BLACK DYE MIXTURES OF FIBER-REACTIVE AZO DYES, METHODS FOR THEIR PREPARATION AND USE THEREOF FOR DYEING HYDROXY- AND/OR CARBOXAMIDO-CONTAINING FIBER MATERIAL

MELANGES DE COLORANTS NOIRS A BASE DE COLORANTS AZOIQUES REAGISSANT AVEC DES FIBRES, LEURS PROCEDES DE PREPARATION ET LEUR UTILISATION POUR LA TEINTURE D'UN MATERIAU FIBREUX CONTENANT UN HYDROXY ET/OU UN CARBOXAMIDO

English Abstract

The present invention discloses a dye mixture comprising a disazo dye
conforming to the formula (1), a monoazo dye conforming to the formula (2),
and monazo dye conforming to the formula (3) in which (1), (2) and (3) are
defined as given in claim 1, a method for its preparation and a process for
dyeing hydroxy- and/or carboxamido containing fiber material in which an
inventive dye mixture is applied to the material.

French Abstract

Cette invention se rapporte à un mélange de colorants comprenant un colorant disazoïque correspondant à la formule (1), un colorant monozoïque correspondant à la formule (2) et un colorant monozoïque correspondant à la formule (3), formules qui sont chacune définies dans la revendication 1, à son procédé de préparation et à une technique de teinture d'un matériau fibreux contenant un hydroxy et/ou un carboxamido, technique selon laquelle on utilise le mélange de colorants selon l'invention.

Claims

37
Claims:
1. A dye mixture, comprising a disazo dye conforming to the formula (1), a
monoazo dye conforming to the formula (2), and monazo dye conforming
to the formula (3)
<IMGS>

38
wherein
Y1 is in each instance, independently of one another, vinyl or is ethyl which
is
substituted in the .beta.-position by a substituent which can be eliminated by
the action of an alkali, forming the vinyl group, such as chlorine,
thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as
acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy;
Y2 has one of the meanings of Y1;
Y3 has one of the meanings of Y2;
M is hydrogen or an alkali metal, such as lithium, sodium and potassium;
X is fluorine or chlorine;
R1 is hydrogen methyl, methoxy or a group of the formula SO3M;
R2 has one of the meanings of R1;
Q is a group of the formula (a) or (b)
<IMG>
wherein
A is hydrogen, C1 to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl,
n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, which may be
substituted by hydroxy, sulfo or sulfato or is phenyl which may be
substituted by one or more halogens such as chloro, fluoro or bromo, by
acetamido- or by sulfo;
A1 is C1 to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl, n-butyl, i-
butyl,
sec-butyl, tert-butyl, pentyl or hexyl, which may be substituted by
hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or
more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo;
B has one of the meanings of A;
B' has one of the meanings of A';

39
D has one of the meanings of A';
or the group of the formula
(a) is a cyclic ringsystem such as morpholino, piperidino or piperazino;
(b) is a cyclic ringsystem such as N-methyl morpholinium or N-ethyl
morpholinium, N-ethyl piperidinium, or is a bicyclic ringsystem such as N-
1,4-diaminobicyclo (2,2,2) octyl, or is pyridinium which may be
substituted by carboxy, such as 3-carboxy-pyridinium or 4-carboxy-
pyridinium, or by carboxamido, such as 3-carboxamidopyridinium;
n is 0 if Q is a group of the formula (a) and n is 1 if Q is a group of
formula
(b) ;
W is a halogenide or the equivalent of a divalent anionic group such as
sulfate
or carbonate.
2. A dye mixture as claimed in claim 1 wherein the dye of formula (1) is
present in the mixture in an amount of from 50 to 95 % by weight; the dye
of the formula (2) is present in the mixture in an amount of from 1 to 30%
by weight; the dye of the formula (3) is present in the mixture in an
amount of from 1 to 20 % by weight.
3. A dye mixture as claimed in claim 1 comprising a monoazo dye of formula
(4) in a total amount of 0.5 to 6.0% by weight and a monoazo dye of
formula (5) in a total amount of 0.5 to 6.0% by weight, calculated on
100% by weight of the dye mixture.
<IMG>

40
<IMG>
wherein:
Y4, Y5 have one of the meanings of Y1;
M is as defined in claim 1.
4. A dye mixture according to claim 1-3 comprising a monoazo dye of
formula (6) in a total amount of 0.5.- 25% by weight based on the dye
mixture
<IMG>
wherein
Y6 has one of the meanings of Y1
M is as defined in claim 1.

41
5. A dye mixture according to claim 1-3 comprising a monoazo dye of
formula (7) in a total amount of 0.5.- 25% by weight based on the dye
mixture
<IMG>
wherein
Y7 has one of the meanings of Y1
M is as defined in claim 1.
6. A dye mixture according to claim 1-3 comprising a monoazo dye of
formula (8) in a total amount of 0.5.- 25% by weight based on the dye
mixture.
<IMG>
wherein
Z is a C1-C4 alkyl, such as methyl, ethyl, n-propyl, i-propyl, or is a

42
phenylgroup, which may be substituted by chlorine nitro or sulfo
Y8 has one of the meanings of Y1
M is as defined in claim 1.
7. A dye mixture according to claim 1-3 comprising a monoazo dye of
formula (9) in a total amount of 0.5.- 25 % by weight based on the dye
mixture
<IMG>
Wherein:
X1 has one of the meanings of X;
Q' is a group of the formula (a')
<IMG>
in which
A1 has one of the meanings of A or is an aryl or alkyl group that is
substituted by sulfo or a group of the formula SO2Y1;
B1 has one of the meanings of A or
(a') has one of the meanings of (a);
Y9 is vinyl or is ethyl which is substituted in the .beta.-position by a
substituent
which can be eliminated by the action of an alkali, forming the vinyl
group, such as chlorine, thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon

43
atoms, such as acetyloxy, phosphato, sulfobenzoyloxy and p-
toluylsulfonyloxy and
M is hydrogen or an alkali metal, such as lithium, sodium or potassium.
8. A dye mixture according to claim 1-3 comprising more than one of the
formulae (6), (7), (8) or (9) in up to a total of 25 % by weight based on the
dye mixture.
9. A process for the preparation of the dye mixture as claimed in one or more
of claims 1-8 comprising mechanically mixing the individual dyes of the
formulae (1) to (9) in the required proportions.
10. A process for the preparation of the dye mixture according to claim 1 by
diazotizing an aniline component of 4-(.beta.-sulfatoethylsulfonyl)aniline in
a
conventional manner in a strongly acid medium and then carrying out the
coupling reaction of the 1-amino-8-napthol-3,6-disulfonic acid with the
diazo component at a pH below 1.5 to form the compound (4) followed by
the second coupling reaction with the monoazo dye (4) products to form
the disazo dye conforming to the formula (1) which is carried out at a pH
between 3 and 6.5 and by addition of the aqueous solution of the sulfo-
napthylamine the coupling reaction to form the dye conforming to the
formula (2) which is carried out at a pH between 3 and 6.5 and subsequent
addition to the dye mixture of a dyestuff of the general formula (3) followed
by the isolation of the dyestuff mixture from the solution in the
conventional manner, for example by salting out with an electrolyte salt.
11. A process for dyeing hydroxy- and/or carboxamido -containing fiber
material, in which dyes are applied to the material and the dyes are fixed to
the material by means of heat or with the aid of an alkali or by means of
heat and with the aid of an alkali, which comprises dyes of the mixture as
claimed in claim 1.

Description

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DyStar Textilfarben GmbH & Co. Deutschland KG
Description
Black Dye Mixtures of Fiber-Reactive Azo Dyes, Methods for their Preparation
and Use Thereof for Dyeing Hydroxy- and/or Carboxamido-containing Fiber
Material
to The present invention relates to the field of fiber-reactive dyes.
Black-dyeing mixtures of fiber-reactive dyes are known from U.S. Patents Nos.
5,445,654 and 5,61 1,821 as well as from Korean Patent Application Publication
No. 94-2560. Deep black dye mixtures are known, for example, from Japanese
Patent Application Publication Sho-58-160 362 which are based on a navy-blue
disazo dye and an orange monoazo dye. However these dye mixtures have some
deficiencies.
With the present invention, deep black-dyeing dye mixtures of improved
2o properties have unexpectedly been found, comprising a disazo dye conforming
to
the general formula (1 ),
Y~ Y~
02S ~ / S02
I
N OH NH2 N
N ~. ~ N
O~ I / / OM
O~S~OM p SAO
(1 )
a monoazo dye conforming to the general formula (2),

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2
Y2
I
S02
\ I
N
~\
I /~NH2
O=S=O
(2)
and a dye of the general formula (3)
OsM X
N j 'N
wIV~N~Q (+)n V1% n
H
s (3)
wherein
Y' is in each instance, independently of one another, vinyl or is ethyl which
is
substituted in the [3-position by a substituent which can be eliminated by
1o the action of an alkali, forming the vinyl group, such as chlorine,
thiosulfato, sulfato, alkanoyloxy of 2 to 5 carbon atoms, such as
acetyloxy, phosphato, sulfobenzoyloxy and p-toluylsulfonyloxy, and is
preferably vinyl, f3-chloroethyl, f3-thiosulfatoethyl or f3-sulfatoethyl and
is in
particular preferably vinyl or (3-sulfatoethyl;
1s Y2 has one of the meanings of Y';
Y3 has one of the meanings of Y2;
M is hydrogen or an alkali metal, such as lithium, sodium and potassium;
X is fluorine or chlorine;

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3
R' is hydrogen methyl, methoxy or a group of the formula S03M, preferably
hydrogen or methoxy and in particular hydrogen;
RZ has one of the meanings of R''
Q is a group of the formula (a) or (b)
s
~+
BiNwA B,iN~A,
D
(a) (b)
wherein
A is hydrogen, C, to Cs alkyl such as methyl, ethyl, n-propyl , i-propyl,
1o n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably C, to
C4
alkyl groups, in particular methyl and ethyl, which may be substituted by
hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or
more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo
and is preferably 4-chlorophenyl and in particular 3-metanilic or 2,5-
15 dimetanilic acid;
A' is C~ to C6 alkyl such as methyl, ethyl, n-propyl , i-propyl,
n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl, preferably C~ to C4
alkyl groups, in particular methyl and ethyl, which may be substituted by
hydroxy, sulfo or sulfato or is phenyl which may be substituted by one or
2o more halogens such as chloro, fluoro or bromo, by acetamido- or by sulfo
and is preferably 4-chlorophenyl and in particular 3-metanilic or 2,5-
dimetanilic acid;
B has one of the meanings of A and is preferably hydrogen, methyl or ethyl;
B' has one of the meanings of A'
D has one of the meanings of A';
or the group of the formula
(a) is a cyclic ringsystem such as morpholino, piperidino or piperazino, in
particular morpholino, or prolino;

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4
(b) is a cyclic ringsystem such as N-methyl morpholinium or N-ethyl
morpholinium, N-ethyl piperidinium, or is a bicyclic ringsystem such as N-
1,4-diaminobicyclo (2,2,2) octyl, or is pyridinium which may be substituted
by carboxy, such as 3-carboxy-pyridinium or 4-carboxy-pyridinium, or by
carboxamido, such as 3-carboxamidopyridinium, and is in particular 3-
carboxy-pyridinium;
n is 0 if Q is a group of the formula (a) and n is 1 if Q is a group of
formula
(b) ;
W- is a halogenide or the equivalent of a divalent anionic group such as
sulfate
to or carbonate and is preferably chloride or fluoride;
Preference is given to dye mixtures comprising an amount of from 50 to 95% by
weight of the diazo dye of the general formula (1), from 1 to 30% by weight of
the monoazo dye of the general formula (2) and from 1 to 20 % by weight of the
dye of the general formula (3) based on the dye mixture.
Special preference is given to dye mixtures comprising an amount of from 70 to
90 % by weight of the disazo dye of the general formula ( 1 ), from 5 to 28 %
by
2o weight of the monoazo dye of the general formula (2) and from 2 to 12 % by
weight of the dye of the general formula (3) based on the dye mixture.
The dye mixtures according to the present invention may optionally also
comprise one or more monoazo dyes of the general formulae (4), (5), (6), (7),
2s (8) or (9) in 0.5 to 25 % by weight based on the dye mixture, preferably
they comprise one monoazo dye of the formulae (4), or (5), or (6), or (7), or
(8),
or (9) in 0.5 to 25% by weight based on the dye mixture.

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Y4
I
/ S02
OH NH2 N
N
O~ ~ / / OM
MO~S~ ~ SAO
(4)
Y5
/ S02
NH2 OH N
N
O~ ~ / / OM
O ~S~OM O S ~O
(5)
Y6 .
~S02
N~ N OH
H2N
O~ ~ / / OM
O ~S~OM O S~ O
(6)

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Y~
~S02
I\
NON OH
\ \
OM
/ /
'~V ~O
O (
Y$
/ S02
O I
z"NH OH N \
1 I
N
O~ I / / OM
O~S~OM p SAO
($)
Ys
1
~ S02
N~N /
\I
Q' N NH OH N
I I
~ N
O~ I / / OM
O~S~OM O S\O
(9)
wherein
Z is a C,-C4-alkyl, such as methyl, ethyl, n-propyl, i-propyl, or is a
1o phenylgroup, which may be substituted by chlorine nitro or sulfo,
preferably methyl and ethyl;
Y4, Y5, Y6, Y' Y$ and Y9 have one of the meanings of Y'.

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7
X, has one of the meanings of X
Q' is a group of the formula (a')
N~
A/ B~
(a')
wherein
A, has one of the meanings of A or is C, to C4 alkoxyalkyl such as
methoxymethyl, methoxyethyl, ethoxyethyl, which may be substituted by
a group of the formula S02Y', or is phenyl which is substituted by sulfo or
a group of the formula S02Y'
B, has one of the meanings of A, or
(a') has one of the meanings of (al.
The dyes according to the general formula (1) are known from the U.S. Patent
No. 2,657,205, from Japanese Patent Application Publication Sho-58-160 362
and also from U.S. Pat. No. 4,257,770 and the references cited therein.
1s Monoazo dyes of the formula (2) are described in the DE-A 19 1 1 427. Dyes
of
the formula (3) wherein Q is a group of formula (a) are described US 5456727
EP -A141367, 395951, 486176, 623655, 630946, 632107, 647683. Dyes of
the formula (3) wherein Q is a group of formula (b) can be obtained in a
conventional manner, for instance by synthesis by means of customary
2o diazotization and coupling reactions in a manner familiar to those skilled
in the art
using appropriate substituted phenylamine derivatives conforming to the
general
formula (3-2)
Y
(3-2)
2s

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8
wherein Y is a alkali eliminable group and R' and R2 are as defined above, and
coupling components, such as diaminophenylsulfonic acid in the necessary
proportions to give the diazo component of the general formula (3-3).
03H
1
~ H
" 2
2 \ N~N \
' / NH2
02Y (3-3)
wherein R', RZ and Y are as defined above.
Reacting this intermediate at pH 9,5-1,5 with cyanuric halogenide gives the
azo
dye conforming to the formula (3-4):
03H
1
2 \ N\ N \ . .
H2
' / HN\ /N\\ /X
Y02 ~ ~S
N\/N
X (3_4)
to wherein X is fluorine or chlorine, and by reaction with a compound of the
general
formula Q' at pH 2-9 eventually under heating wherein Q' is a group of the
formula:
I BiD~A
B~N~A
(a) ~ or
in which
(b)'
A, B, D and n are as defined above to give a claimed dyestuff of the formula
(3):

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9
03H
NH2
2 N~ N \ . ~+)n
' / HN\ /N\ /Q
Y02 ~' ~~S
N / N Wn
X (3)
with X, Y, W, n, Q', R' and R2 as defined above
s The resulting dyestuff can be isolated from the solution in the conventional
manner, for example by salting out with an electrolyte salt, such as sodium
chloride or potassium chloride, or by spray-drying.
Dyes of the general formula (4) are described in EP-A 832 939 and dyes of the
general formula (5) are described in EP-B 94 055.
to
The dyes of the formulae (6) through (9) are well known in the literature and
can
be synthesised by the standard methology. They are generally added as shading
components.
15 The groups "sulfo", "thiosulfato", "phosphate," "carboxy" and "sulfate"
include both the acid form and the salt form of these groups. Accordingly,
sulfo
groups are groups of the formula -S03M , thiosulfato groups are groups of the
formula -S-S03M , phosphate groups are groups of the formula -OP03M2,
carboxy groups are groups of the formula -COOM and sulfate groups are groups
20 of the formula -OS03M , in which M is defined as above. Carboxyamido groups
are groups of the formula -CONH2.
The dyes of the general formulae (1 ), (2), (3), (4), (5), (6), (7), (8), (9)
in
particular if those corresponding to the same general formula, have the same
2s chromophore, can have, within the meaning of Y' to Y9, structurally
different
fiber-reactive groups -SO2-Y' to -SOZ Y9. In particular, the dye mixture can

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contain dyes of the same chromophore conforming to the formula (1 ) and dyes
of the same chromophore conforming to formula (2) and dyes of the same
chromophore conforming to formula (3) and optionally likewise of the general
formula (4) through (9) in which the fiber-reactive groups -SOZ Y' to -S02 Y9
are
5 partly vinylsulfonyl groups and partly groups in which Y' to Y9 is a ~i-
ethyl
substituted group as defined above, such as f3-chloroethylsulfonyl, f3-
thiosulfatoethylsulfonyl or, preferably, f3-sulfatoethylsulfonyl groups.
If the dye mixtures contain the respective dye components in the form of a
1o vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to
the
respective dye with Y being a (3-ethyl substituted groups as defined above,
such
as a 13-chloro- or f3-thiosulfato- or f3-sulfatoethyl-sulfonyl dye, will be up
to about
30 mol-%, based on the respective dye chromophore. Preference is here given to
the dye mixtures in which the proportion of vinylsulfonyl dye to said (3-ethyl
1s substituted dye, such as f3-sulfatoethylsulfonyl dye is in terms of the
molar ratio
between 5 : 95 and 30 : 70.
The dye mixtures of the invention can be present as a preparation in solid or
liquid (dissolved) form. In solid form they generally contain the electrolyte
salts
customary in the case of water-soluble and in particular fiber-reactive dyes,
such
as sodium chloride, potassium chloride and sodium sulfate, and also the
assistants customary in commercial dyes, such as buffer substances capable of
establishing a pH in aqueous solution between 3 and 7, such as sodium acetate,
sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate
and disodium hydrogenphosphate, small amounts of siccatives or, if they are
present in liquid, aqueous. solution (including the presence of thickeners of
the
type customary in print pastes), substances which ensure the permanence of
these preparations, for example mold preventatives.

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If the dye mixtures take the form of dye powders, they contain, as a rule, 10
to
80 % by weight, based on the dye powder or preparation, of a strength-
standardizing colorless diluent electrolyte salt, such as those mentioned
above.
These dye powders may in addition contain the abovementioned buffer
s substances in a total amount of up to 5 %, based on the dye powder. If the
dye
mixtures of the invention are present in aqueous solution, the total dye
content
of these aqueous solutioris is up to about 50 % by weight, the electrolyte
salt
content of these aqueous solutions preferably being below 10 % by weight,
based on the aqueous solutions. Liquid preparations can in general contain the
to abovementioned buffer substances in an amount of up to 5 % by weight,
preferably up to 2 % by weight.
The dye mixtures of the invention can be obtained in a conventional manner,
for
instance by mechanically mixing the individual dyes in the required
proportions or
15 by synthesis by means of the customary diazotization and coupling reactions
using appropriate mixtures of the diazo and coupling components in a manner
familiar to those skilled in the art and the necessary proportions. One option
is
for example to prepare aqueous suspensions of the coupling components 1-
amino-8-naphthol-3,6-disulfonic acid, a sulfonaphtylamine, and, as diazo
2o components, aniline compounds of the formula (10).
Y~
I
SO2
NH2 (10)
25 Thus the dye mixture can be produced by diazotizing 4-(f3-
sulfatoethylsulfonyl)aniline in a conventional manner in a strongly acid
medium
and then carrying out the coupling reaction of the 1-amino-8-napthol-3,6-
disulfonic acid with the diazo component at a pH below 1.5 to form the

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12
compound (4). The second coupling reaction with the monoazo dyes (4) products
to form the disazo dyes conforming to the formula (1 ) is carried out at a pH
between 3 and 6.5. Then, by addition of the aqueous solution of the sulfo-
napthylamine the coupling reaction to form the dye conforming to the formula
(2)
is carried out at a pH between 3 and 6.5. To the dye mixture thus obtained is
added a dyestuff of the general formula (3). The resulting dyestuff mixture
can
be isolated from the solution in the conventional manner, for example by
salting
out with an electrolyte salt, such as sodium chloride or potassium chloride,
or by
spray-drying.
Dye mixtures which contain the respective dye components in form of the
vinylsulfonyl dye can be prepared by the above mentioned method using
appropriate vinylsulfonyl starting anilines, or alternately by reacting the
dye
mixture in which Y' to Y9 is a f3-chloroethyl, f3-thiosulfatoethyl, or (3-
sulfatoethyl
radical with an appropriate amount of alkali by generally known methods. If
the
dye mixtures contain the respective dye components in the form of a
vinylsulfonyl dye within the proportion as defined above, the respective dye
with
Y' to Y9 being a (3-ethyl substituted group is reacted with the required
amount of
alkali to convert said f3-substituted ethylsulfonyl groups into vinylsulfonyl
groups
2o in the required proportion.
The dye mixtures of the instant invention are well suitable for dyeing (which
includes printing) hydroxy- and/or carboxamido-containing fiber materials by
the
application and fixing methods numerously described in the art for fiber-
reactive
dyes, in deep black shades with good color build-up and good wash-off in
respect of unfixed dye portions. Moreover, the dyeings obtained surprisingly
show very little or no staining on polyamide fibers.
The present invention therefore also provides for use of the inventive dye
3o mixtures for dyeing (including printing) hydroxy- and/or carboxamido-
containing
fiber materials and processes for dyeing such materials using a dye mixture
according to the invention by applying the dye mixture to the substrate in

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13
dissolved form and fixing the dyes on the fiber by the action of an alkali or
by
heating or both.
Hydroxy-containing materials are natural or synthetic hydroxy-containing
materials, for example cellulose fiber materials, including in the form of
paper, or
their regenerated products and polyvinyl alcohols. Cellulose fiber materials
are
preferably cotton but also other natural vegetable fibers, such as linen,
hemp,
jute and ramie fibers; regenerated cellulose fibers are for example staple
viscose
and filament viscose.
to
Carboxamido-containing materials are for example synthetic and natural
polyamides and polyurethanes, in particular in the form of fibers, for example
wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11, and
nylon-4.
is
Application of the inventive dye mixtures is by generally known processes for
dyeing and printing fiber materials by the known application techniques for
fiber-
reactive dyes. Since the dyes of the dye mixtures according to the invention
are
highly compatible with one another, the dye mixtures of the invention are also
2o advantageously useful in exhaust dyeing processes. Applied in this way for
example to cellulose fibers from a long liquor ratio at temperatures between
40
and 105°C, optionally at temperatures up to 130°C, under
superatmospheric
pressure, and optionally in the presence of customary dyeing assistants with
the
use of acid-binding agents and optionally neutral salts, such as sodium
chloride
2s or sodium sulfate, they produce dyeings in very good color yields with
excellent
color build-up and consistent shade. One possible procedure is to introduce
the
material into the warm bath, gradually heat the bath to the desired dyeing
temperature, and complete the dyeing process at that temperature. The neutral
salts which speed up the exhaustion of the dyes can also if desired not be
added
3o to the bath until the actual dyeing temperature has been reached.

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Similarly, the conventional printing processes for cellulose fibers, which can
either be carried out in single-phase, for example by printing with a print
paste
containing sodium bicarbonate or some other acid-binding agent and the
colorant, and subsequent steaming at from 100 to 103°C, or in two
phases, for
example by printing with a neutral or weakly acid print paste containing the
colorant and subsequent fixation either by passing the printed material
through a
hot electrolyte-containing alkaline bath or by overpadding with an alkaline
electrolyte-containing padding liquour and subsequent batching of this treated
material or subsequent steaming or subsequent treatment with dry heat, produce
1o strong prints with well defined contours and a clear white ground. Changing
fixing conditions has only little effect on the outcome of the prints. Not
only in
dyeing but also in printing the degrees of fixation obtained with dye mixtures
of
the invention are very high. The hot air used in dry heat fixing by the
customary
thermofix processes has a temperature of from 120 to 200°C. In addition
to the
customary steam at from 101 to 103°C, it is also possible to use
superheated
steam and high pressure steam at up to 160°C.
Acid-binding agents responsible for fixing the dyes to cellulose fibers are
for
example water-soluble basic salts of alkali metals and of alkaline earth
metals of
2~ inorganic or organic acids, and compounds which release alkali when hot. Of
particular suitability 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. These acid-binding agents are for
example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium
bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate
and disodium hydrogenphosphate.
Treating the dyes of the dye mixtures according to the invention with the acid-
binding agents with or without heating bonds the dyes chemically to the
3o cellulose fiber; especially the dyeings on cellulose, after they have been
given the
usual aftertreatment of rinsing to remove unfixed dye portions, show excellent

CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
wet fastness properties, in particular since the unfixed dye portions are
readily
washed off because of their good cold water solubility.
The dyeings of polyurethane and polyamide fibers are customarily carried out
5 from an acid medium. The dyebath.may contain for example acetic acid and/or
ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate
to bring it to the desired pH. To obtain a dyeing of acceptable levelness it
is
advisable to add customary leveling assistants, for example based on a
reaction
product of cyanuric chloride with three times the molar amount of an
to aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a
reaction product of for example stearylamine with ethylene oxide. In general
the
material to be dyed is introduced into the bath at a temperature of about
40°C
and agitated therein for some time, the dyebath is then adjusted to the
desired
weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is
carried
15 out at temperature between 60 and 98°C. However, the dyeings can
also be
carried out at the boil or at temperatures up to 120°C (under
superatmospheric
pressure) .
The examples which follow illustrate the invention. Parts and percentages are
by
2o weight, unless otherwise stated. The parts by weight bear the same relation
to
parts by volume as the kilogram to the Titer.

CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
16
Example 1
200 parts of an electrolyte-containing dye powder which contains the navy-
dyeing disazo dye of the formula (A)
Na03SOCH2CH202S ~ ~ ~ S02CH~CH20S03Na
OH NH2
N=N / ~ N=N
Na03S ~ ~ S03Na (
in a proportion of 50% are mechanically mixed with 75 parts of an electrolyte-
containing dye powder which contains the orange-dyeing monoazo of the
formula (B) in a 70% proportion
/ S02CH2CH20S03Na
=N
NH2
~J
to ~ c$>
and a 25 parts of an electrolyte-containing dye powder which contains the
yellow-dyeing azo dye of the formula (C) in a 60% proportion
Na03S
Na
CI
SOZ
Na03S0
1s (C )

CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
17
The resulting dye mixture according to the invention, when employed according
to the application and fixing methods customary in the art for fiber-reactive
dyes,
produces for example on cellulose fiber materials dyeings and prints in deep
black
s shades.
Example 2
A dye mixture according to the invention is prepared by diazotizing a
suspension
of 281 parts of 4-(f3-sulfatoethylsulfonyl)aniline in 650 parts of ice-water
and
l0 180 parts of 30 % aqueous hydrochloric acid with 173 parts of 40 % strength
aqueous sodium nitrite solution. 120 parts of 1-amino-8-napthol-3,6-disulfonic
acid are added and the first coupling is carried out at a pH between 1 and 1.3
and at a temperature below 20°C (the pH is maintained with about 50
parts of
sodium bicarbonate). 72 parts 1-Aminonaphtaline-4-sulfonic acid are added to
is the mixture and the pH is raised to 6 with sodium carbonate at a
temperature
below 30°C.
To the resulting solution containing the dyes of formulae (A) and (D) are
added
50 parts of a yellow dye of the formula (C). The resulting dye mixture
comprises
2o the dyes of the formulae (A), (D) and (C) in a the ratio of about 70 % : 22
% : 8
%.
/ S02CH2CH20S03Na
NH2
N=N
/ / .
~\
S03Na
(D)
This dye solution can be adjusted to pH 4.5 by adding 5. parts of a sodium
25 phosphate buffer. By further diluting with water or by evaporating the
solution,
this liquid dye mixture can then be standardized to the desired strength for a

CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
18
liquid preparation. The dye mixture affords deep black shades on cellulosic
materials.
Examples 3 to 1 12
The table examples which follow describe further dye mixtures according to the
invention of the dyes conforming to the formulae (1)-(9) as the sodium salts
of
the f3-sulfatoethyl, and the mixing ratios of the dyes by percent by weight.
When
employed according to the application and fixing methods customary in the art
1o for fiber-reactive dyes, these dye mixtures produce, for example, on
cellulose
fiber materials, deep black dyeings.

CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
19
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
24
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CA 02417232 2003-O1-24
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
26
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
27
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
28
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
29
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
31
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
32
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
33
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CA 02417232 2003-O1-24
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34
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CA 02417232 2003-O1-24
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CA 02417232 2003-O1-24
WO 02/08339 PCT/EPO1/08462
36
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Z
m
p
N
Z
V
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U
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Z
U
N
O
N
z
z ~ z
z z
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0
0 o p o 0
o D D D D
a~
a
x o 0 0 0 0 0
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