if appropriate, D4 and optionally D6, D7 as per
the general formulae (I) and (II) and, if appropriate, (100) and (Gb) have the same
meaning, which comprises an amine of the general formula (20)
D1-NH2 (20),
where D1 is as defined above, being diazotized in a conventional manner and
coupled onto a mixture of in each case at least one coupling component (21) and
(15) and also optionally (22)
where R*, R**, R°, R32, T, b, f, v 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 (II) and optionally (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 (II) and optionally (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 b-chloroethylsulfonyl or (i-thiosulfatoethylsulfonyl or
b-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, nyIon-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
glycof 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'-
dimethylurea, 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-imidazoIidinone, 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 Theological additives, for example:
polyvTnylcaprolactam, 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
aminonaphthalenesulfonic 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 40QC, 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
30 parts of an electrolyte-containing dye powder which contains the scarlet disazo
dye of formula (1-1)
in a 75% fraction and 70 parts of an electrolyte-containing dye powder containing the
red azo dye of the formula (II-1)
in a 70% fraction are mechanically mixed with each other.
The resulting dye mixture according to the present invention provides red dyeings
and prints on cotton for example under the dyeing conditions customary for reactive
dyes.
Example 2
40 parts of an electrolyte-containing dye powder containing the red disazo dye of the
formula (I-2)
in a 75% fraction and 60 parts of an electrolyte-containing dye powder containing the
red disazo dye of the formula (II-100)
in a 70% 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 red dyeings and prints on cotton under the dyeing conditions customary for
reactive dyes.
Example 3
281 parts of 4-(b--sulfatoethyIsulfonyl)aniline are suspended in 700 parts of ice-water
and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of
173 parts of 40% sodium nitrite solution. After excess nitrite had been removed with
sulfamic acid solution, the diazo suspension obtained is pumped into an aqueous
solution of 397 parts of the scarlet monoazo dye of the formula (15-1)
which was obtained by diazotization of 180.5 parts of 2-amino-5-(b-sulfatoethyl-
sulfonyl)benzenesulfonic acid with 87 parts of 40% sodium nitrite solution in an acidic
medium and subsequent coupling onto 166.5 parts of 4-hydroxy-
7-(sulfomethylamino)naphthalene-2-sulfonic acid at pH 1.5.140.5 parts of
7-acetylamino-4-hydroxynaphthalene-2-sulfonic acid are subsequently added as a
second coupling component and pH 5 - 6 is set at below 25°C and maintained with
sodium carbonate.
The 65 : 35 mixture of the two dyes (I-3) and (II-2) which is formed after the coupling
reaction has ended can be isolated by evaporation under reduced pressure or by
spray drying; 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.
The dye mixture obtained according to the present invention dyes cotton in reddish
orange shades.
Example 4
422 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in 1000 parts of ice-
water and 270 parts of 30% hydrochloric acid and diazotized by dropwise addition of
260 parts of 40% sodium nitrite solution. After excess nitrite has been removed with
sulfamic acid solution, the diazo suspension obtained is admixed with an aqueous
solution of 166.5 parts of 4-hydroxy-7-(sulfomethylamino)naphthalene-2-sulfonic acid
(obtained by reaction of 119.5 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid
with 75 parts of formaldehyde sodium bisulfite in an aqueous medium at pH 5.5 - 6
and 45°C) and adjusted to pH 1.5 with solid sodium bicarbonate. After the acidic
coupling has ended, this reaction mixture has added to it an aqueous solution of
335 parts of the second coupling component (18-1) and is adjusted to and
maintained at pH 5 - 6 with sodium carbonate below 25°C.
The 50 : 50 mixture of the two dyes (I-4) and (II-3) 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 red
shades.
Example 5
A binary mixture prepared similarly to the procedure described in example 3 from
554 parts of the scarlet disazo dye of the formula (I-3) and 277 parts of the red dye of
the formula (II-4) is admixed with 277 parts of the red disazo dye of the formula
(II-100), adjusted to a pH of 5.5 - 6.5 and isolated by evaporation of the aqueous
solution. The resulting 50 : 25 : 25 mixture of the three dyes (I-3), (II-4) and (11-100)
which is according to the present invention dyes cotton in red shades.
Example 6
25 parts of an electrolyte-containing dye powder containing the red disazo dye of the
formula (I-5)
in a 75% fraction and 75 parts of an electrolyte-containing 1:1 dye mixture containing
the two red azo dyes of the formulae (H-3) and (II-4) in a 70% fraction are
mechanically mixed with each other.
The resulting dye mixture according to the present invention provides red dyeings and
prints on cotton for example under the dyeing conditions customary for reactive dyes.
Example 7
a) 312 parts of 2-(b-sulfatoethylsulfonyl)aniline are suspended in 800 parts of ice-
water by addition of 165 parts of concentrated sulfuric acid and diazotized by
dropwise addition of 195 parts of 40% sodium nitrite solution. After excess nitrite has
been removed with sulfamic acid, a mixture of 250 parts of 4-hydroxy-7-(sulfomethyl-
amino)naphthalene-2-sulfonic acid and 120 parts of 4-hydroxy-6-(sulfomethyl-
amino)naphthalene-2-sulfonic acid (prepared by reaction of 179 parts of 7-amino-
4-hydroxynaphthalene-2-sulfonic acid and 86 parts of 6-amino-4-hydroxy-
naphthalene-2-sulfonic acid with 171 parts of formaldehyde sodium bisulfite in an
aqueous medium at pH 5.5 - 6 and 45°C) is added and coupled in a first stage at
pH 1 to 2 below 20°C to form a mixture of two monoazo dyes as per the
formulae (15-2) and (II-5). The stated pH range is set (and maintained during the
coupling reaction) by addition of solid sodium bicarbonate.
b) Separately, 211 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in
520 parts of ice-water and 137 parts of 30% hydrochloric acid and diazotized by
dropwise addition of 132 parts of 40% sodium nitrite solution. After excess nitrite has
been removed with sulfamic acid, this diazo suspension is added dropwise to the
mixture of the first coupling stage from a) and pH 5.5 - 6.5 is set at below 25°C with
sodium carbonate. The 3 : 1 mixture of the two azo dyes (I-6) and (II-5) which has
formed after the second coupling reaction has ended is subsequently isolated by
spray drying.
The resulting dye mixture according to the present invention dyes cotton in brownish
red shades.
Example 8
25 parts of an electrolyte-containing dye powder containing the brownish red disazo
dye in the formula (I-7)
in a 75% fraction, 35 parts of an electrolyte-containing dye powder containing the red
disazo dye of the formula (II-1) again in a 75% fraction and 40 parts of an electrolyte-
containing dye powder containing the red disazo dye of the formula (II—3) in a 70%
fraction are dissolved in 500 parts of water and the dye solution obtained is adjusted
to pH 5.5-6.5. Evaporation or spray drying of this dye solution provides a dye mixture
which provides red to reddish brown dyeings and prints on cotton under the dyeing
conditions customary for reactive dyes.
Example 9
326 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in 800 parts of ice-water
and 212 parts of 30% hydrochloric acid and diazotized by dropwise addition of
204 parts of 40% sodium nitrite solution. After excess nitrite has been removed with
sulfamic acid, this diazo suspension is added dropwise to an aqueous solution of
397 parts of the scarlet monoazo dye of the formula (15-1) (prepared as described in
example 3), 147 parts of 4-aminonaphthalene-1-sulfonic acid are added as a second
coupling component, and a pH of 5.5 - 6.5 is set with sodium carbonate at below
25°C. The 60 : 40 mixture of the two azo dyes (I-3) and (II-6) which has formed after
the coupling reaction has ended is subsequently isolated by spray drying.

The resulting dye mixture according to the present invention dyes cotton in reddish
orange shades.
Example 10
333 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in 850 parts of ice-water
and 214 parts of 30% hydrochloric acid and diazotized by dropwise addition of
205 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 339 parts of the scarlet monoazo dye of the formula (15-3)

which was obtained by diazotization of 180.5 parts of 2-amino-5-(b-sulfatoethyl-
sulfonyl)benzenesulfonic acid with 87 parts of 40% sodium nitrite solution in an acidic
medium and subsequent coupling onto 119 parts of 7-amino-4-hydroxy-naphthalene-
2-sulfonic acid at pH 1.5 to 2. This is followed by the addition of 140 parts each of the
two further coupling components (18-2) and (18-3)

and pH 5 — 6 is set and maintained with sodium carbonate below 25CC.
The 50 : 25 : 25 mixture of the three dyes (1-1), (II-7) and (II-8) 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 orange
shades.
Example 11
281 parts of 4-(li-suIfatoethylsulfonyl)aniline are suspended in 700 parts of ice-water
and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of
173 parts of 40% sodium nitrite solution. After excess nitrite has been removed with
sulfamic acid solution, the diazo suspension obtained is admixed with an aqueous
solution of 83 parts of 4-hydroxy-7-(sulfomethylamino)naphthalene-2-sulfonic acid
(obtained by reaction of 60 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid
with 37.5 parts of formaldehyde sodium bisulfite in an aqueous medium at pH 5.5 - 6
and 45°C) and adjusted to pH 1.5 with solid sodium bicarbonate. After the acidic
coupling has ended, this reaction mixture has added to it an aqueous solution of
111 parts of 4-amino-phthalene-1-sulfonic acid as the second coupling component
and is adjusted to and maintained at pH 5 - 6 with sodium carbonate below 25°C.
After the coupling reaction has ended, the reaction mixture is admixed with 73 parts
of the golden yellow azo dye of the formula (Ga-1) and the resulting
42 : 46 : 12 mixture of the three azo dyes (I-4), (II-6) and (Ga-1) is isolated by spray
drying.
The resulting dye mixture according to the present invention provides orange dyeings
and prints on cotton for example under the dyeing conditions customary for reactive
dyes.
Example 12
281 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in 700 parts of ice-water
and 180 parts of 30% hydrochloric acid and diazotized by dropwise addition of
173 parts of 40% sodium nitrite solution. After excess nitrite has been removed with
sulfamic acid solution, the diazo suspension obtained is added to an aqueous
solution of 397 parts of the scarlet monoazo dye of the formula (15-1), which was
obtained by diazotization of 180.5 parts of 2-amino-5-(b-sulfatoethylsulfonyl)-
benzenesulfonic acid with 87 parts of 40% sodium nitrite solution in an acidic medium
and subsequent coupling onto 166.5 parts of 4-hydroxy-7-(sulfomethylamino)-
naphthalene-2-sulfonic acid at pH 1.5.
This is followed by the addition of 258 parts of the further coupling component (18-4)

in the form of an aqueous solution and pH 5 - 6 is set and maintained with sodium
carbonate below 25°C.
After the coupling reaction has ended, the reaction mixture is admixed with 242 parts
of the golden yellow azo dye of the formula (Ga-3) and the resulting
46 : 34 : 20 mixture of the three azo dyes (I-3), (II-9) and (Ga-3) is isolated by
evaporation under reduced pressure or spray drying. Alternatively, the dye solution
obtained can also be buffered at pH 5.5 - 6 by addition of a phosphate buffer and
further diluted or concentrated to provide a liquid brand of defined strength.

The resulting dye mixture according to the present invention dyes cotton in orange
shades.
Example 13
200 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in 500 parts of ice-water
and 129 parts of 30% hydrochloric acid and diazotized by dropwise addition of
125 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-hydroxynaphtha!ene-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
initially coupled in a first stage at pH 1 to 2 below 20°C to form a mixture of 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, 27 parts of the further coupling component (18-5)

are added and pH 5.5 - 6.5 is subsequently set with sodium carbonate below 25°C.
The 58 :13 : 29 mixture of the three azo dyes (I-4), (II-10) 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 14
169 parts of 4-(b-sulfatoethylsulfonyl)aniline are suspended in 430 parts of ice-water
and 109 parts of 30% hydrochloric acid and diazotized by dropwise addition of
105 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 159 parts of the scarlet monoazo dye of the formula (15-1)
and 188 parts of the yellow monoazo dye of the formula (Ga-4)

which was formed by diazotization of 180.5 parts of 2-amino-5-(b-sulfatoethyl-
sulfonyl)benzenesulfonic acid with 87 parts of 40% sodium nitrite solution in a sulfuric
acid medium and subsequent coupling onto a mixture of 66.5 parts of 4-hydroxy-7-
(sulfomethylamino)naphthalene-2-sulfonic acid and 56.5 parts of
2,4-diaminobenzenesulfonic acid at pH 1.5 to 2. This is followed by the addition of
22.5 parts of 4-aminonaphthalene-1-sulfonic acid as a further coupling component
and pH 5 - 6 is set and maintained with sodium carbonate. The 40 : 10 : 50 mixture
of the three dyes (I-3), (II-6) and (Gb-2) which has formed after the coupling reaction
has ended can be isolated by evaporation under reduced pressure or by spray
drying. Alternatively, the dye solution obtained can be buffered at pH 5.5 - 6 by
addition of a phosphate buffer and further diluted or concentrated to provide a liquid
brand of defined strength.

The resulting dye mixture according to the present invention dyes cotton in orange to
reddish orange shades.
Examples 15 to 163
The table examples which follow describe further inventive mixtures of the dyes of
the general formulae (I) and (II) and if appropriate (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 provide orange/scarlet to brownish red dyeings on cotton for
example by the dyeing methods customary for reactive dyes.
Use example 1
2 parts of a dye mixture obtained as per example 1-14 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 soaked off at the boil with a laundry detergent
for 15 minutes, rinsed once more and dried to provide a strong reddish orange to
brownish red dyeing having very good fastness properties.
Use example 2
4 parts of a dye mixture obtained as per example 1-14 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 a scarlet dyeing 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, 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 any of examples 1-14
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 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, 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 any of examples 1-14
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 an orange to red print having excellent service fastnesses.
What is claimed is:
1. Reactive dye mixtures which comprise one or more dyes of the hereinbelow
indicated and defined general formula (I)

and one or more dyes of the hereinbelow indicated and defined general formula (II)

where
D1 to D3 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 D3 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 D3 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)-
alkylmercapto, 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;
R9 and 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)-
alkylenearylene 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 D3 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)
-(CR 19 R 20)k- (12)
where
k is an integer greater than 1 and
R19 and 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
R0 is hydrogen or a group of the general formula (4) or (5) or
Ro is a group of the general formula (13)

where
R21 is (C1-C6)-alkyl, sulfo-(C1-C6)-alkyl, carboxy-(C1-C6)-a!kyl or phenyl
which is unsubstituted or substituted by (C1-C4)-alkyl, (C1-C4)-alkoxy,
sulfo, halogen, carboxyl, acetamido, ureido;
or
R° is a group of the general formula (100)

where
D4 has one of the meanings of D1 to D3,
X is halogen or hydroxyl,
d is 0 or 1; and
R*, R** are independently hydrogen, (Ci-C4)-alkyl or a group of the formula (14)
-CH2-SO3M (14);
b, f, v are independently 0 or 1; and
T is hydroxyl or NH2 wherein v is 0 when T is NH2;
M is hydrogen, an alkali metal or one equivalent of an alkaline earth metal
wherein
the dyes of the general formulae (I) and (II) contain at least one fiber-reactive
group of the formula -SO2-Z or -Z2.
2. Reactive dye mixtures as per claim 1, wherein R** in the general formula (I) is
hydrogen.
3. Reactive dye mixtures as per claim 2, wherein R* in the general formula (I) is a
group of the general formula (14)
-CH2-SO3M (14)
and M is as defined in claim 1.
4. Reactive dye mixtures as per at least one of claims 1 to 3, comprising one or
more monoazo dyes of the general formulae (15) to (16), each in an amount of
0-10% by weight

where M, R*, R** and D1 are each as defined in claim 1.
5. Reactive dye mixtures as per at least one of claims 1 to 4, further comprising,
as a further blending or shading component, at least one dye conforming to the
hereinbelow indicated and defined general formulae (Ga") - (Gf)


where
D5, D6, D7, D8, D9 have one of the meanings of D1, D2 or D3; wherein D5, when R31
is not a group of the general formula (4) or (5), and also D6 or D7 and D9
contain at least one fiber-reactive group of the formula -SO2Z or Z2;
R31 is hydrogen, acetyl, carbamoyl, sulfomethyl or
a group of the general formula (4-1) or (5-1)

where
V1 is fluorine or chlorine;
U11, U21 are independently fluorine, chlorine or hydrogen;
and
Q11 , Q21 are independently chlorine, fluorine, cyanamido, hydroxyl,
(C1-C6)-alkoxy, phenoxy, sulfophenoxy, mercapto, (C1-C6)-alkylmercapto,
pyridino, carboxypyridino, carbamoylpyridino or a group of the general
formula (7-1) or (8-1)

where
R81 is hydrogen or (C1-C6)-alkyi, sulfo-(C1-C6)-alkyl
or phenyl which is unsubstituted or substituted by (C1-C4)-
alkyl, (C1-C4)-alkoxy, sulfo, halogen, carboxyl, acetamido,
ureido;
R91 and R100 independently have one of the meanings of R81 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;
W1 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-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 in claim 1,
R32 is hydrogen or sulfomethyl,
R33 is methyl, carboxyl or carboxyalkyl with C1- to C4-alkyl,
R34 is hydrogen or methyl,
R35 is hydrogen, cyano, carbamoyl, carboxyl or sulfomethyl,
R36 is methyl, ethyl or b-sulfoethyl,
R37 is methyl, carboxyl or carboxyalkyl with C1- to C4-alkyl,
38
R is acetamido, ureido or methyl,
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 and Z are each as defined in claim 1.
6. Reactive dye mixtures as per at least one of claims 1 to 5, wherein Z is vinyl,
b-chloroethyl or b-sulfatoethyl.
7. Reactive dye mixtures as per at least one of claims 1 to 6, wherein 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-(vinylsulfonyl)phenylamino, N-methyl-N-(2-(2-
suifatoethylsulfonyl)ethyl)amino or N-phenyl-N-(2-(2-sulfatoethylsulfonyl)ethyl)-
amino.
8. Reactive dye mixtures as per at least one of claims 1 to 7, comprising one or
more dyes of the formula (I) in a fraction from 1% to 99% by weight and one or
more dyes of the formula (II) in a fraction from 1 % to 99% by weight.
9. Reactive dye mixtures as per claim 5, comprising one or more dyes of the
formula (I) in a fraction from 1 % to 98% by weight and one or more dyes of the
formulae (II) and (G) independently each in a fraction from 1% to 98% by weight.
10. A process for preparing dye mixtures as per one or more of claims 1 to 9, which
comprises the individual dyes of the formulae (I), (II), (15), (16) and, if appropriate,
(G) either being mechanically mixed in solid form or in the form of aqueous
solutions in the mandated ratio.
11. A process for preparing dye mixtures as per one or more of claims 1, to 9 when D2
and D3 and, if appropriate, D4 and optionally D7 as per the general formulae (I)
and (II) and, if appropriate, (100) and (Gb) have the same meaning, which
comprises an amine of the general formula (17)
D2-NH2 (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
(18) and optionally of a monoazo dye as per the general formula (19)

where D1, D6, R\ R**, R°, R32, T, b, f, v and M are each as defined in claim 1.
12. A process for preparing dye mixtures as per at least one of claims to 9 when
the groups D1, D2 and D3 and, if appropriate, D4 and optionally D6, D7 as per the
general formulae (I) and (II) and, if appropriate, (1007 and (Gb) have the same
meaning, which comprises an amine of the general formula (20)
D1-NH2 (20),
where D1 is as defined in claim 1, being diazotized in a conventional manner and
coupled onto a mixture of in each case at least one coupling component (21) and
(18) and also optionally (22)

where R*, R**, R°, r32 t, b, f, v and M are each as defined in claim 1, in a first
stage and subsequently further coupled to form a mixture of the dyes of the
general formulae (I) and (II) with or without (Gb).
13. Aqueous liquid product comprising a dye mixture according to at least one of
claims 1 to 12 having a total dye content of 5 - 50% by weight.
14. A process for dyeing or printing hydroxyl-and/or earboxamido-containing
fiber material by reactive dye mixtures as claimed in one or more of claims 1 to
13.
15. Aqueous printing inks for textile printing by the inkjet process, comprising
dye mixtures as per claims 1 to 9 in amounts from 0.01% by weight to 40% by
weight based on the total weight of the inks.
16. A process for dyeing, conventionally printing and also inkjet printing textile
fiber materials, which comprises dyelng/prfnting by dye mixtures as claimed in
claims 1 to 9.
Reactive dye mixtures which comprise one or more dyes of the indicated general
formula (I)
and one or more dyes of the hereinbelow indicated and defined general formula (II)
where D1, D2, D3, R°, R*. R**,T, b, f, v and M are each as defined in claim 1, the dyes
of the general formulae (I) and (II) containing at least one fiber-reactive group of the
formula -SO2-Z or -Z2, their preparation and their use for dyeing and printing
hydroxyl- and/or carboxamido-containing fiber material.

Documents:

454-KOL-2004-(09-11-2012)-ASSIGNMENT.pdf

454-KOL-2004-(09-11-2012)-CORRESPONDENCE.pdf

454-KOL-2004-(09-11-2012)-FORM-16.pdf

454-KOL-2004-(09-11-2012)-PA.pdf

454-KOL-2004-CORRESPONDENCE-1.1.pdf

454-KOL-2004-CORRESPONDENCE-1.pdf

454-KOL-2004-CORRESPONDENCE.pdf

454-KOL-2004-FORM-27.pdf

454-kol-2004-granted-abstract.pdf

454-kol-2004-granted-claims.pdf

454-kol-2004-granted-correspondence.pdf

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

454-kol-2004-granted-examination report.pdf

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

454-kol-2004-granted-form 18.pdf

454-kol-2004-granted-form 3.pdf

454-kol-2004-granted-form 5.pdf

454-kol-2004-granted-gpa.pdf

454-kol-2004-granted-priority document.pdf

454-kol-2004-granted-reply to examination report.pdf

454-kol-2004-granted-specification.pdf

454-kol-2004-granted-translated copy of priority document.pdf


Patent Number 224165
Indian Patent Application Number 454/KOL/2004
PG Journal Number 40//2008
Publication Date 03-Oct-2008
Grant Date 01-Oct-2008
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 WERNER RUSS BAD-WEILBACH-STRASSE 9, 65439 FLORSHEIM-WICKER
3 STEFAN MEIER GEISENHEIMER STRASSE 88 60529 FRANKFURT
PCT International Classification Number C09B62/00
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10337636.4 2003-08-16 Germany