DESCRIPTION
The invention relates to the technical field of fiber-reactive azo dye stuffs.
U.S. Patent No. 4,725,675 and European Patent Application Publication No. 0
094 055 disclose monoazo dyestuffs which contain a fiber-reactive redicai from
the vinyl-sutfone series and, as a further fiber-reactive radical, an amlno-
substituted chlorotriazinylamino radical. However, the dyestuffs described therein
have certain deficiencies with regard to their use, such as, for example, too great
a dependency of the color yield on varying dyeing parameters in the dyeing
process, an inadequate solubility in an aqueous dyebath at higher dyestuff
concentrations in the presence of electrolyte salts or an inadequate color build-up
on cotton and, in particular, viscose (a good color build-up results from the ability
of a dyestuff to produce the dyeing of correspondingly stronger color when
increased dyestuff concentrations are used in the dyebath). The consequence of
these deficiencies can be a poor reproducibility of the dyeings obtainable.
However, it is particularly important to obtain dyeings with a good color yield, i.e.
dyeings of which the depth of color in relation to the amount of dyestuff employed
is as high as possible, for example in comparison with other dyestuffs, because
of the color property of the dyestuff Itself (high extinction value) and because of
the dyeing properties of this dyestuff, such as good exhaustion capacity and high
fixing value. If mixtures of dyestuffs of a particular color yield are employed, the
rule is that the color yield of this mixture results from
the average of the sum of the color yields of the indivi-
dual dyestuffs. The color yield of a mixture of, for ex-
ample, two dyestuffs will then be lower than the color
yield of that individual dyestuff having the higher color
yield property in respect to the other individual dye-
stuff.
With the present invention, it has now been found that
the color yields of the dyestuff mixtures according to
the invention described below are surprisingly
siRnificantlv higher than the average of the sum of the color yields
given by the individual dyestuffs of the dyestuff
mixture. This synergistic effect furthermore manifests
itself in improved build-up properties of the mixture
according to the invention compared with the individual
dye'stu?fs of the mixture.
The invention relates to dyestuff mixtures which comprise
one or more, such as two or three, azo dyestuffs corres-
ponding to the formula (1) and one or more, such as two
or three, azo dyestuffs corresponding to the formula (2).

In these formulae;
M is hydrogen or an alkali metal, such as lithium,
sodium or potassium, or the stoichiometric equiva-
lent of an alkaline earth metal, such as of calcium,
preferably hydrogen, sodium, potassium or lithium;
D1 is the radical of a benzene or naphthalene nucleus,
the azo group preferably being bonded in the 2-
position in the case of the naphthalene nucleus;
D2 has one of the meanings of D1;
R1 is hydrogen or alkyl having 1 to 4 carbon atoms,
such as ethyl and, in particular, methyl, or alkoxy
having 1 to 4 carbon atoms, such as ethoxy and, in
particular, methoxy, if D1 or D2 is the radical of a
benzene nucleus, or is hydrogen or sulfo if D1 or D2
is the radical of a naphthalene nucleus;
R2 is hydrogen, alkyl having 1 to 4 carbon atoms, such
as ethyl and, in particular, methyl, alkoxy having
1 to 4 carbon atoms, such as ethoxy and, in particu-
lar, methoxy, or sulfo, if D1 or D2 is the radical of
a benzene nucleus, or is hydrogen or sulfo, if D1 or
D2 is the radical of a naphthalene nucleus;
R3 is hydrogen, alkyl having 1 to 4 carbon atoms, such
as ethyl and, in particular, methyl, or alkoxy
having 1 to 4 carbon atoms, such as ethoxy and, in
particular, methoxy;
R* is hydrogen or alkyl having 1 to 4 carbon atoms,
such as ethyl and, in particular, methyl, or alkoxy
having 1 to 4 carbon atoms, such as ethoxy and, in
particular, methoxy;
R5 is hydrogen, alkyl having 1 to 4 carbon atoms, such
as ethyl and, in particular, methyl, alkoxy having
1 to 4 carbon atoms, such as ethoxy and, in particu-
lar, methoxy, or sulfo;
R6 is hydrogen, alkyl having 1 to 4 carbon atoms, such
as ethyl and, in particular, methyl, or alkoxy
having 1 to 4 carbon atoms, such as ethoxy and, in
particular, methoxy;
R7 is hydrogen, alkyl having 1 to 4 carbon atoms, such
as ethyl and, in particular, methyl, alkoxy having
1 to 4 carbon atoms, such as ethoxy and, in particu-
lar, methoxy, or sulfo;
R is hydrogen or alkyl having 1 to 4 carbon atoms,
such as ethyl and, in particular., methyl, preferably
hydrogen;
Y1 is vinyl, /S-sulfatoethyl, /S-thiosulfatoethyl or /S-
chloroethyl, preferably vinyl or /J-sulfa toe thy 1;
Y2 has one of the meanings of Y1;
Y3 has one of the meanings of Y1;
X1 is fluorine, bromine or chlorine, preferably fluor-
ine, and in particular chlorine;
X2 has one of the meanings of X1; and
the groups -SOj-Y1, -S02-Y3 and -S02-Y3 are in the meta- or
para-position relative to the azo group on the
benzene nucleus of D1 and D2 or are bonded in the
meta- or para-position relative to the amino group.
The individual formula members in the formulae (1) and
(2) and likewise in the formulae mentioned below can have
meanings which are the same as one another or different
from one another in the context of their definition.
In general, the azo dyestuff or dyestuffs of the formula
(1) and the azo dyestuff or dyestuffs of the formula (2}
are contained in the mixture in a mixing ratio of 90:10%
by weight to 10:90% by weight, preferably in the ratio of
70:3 0% by weight to 30:70% by weight. They are particu-
larly preferably contained in the mixture in a ratio of
55:45 to 45:55% bv weighty.
Radicals of the formulae Y1-OaS-D1-(R1, R2) - and
Y3-02S-D2(R4,R5) - of the azo dyestuffs of the formulae (1)
and (2) are, for example, 3- (/S-sulf atoethylsulfonyl) -
phenyl, 4- (/3-sulf atoethylsulfonyl) -phenyl, 2-methyl-5-(/?-
sulfatoethylsulfonyl) -phenyl, 2-methoxy-5- (/S-sulfato-
ethylsulfonyl)-phenyl, 4-methyl-3-(/3-sulfatoethylsulfon-
yl) -phenyl, 2, 5-dimethyl-4- (/3-sulf atoethylsulfonyl) -
phenyl, 2, 6-dimethyl-4- (/3-sulf atoethylsulfonyl) -phenyl,
2-methoxy-4- (/S-sulfatoethylsulfonyl) -phenyl, 4-methoxy-5-
(0-sulfatoethylsulfonyl) -phenyl, 2-methoxy-5-methyl-4- (/S-
sulfatoethylsulfonyl) -phenyl, 2, 4-dimethoxy-5- (/8-sulfato-
ethyleulfonyl) -phenyl, 2, 5-dimethoxy-4- (0- sulfa toe thyl-
sulfonyl) -phenyl, 6- (/5-sulfatoethylsulfonyl) -1-sulfo-
naphth-2-yl and 8- (/S-sulfatoethylsulfonyl) -6-sulfonaphth-
2-yl, and of these in particular 4-(/8-sulfatoethylsulfon-
yl)-phenyl, and derivatives of these radicals in which
the 0-sulfatoethylsulfonyl group is replaced by the
vinylsulfonyl or /S-thiosulfatoethylsulfonyl or /S-chloro-
ethylsulfonyl group.
Benzene radicals which contain the substituents R3 and
-SOj-Y2 in the formula (1) are, for example, 3-(/S-
sulfatoethylsulfonyl)-phenyl, 2-methoxy-5- (/S-sulfato-
ethylsulfonyl)-phenyl, 2, 5-dimethoxy-4- (/S-sulfatoethyl-
sulfonyl) -phenyl, 2-methoxy-4- (/S-sulfatoethylsulfonyl) -
phenyl, 4-methoxy-5- (/S-sulfatoethylsulfonyl) -phenyl, 2,4-
dimethoxy-5- (/3-sulfatoethylsulfonyl) -phenyl, 2-methcxy-5-
methyl-4- (/S-sulfatoethylsulfonyl) -phenyl, 2-methyl-5- (/S-
sulfatoethylsulfonyl) -phenyl, 2, 5-dimethyl-4- (/S-sulfato-
ethylsulfonyl) -phenyl, 2,6-dimethyl-4- (/3-sulfatoethyl-
sulfonyl) -phenyl, 4-methyl-3- (/S-sulfatoethylsulfonyl) -
phenyl and, in particular, 4-(/S-sulfatoethylsulfonyl)-
phenyl, and the derivatives of these radicals in which
the /S-sulfatoethylsulfonyl group is replaced by the
vinylsulfonyl or /S-thiosulfatoethylsulfonyl or the §-
chloroethylsulfonyl group.
Benzene radicals which contain a radical R*, R7 and a
sulfo group -S03M as substituents in the formula (2) are,
for example, 2-methoxy-5-sulfo-phenyl, 2, 5-dimethoxy-4-
sulfo-phenyl, 2-methoxy-4-sulfo-phenyl, 4-methoxy-5-
sulfo-phenyl, 2,4-dimethoxy-5-sulfo-phenyl, 2-methoxy-5-
methyl-4-sulfo-phenyl, 2-methyl-5-sulfo-phenyl, 2,5-
dimethyl-4-sulfo-phenyl, 2,6-dimethyl-4-sulfo-phenyl, 4-
methyl-3-sulfo-phenyl and, in particular, 4-sulfo-phenyl
and 3-sulfo-phenyl.
Preferably, in the formulae (1) and (2) , the radicals Da
and D2 are benzene nuclei, and in the case where D1 and D2
are benzene nuclei, Rl, R2, R4 and R5 are preferably each
hydrogen, or R1 and R4 are each preferably hydrogen and R2
and R5 are each hydrogen or sulfo if D1 and D2 are
naphthalene nuclei. Furthermore, R3, Rs and R7 as well as
R are each preferably hydrogen.
Above and below, a sulfo group is a group of the formula
-SOjM, a carboxy group is a group of the formula -COOK,
a sulfato group is a group of the formula -OS03M and a
thiosulfato group is a group of the formula -S-S03M, in
each case where M has the abovementioned meaning.
The dyestuff mixtures according to the invention can be
in the form of a preparation in solid or in liquid
(dissolved) form. In the solid form, they in general
comprise the electrolyte salts customary with water-
soluble and, in particular, fiber-reactive dyestuffs,
such as sodium chloride, potassium chloride and sodium
sulfate, and they can furthermore comprise the auxili-
aries customary in commercial dyestuffs, such as buffer
substances which are capable of establishing a pH in
aqueous solution of between 3 and 7, such as sodium
acetate, sodium borate, sodium bicarbonate, sodium
dihydrogen phosphate and disodium hydrogen phosphate,
small amounts of siccatives or, if they are present in
liquid, aqueous solution (including the content of
thickeners such as are customary in printing pastes),
substances which guarantee the storage stability of these
preparations, such as, for example, mold-preventing
agents.
The dyestuff mixtures according to the invention are in
general in the form of dyestuff powders having a content
of 10 to 80% by weight, based on the dyestuff powder or
the preparation, of an electrolyte salt, which is also
called a standardizing agent. This dyestuff powder can
furthermore comprise the buffer substances mentioned in
a total amount of up to 5% by weight, based on the
dyestuff powder. If the dyestuff mixtures according to the invention are present in
aqueous solution, the total dyestuff content in these aqueous solutions is up to
about 50% by weight, such as, for example, between 5 and 50% by weight, the
electrolyte salt content in these aqueous solutions preferably being below 10%
by weight, based on the aqueous solution; the aqueous solutions (liquid
preparations) can as a rule comprise the buffer substances mentioned in an
amount of up to 5% by weight, preferably up to 2% by weight.
The dyestuff mixtures according to the invention can be prepared in the
customary manner, for example by mechanical mixing of the Individual dyestuffs
known from the abovementioned European Patent Application Publications in the
required amounts. They may also be prepared by synthesis by means of the
customary diazotization and coupling reactions and reactions with the
halotriazlne component using corresponding mixtures of such components, in a
manner with which the expert is familiar and with the amounts necessary for this
and which form the subject matter of parent application 1530/cal/95. Thus, for
example,a procedure can be followed in which one or more, such as two or
three, azo compounds of the formula (3A) and one or more, such as two or three,
azo compounds of the formula (3B)

in which M, D1, R1, R2, Ya, D2, R*, R5, Y3, X1 and X2 have
the abovementioned meanings, are reacted in mixture
with one or more, such as two or three, amino compounds
of the formula (4A) and one or more, such as two or
three, amino compounds of the formula (4B)

in which R, R3, Y2, R$, R7 and M have the abovementioned
meanings, in a procedure known per se, such as, for
example, at a temperature between 10 and 60°C, preferably
between 20 and 30°C, and at a pH of between 2 and 8,
preferably between 4 and 5, or in which one or more, such
as two or three, azo compounds of the formula (5)

in which M has the abovementioned meaning, Y has one of
the meanings of Y1 or Y3, R10 has one of the meanings of R1
or R4, R11 has one of the meanings of R2 or R5 and D has
one of the meanings of D or D", are reacted in mixture
with one or more, such as two or three, compounds of the
formula (6A) and one or more, such as two or three, com-
pounds of the formula (6B)

in which X1, X2, R, Y2, R3, Rs, R7 and M have the above-
mentioned meanings, in a procedure known per se, for
example at a temperature between 20 and 60°C, preferably
between 40 and 50 °C, and at a pH of between 3 and 7,
preferably between 4 and 5, or in which one or more, such
as two or three, compounds of the formula (7A)

in which M, X1, R, R3 and Y2 have the abovementioned
meanings, and one or more, such as two or three, com-
pounds of the formula (7B)

in which M, X2, R, Rs and R7 have the abovementioned
meanings, are coupled in mixture with one or more, such
as two or three, diazotized amino compounds of the
formula (8)

in which R10, Ru, Y and D have the abovementioned mean-
ings, in a procedure known per se, such as, for example,
at a temperature between 0 and 3 0°C, preferably between
10 and 20°C, and at a pH of between 3 and 7.5, preferably
between 4.5 and 6.5.
Starting compounds of the formula (8) are, for example,
3- (/3-sulfatoethylsulfonyl) -aniline, 4- (/3-sulfatoethyl-
sulfonyl) -aniline, 2-methyl-5- (/3-sulfatoethylsulfonyl) -
aniline, 2-methoxy-5-(/3-sulfatoethylsulfonyl)-aniline, 4-
methyl-3- (/8-sulf atoethylsulf onyl) -aniline, 2, 5-dimethyl-
4- (/3-sulfatoethylsulfonyl) -aniline, 2. 6-dimethyl-4- (/3-
sulfatoethylsulfonyl) -aniline, 2-methoxy-4- (/3-sulfato-
ethylsulfonyl) -aniline, 4-methoxy-5- (/S-sulfatoethylsulf-
onyl) -aniline, 2-methoxy-5-methyl-4- (/3-sulfatoethylsulf-
onyl) -aniline, 2, 4-dimethoxy-5-(/3-sulfatoethylsulfonyl) -
aniline, 2, 5-dimethoxy-4- (/S-sulfatoethylsulfonyl) -
aniline, 6- (/3-sulfatoethylsulfonyl) -l-sulfo-2-amino-
naphthalene and 8-(0-sulfatoethylsulfonyl)-6-sulfo-2-
amino-naphthalene, and of these in particular 4-(/3-
sulfatoethylsulfonyl)-aniline, and derivatives of these
compounds in which the /S - sulfa toe thy lsulf onyl group is
replaced by the vinylsulfonyl or /S-thiosulf atoethylsulf -
onyl or j3-chloroethylsulfonyl group.
The starting compounds of the formulae (3A) and (3B) can
be prepared by a known procedure by reacting an amino
compound of the formula (8) with a 1-(dihalogeno-s-
triazinyl)-amino-3,6-disulfo-8-naphthol compound, or
reacting an azo compound of the formula (5) with a
trihalo-s-triazine.
Starting compounds of the formulae (6A) and (6B) can be
prepared by a procedure known per se by reacting a
trihalo-s-triazine with an amino compound of the formula
(9) or (10)

in which R, R3, Y2, R6, R7 and M have the abovementioned
meanings.
Trihalo-s-triazine compounds are, in particular,
trichloro-s-triazine (cyanuric chloride) and trifluoro-s-
triazine (cyanuric fluoride).
Amino compounds of the formula (9) are, for example, 3-
(0-sulf atoethylsulf onyl) -aniline, 2-methoxy-5- (/S-sulfato-
ethylsulfonyl) -aniline, 2, 5-dimethoxy-4- (/3-sulfatoethyl-
sulfonyl) -aniline, 2-methoxy-4- (/S-sulf atoethylsulf onyl) -
aniline, 4-methoxy-5-(0-sulfatoethylsulfonyl)-aniline,
2, 4-dimethoxy-5- (/S-sulfatoethylsulfonyl) -aniline, 2-
methoxy-5-methyl-4-(0-sulfatoethylsulfonyl)-aniline, 2-
methyl-5- (/S-sulf atoethylsulf onyl) -aniline, 2, 5-dimethyl-
4- (j8-sulfatoethylsulfonyl) -aniline, 2, 6-dimethyl-4- (/S-
sulfatoethylsulfonyl) -aniline, 4-methyl-3- (/5-sulfato-
ethylsulfonyl) -aniline and, in particular, 4- (/S-sulfato-
ethylsulfonyl)-aniline and the derivatives of these
compounds in which the /5-sulfatoethylsulfonyl group is
replaced by the vinylsulfonyl or /9-thiosulfatoethylsulf -
onyl or the /8-chloroethylsulfonyl group.
Amino compounds of the formula (10) are, for example, 2-
methoxy-5-sulfo-aniline, 2, 5-dimethoxy-4-sulfo-aniline,
2-methoxy-4-sulfo-aniline, 4-methoxy-5-sulfo-aniline,
2,4-dimethoxy-5-sulfo-aniline, 2-methoxy-5-methyl-4-
sulfo-aniline, 2-methyl-5-sulfo-aniline, 2,5-dimethyl-4-
sulfo-aniline, 2,6-dimethyl-4-sulfo-aniline, 4-methyl-3-
sulfo-aniline and, in particular, 4-sulfo-aniline and 3-
sulfo-aniline.
The dyestuff mixtures according to the invention prepared
by a chemical route can be separated out from their
synthesis solution by generally known methods, thus, for
example, either by precipitation from the reaction medium
by means of electrolytes, such as, for example, sodium
chloride or potassium chloride, or by evaporation or
spray drying of the reaction solution, it being possible
for a buffer substance to be added to this reaction
solution.
The dyestuff mixtures according to the invention can
comprise further fiber-reactive dyestuffs, which serve to
shade the dyestuff mixture, in an amount of up to 5% by
weight. These "shading dyestuffs" can be added by custom-
ary mixing or else, if one or more of the components of
the shading dyestuff are identical to the components of
the dyestuffs of the formulae (1) and/or (2), can be
prepared and introduced into the dyestuff mixture by a
chemical route in the same reaction batch together with
the synthesis described above for a dyestuff mixture
according to the invention. Thus, to prepare a dyestuff
mixture according to the invention having a content of a
shading dyestuff with a particular chromophore, for
example, those additional starting compounds which
contain 4,6-disulfo-l-amino-8-naphthol or 2- or 3-amino-
6-sulfo-8-naphthol or a 1-(aminopheny1)-3-carboxy- or -3-
methyl-5-pyrazolone as a component instead of the 3,6-
disulfo-l-amino-8-naphthol component of the dyestuffe (1)
and (2) can be employed in the reaction batch. I
The dyestuff mixtures according to the invention have
valuable properties regarding their use. They are used
for dyeing or printing materials containing hydroxy
and/or carboxamide groups, for example in the form of
sheet-like structures, such as paper and leather, or of
films, such as, for example, of polyamide, or in bulk,
such as, for example, polyamide and polyurethane, but in
particular these materials in fiber form. The solutions
of the dyestuff mixtures according to the invention
obtained during synthesis of the azo compounds can also
be used for dyeing directly as a liquid preparation, if
appropriate after addition of a buffer substance and if
appropriate also after concentration or dilution.
The present invention thus also relates to the use of the
dyestuff mixtures according to the invention for dyeing
or printing these materials and to processes for dyeing
or printing such materials by procedures which are
customary per se in which a dyestuff mixture according to
the invention is employed as the coloring agent. The
materials are preferably used in the form of fiber
materials, in particular in the form of textile fibers,
such as woven fabrics or yarns, such as in the form of
hanks or wound packages.
Materials containing hydroxy groups are those of natur-
ally occurring or synthetic origin, such as, for example,
cellulose fiber materials or regenerated products there-
of, and polyvinyl alcohols. Cellulose fiber materials are
preferably cotton, but also other plant fibers, such as
linen, hemp, jute and ramie fibers; regenerated cellulose
fibers are, for example, viscose staple and filament
viscose.
Materials containing carboxamide groups are, for example,
synthetic and naturally occurring polyamides and
polyurethanes, in particular in the form of fibers, for
example wool and other animal hair, silk, leather, nylon
6,6, nylon 6, nylon 11 and nylon 4.
The dyestuff mixtures according to the invention can be
applied to and fixed on the substrates mentioned, in
particular the fiber materials mentioned, by the applica-
tion techniques known for water-soluble dyestuffs, in
particular for fiber-reactive dyestuffs.
Dyeings with very good color yields which are improved
with respect to the individual dyestuffs are those
obtained with them on cellulose fibers by the exhaustion
process from a long liquor using the most diverse acid-
binding agents and if appropriate neutral salts, such as
sodium chloride or sodium sulfate. Dyeing is preferably
carried out in an aqueous bath at temperatures between 4 0
and 105°C, if appropriate at a temperature of up to 130°C
under pressure, and if appropriate in the presence of
customary dyeing auxiliaries. A procedure can be followed
here in which the material is introduced into the hot
bath, this is gradually heated to the desired dyeing
temperature and the dyeing process is brought to
completion at this temperature. If desired, the neutral
salts which accelerate exhaustion of the dyestuffs can
also be added to the bath only after the actual dyeing
temperature has been reached.
Excellent color yields and a very good color build-up are
likewise obtained by the padding process on cellulose
fibers, it being possible for the dyeings to be fixed in
the customary manner by batching at room temperature or
elevated temperature, for example up to about 60°C, by
steaming or with dry heat.
Strong prints with a good contour level and a clear white
background are likewise obtained by the customary print-
ing processes for cellulose fibers, which can be carried
out in one phase - for example by printing with a print-
ing paste comprising sodium bicarbonate or another acid-
binding agent and subsequent steaming at 100 to 103°C, -
or in two phases - for example by printing with neutral
or weakly acid printing ink and subsequent fixing either
by passing the goods through a hot electrolyte-containing
alkaline bath or by over-padding with an alkaline
electrolyte-containing padding liquor and subsequent
batching or steaming or dry heat treatment of the
material over-padded under alkaline conditions. The
printing result depends only little on the varying fixing
conditions.
Hot air at 120 to 200°C is used for fixing by means of
dry heat by the customary thermofixing processes. In
addition to customary steam at 101 to 103°C, it is also
possible to employ superheated steam and pressurized
steam at temperatures of up to 160°C.
The acid-binding agents and the agents which effect
fixing of the dyestuffs of the dyestuff mixtures accord-
ing to the invention to the cellulose fibers are, for
example, water-soluble basic salts of the alkali metals
and likewise alkaline earth metals with inorganic or
organic acids, or compounds which liberate alkali under
the influence of heat. The alkali metal hydroxides and
alkali metal salts of weak to moderately strong inorganic
or organic acids are to be mentioned in particular, the
alkali metal compounds preferably meaning sodium and
potassium compounds. Such acid-binding agents are, for
example, sodium hydroxide, potassium hydroxide, sodium
carbonate, sodium bicarbonate, potassium carbonate,
sodium formate, sodium dihyc'rogen phosphate, disodium
hydrogen phosphate, sodium trichloroacetate, water-glass
or trisodium phosphate.
The dyestuff mixtures according to the invention are
distinguished by a high fixing yield when used in dyeing
and printing processes on cellulose fiber materials.
After customary after-treatment by rinsing to remove non-
fixed portions of dyestuff, the dyeings on cellulose show
excellent wet-fastnesses, especially since non-fixed
portions of dyestuff can easily be washed out because of
their good solubility in cold water.
The dyeings and prints obtainable with the dyestuff
mixtures according to the invention have clear shades; in
particular, the dyeings and prints on cellulose fiber
materials have a good lightfastness and very good wet-
fastnesses, such as fastness to washing, milling, water,
seawater, cross-dyeing and acid and alkaline perspira-
tion, and furthermore a good fastness to pleating,
fastness to ironing and fastness to rubbing.
The dyestuff mixtures according to the invention can
furthermore also be used for fiber-reactive dyeing of
wool. Wool which has been given an antifelting or low-
felting treatment (cf., for example, H. Rath, Lehrbuch
der Textilchemie [Textbook of Textile Chemistry],
Springer-Verlag, 3rd edition (1972), pages 295-299, in
particular treatment by the so-called Hercosett process
(page 298); J. Soc. Dyers and Colourists 1972, 93-99, and
1975, 33-44) can also be dyed with very good fastness
properties.
The process for dyeing on wool is carried out here by the
customary and known dyeing procedure from an acid medium.
Thus, for example, acetic acid and/or ammonium sulfate or
acetic acid and ammonium acetate or sodium acetate can be
added to the dyebath in order to obtain the desired pH.
To achieve a usable levelness of the dyeing, it is
advisable to add customary leveling auxiliaries, such as,
for example, those based on a reaction product of
cyanuric chloride with 3 times the molar amount of an
aminobenzenesulfonic acid and/or of an aminonaphthalene-
sulfonic acid, or based on a reaction product of, for
example, stearylamine with ethylene oxide. Thus, for
example, the dyestuff mixture according to the invention
is preferably first subjected to the exhaustion process
from an acid dyebath with a pH of about 3.5 to 5.5, the
pH being controlled, and, towards the end of the dyeing
5 time, the pH is shifted into the neutral and, if approp-
riate, weakly alkaline range up to a pH of 8.5, in order
to bring about a complete reactive bond between the
dyestuffs of the dyestuff mixtures according to the
invention and the fiber in particular to achieve good
lb depths of color. At the same time, the dyestuff portion
which has not been bonded reactively is dissolved off.
The procedure described here also applies to the produc-
tion of dyeings on fiber materials of other naturally
occurring polyamides or of synthetic polyamides and
15 polyurethane. As a rule, the material to be dyed is
introduced into the bath at a temperature of about 40°C
and is agitated therein for some time, the dyebath is
then adjusted to the desired weakly acidic pH, preferably
with acetic acid, and the actual dyeing is carried out at
2b a temperature between'60 and 98°C. The dyeings can also
be carried out at the boiling point or in closed dyeing
apparatuses at temperatures of up to 106°C. Since the
water-solubility of the dyestuff mixtures according to
the invention is very good, they can also advantageously
2|5 be employed in customary continuous dyeing processes. The
tinctorial strength of the dyestuff mixture according to
the invention is very high.
The dyestuff mixtures according to the invention give
clear yellowish-tinged to bluish-tinged red dyeings on
3p the materials mentioned, preferably fiber materials.
The following Examp 1es serve to illustrate the invention.
The parts are parts by weight and the percentage data are
percentages by weight, unless stated otherwise. Parts by
weight bear the same relation to parts by volume as the
3b kilogram to the liter. The compounds described by their
free acids; they are in general 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 mentioned in the form of the free
acid in the following Examples, in particular the Tabular
Examples, can likewise be employed in the synthesis as
such or in the form of their salts, preferably alkali
metal salts, such as sodium or potassium salts.
Example 1
a) 190.1 parts of cyanuric chloride are introduced into
a suspension of 319.2 parts of l-amino-8-naphthol-
3,6-disulfonic acid in 1000 parts of water and
300 parts of ice, while stirring thoroughly; the
reaction batch is further stirred at between 0 and
15°C and a pH of between 1.7 and 2.2, by means of
sodium bicarbonate, for another four hours.
b) In a separate operation, the diazonium salt of the
diazo component is prepared: 183 parts of a 38%
strength aqueous sodium nitrite solution are added
to a solution of pH 6.7 to 6.8 of 281.4 parts of 4-
(/3-sulfatoethylsulfonyl)-aniline in 500 parts of
water. This mixture is allowed to run into a mixture
of 800 parts of crushed ice and 215 parts of 96%
strength aqueous sulfuric acid, while stirring
thoroughly. The mixture is stirred at a temperature
of between 0°C and 5°C for a further hour and excess
nitrous acid is then destroyed with a little amido-
sulfonic acid in the customary manner.
c) The primary condensation product, prepared under a),
of cyanuric chloride and the aminonaphtholdisulfonic
acid is combined with the diazonium salt solution!
described under b) . For carrying out the coupling
reaction, the strongly acidic reaction mixture is
brought to a pH of 4.0 to 4.5 by means of sodium
carbonate at a temperature of about 15 °C and the*'
temperature is increased to 15 to 20°C. The mixture
is further stirred at this pH and this temperature
for a few more hours, until the coupling has ended.
d) The solution of the monoazo compound of c) is com-
bined with a solution of pH 5.5 to 6.0 of
133.0 parts of 4-(/8-sulfatoethylsulfonyl)-aniline
and 86.5 parts of aniline-4-sulfonic acid in
640 parts of water. The pH is kept at about 5 and
the reaction mixture is heated to a temperature of
60 to 65°C in the course of one to two hours. A pH
of between 6.0 and 6.5 is then established by means
of sodium carbonate, the batch is clarified by
filtration and the filtrate is spray dried.
About 1350 parts of a powder comprising electrolyte salt
(chiefly sodium chloride and sodium sulfate), which
comprises the sodium salt of the compound of the formula
(A)

to the extent of about 35% and the sodium salt of the
compound of the formula (B)

to the extent of about 35% are obtained. This mixture
shows very good dyestuff properties and gives strong red
dyeings and prints with very good fastness properties, of
which above all the very good fastnesses to washing,
light, alkali, acid, water, seawater, perspiration and
rubbing can be singled out, on the materials mentioned in
the description, such as cellulose fiber materials, in
particular cotton and viscose, by the application and
fixing methods customary in the art for fiber-reactive
dyestuffs. The dyeings are furthermore distinguished by
their high degree of fixing and good build-up from the
cellulose materials.
Example 2
19.4 parts of cyanuric chloride and 31.9 parts of 1-
amino-8-naphthol-3,6-disulfonic acid are introduced
rapidly into a mixture of 330 parts of water and 40 parts
of ice, while stirring thoroughly, the batch is further
stirred at a pH of between 1.5 and 2.0 and at a tempera-
ture of between 10 and 15 °C for about a further 3.5 hours
and the solution of this primary condensation product is
clarified by means of kieselguhr and filtration.
The solution is combined with a suspension, prepared by
the customary route by diazotization by means of sodium
nitrite and sulfuric acid in an aqueous medium, of the
diazonium salt of 41.1 parts of 6-(/3-sulfatoethylsulfon-
yl)-2-amino-naphthalene-1-sulfonic acid, the strongly
acidic coupling mixture is then brought to a pH of 4.0 to
4.5 by means of calcium carbonate at a temperature of
about 10°C and the mixture is further stirred at 10 to
14°C and within this pH range for a few more hours.
A solution of pH 5 of 16.1 parts of N-ethyl-4-(/S-sulfato-
ethylsulfonyl)-aniline and 9.1 parts of aniline-3-
sulfonic acid in 100 parts of water is then added, and
the batch is stirred at a temperature of 18 to 22°C for
two to three hours, subsequently heated to 50 to 55°C and
kept at this temperature for 30 minutes, while keeping
the pH constant at 4.0 to 4.5 by means of calcium carbon-
ate. The mixture is subsequently stirred at 18 to 20°C
for a few more hours, the calcium sulfate is filtered off
with suction and rinsed with water and the calcium ions
are precipitated in this combined filtrate and wash water
by means of sodium oxalate at a pH of 4.5 to 5.0 and a
temperature of 30°C. After the mixture has been stirred
for one hour, the precipitate is filtered off and the
dyestuff mixture according to the invention is isolated
from the filtrate by spray drying.
About 150 parts of a dark red powder which, in addition
to electrolyte salts, is about 36% strength in the sodium
salt of the compound of the formula (C)

and about 3 6% strength in the sodium salt of the compound
of the formula (D)

are obtained. This dyestuff mixture according to the
invention has very good properties with regard to its use
and gives strong red dyeings and prints with very good
fastnesses to manufacturing processes and use, among
which the lightfastness, the fastnesses to washing,
perspiration, water and seawater and the resistance to
chlorinated drinking water (chlorinated pool water) may
be mentioned in particular, by the printing and dyeing
procedures customary in the art for fiber-reactive
dyestuffs, for example on cellulose fiber materials. The
fixing ratio of this dyestuff mixture according to the
invention on cellulose fiber materials is very high.
Example 3
92 parts of aniline-3-sulfonic acid and 149 parts of 4-
(/3-sulfatoethylsulfonyl) -aniline are introduced into a
suspension of 195 parts of cyanuric chloride in
1000 parts of water and 500 parts of ice, while stirring
thoroughly. The batch is further stirred at a pE of 2.5
to 3 and a temperature of 0 to 10 "C for about three
hours, until the reaction has ended.
Thereafter, 320 parts of l-amino-3,6-disulfo-8-naphthol
are added, while stirring further, a pH of 4 to 5 is
established with sodium carbonate and the second conden-
sation reaction is brought to completion at a temperature
of 45°C and a pH of about 4.5 in the course of three to
four hours.
The batch is then cooled to about 10°C and the equivalent
amount of the diazonium salt suspension described in
Example lb is added, while stirring further and maintain-
ing a pH of 6 and a temperature of 10 to 15°C. The deep
red solution obtained when the coupling reaction has
ended is clarified by filtration and the dyestuff mixture
is isolated from the filtrate by spray drying.
About 1350 parts of a red powder comprising electrolyte
salt and with a content of about 3 5% of the sodium salt
of the compound of the. formula (A) described in Example
1 and about 35% of the sodium salt of the compound of the
formula (D) described in Example 2 are obtained.
This dyestuff mixture according to the invention has very
good properties with regard to its use and gives strong
red dyeings and prints of good reproducibility and with
good fastnesses to manufacturing processes and use, among
which the fastnesses to washing may be mentioned in
particular, by the printing and dyeing procedures custom-
ary in the art for fiber-reactive dyestuffs, for example
on cellulose fiber materials. The fixing ratio of this
dyestuff mixture according to the invention on cellulose
fiber materials is very high and the color build-up of
the dyeings very good.
Examples 4 to 105
Further dyestuff mixtures according to the invention of
monoazo compounds of the formula (1A) and (2A)

are described with the aid of their components in the
following Tabular Examples. They can be prepared in the
manner according to the invention either by mechanical
mixing of the individual dyestuffs or else by a chemical
route, for example analogously to one of the above
Embodiment Examples. with the aid of their starting
components (cyanuric chloride, cyanuric bromide or
cyanuric fluoride, an amino compound D1-NH2 and D2-NH2 as
the diazo component, l-amino~8-naphthol-3,6-disulfonic
acid as the coupling component and an amino compound of
the formula A-NH2 and B-NH3) .
The dyestuff mixtures according to the invention have
very good properties with regard to their use and give
strong dyeings and prints with good fastness properties
and a good color build-up in the color shade stated in
the particular tabular example on the materials mentioned
in the description, such as, in particular, cellulose
fiber materials, by the application methods in dyeing and
printing customary in the art, preferably by the applica-
tion and fixing methods for fiber-reactive dyestuffs
customary in the art.
The numerical ratios stated in the column WR indicate the
weight ratio in percent of the dyestuff or dyestuffs of
the formula (1A) to the dyestuff or dyestuffs of the
formula (2A) in which the dyestuffs are present in the
particular dyestuff mixture.
WE CLAIM:
1. A process for preparing a dyestuff mixture by mechanical mixing the
individual dyestuffs, corresponding to the general formulae (1) and (2) in a ratio
of 90:10% by weight to 10:90% by weight

in which:
M it hydrogen or an alkali metal or the stoichiometric equivalent of an aHcaflne
earth metal;
D1 is the radical of a benzene or naphthalene nucleus;
D2 has one of the meanings of D1;
R1 Is hydrogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon
atoms If D1 or D2 is the radical of a benzene nucleus, or is hydrogen or suifo If D1
or D2 is the radical of a naphthalene nucleus;
R2 Is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon
atoms or sulfo if D1 or D2 is the radical of a benzene nucleus, or Is hydrogen or
sulfo if D1 or O2 is the radical of a naphthalene nucleus;
R3 is hydrogen, alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon
atoms;
R4 is hydrogen, aflcyl having 1 to 4 carbon atoms or aflcoxy having 1 to 4 carbon
atoms;
R5 is hydrogen, aflcyl having to 4 carbon atoms, afcoxy having 1 to 4 carbon
atoms or suito;
R8 is hydrogen, aNcyi having 1 to 4 carbon atoms or aflcoxy having 1 to 4 carbon
atoms;
R7 is hydrogen, aNcyi having 1 to 4 carbon atoms, aNcoxy having 1 to 4 carbon
atoms or sufto;
R is hydrogen or aNcyi having 1 to 4 carbon atoms;
Y1 is vinyl, p-suffatoethyl, p-IWoeiflfatoethyl or p-cNoroethyl;
Y2 has one of the meanings of Y1;
Y3 has one of the meanings of Y1;
X1 is fluorine, bromine or chlorine;
X3 has one of the meanings of X1; and
the groups -SOyY1, -SO2-Y2 and -SO2-Y3 are in the meta- or para-position
relative to the azo group on the benzene nucleus of D1 and D2 or are bonded hi
the meta- or para-position relative to the amino group.
2. The process as claimed in claim 1, wherein one or more azo dyestuffs
corresponding to the formula (1) and one or more azo dyestuffs corresponding to
the formula (2) m a mixing ratio of 70:30% by weight to 30:70% by weight.
3. The process as claimed in claim 1, wherein one or more azo dyestuffs
corresponding to the formula (1) and one or more azo dyestuffs corresponding to
the formula (2) in a mixing ratio of 55.45% by weight to 45:55% by weight.
4. The process as claimed in one of claims 3, wherein hi the dyestuffs of the
formulae (1) and (2), the radical R is hydrogen.
5. The process as claimed in claim one of claim 1 to 4, wherein D1 and D2
are both the radical of a benzene nucleus.
6. The process as claimed in claim 5, wherein R1 is hydrogen, methoxy or
methyl, R3 is hydrogen or methoxy, R4 is hydrogen, methoxy or methyl, R5 is
hydrogen or methoxy and Y1 and Y3 independently of one another are vinyl or B-
suffatoethyl.
7. The process as claimed in one of claims 1 to 6, wherein X1 and X2 are
both chlorine.
8. The process as claimed m one of claims 1 to 6, wherein X1 and X2 are
both fluorine.
9. The process as claimed in one of claim• 1 to 8, wherein R3 is hydrogen
and Y2 is vinyl or p-sufatoethyl.
10. The process as claimed in one of claims 1 to 9, wherein R° is hydrogen
and R7 Is hydrogen or suVo.

A process for preparing a dyestuff mixture by mechanical mixing the individual
dyestuffs, corresponding to the general formulae (1) and (2) in a ratio of 90:10%
by weight to 10:90% by weight

in which: M is hydrogen or an alkali metal or the stoichiometric equivalent of an
alkaline earth metal; D1 is the radical of a benzene or naphthalene nucleus; D2
has one of the meanings of D1; R1 is hydrogen, alkyl having 1 to 4 carbon atoms
or alkoxy having 1 to 4 carbon atoms if D1 or D2 is the radical of a benzene
nucleus, or is hydrogen or sulfo if D1 or D2 is the radical of a naphthalene
nucleus; R2 is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4
carbon atoms or sulfo if D1 or D2 is the radical of a benzene nucleus, or is
hydrogen or sulfo if D1 or D2 is the radical of a naphthalene nucleus;
R3 is hydrogen, alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon
atoms; R4 is hydrogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4
carbon atoms; R5 is hydrogen, alkyl having to 4 carbon atoms, alkoxy having 1 to

4 carbon atoms or sulfa; R6 is hydrogen, alkyl having 1 to 4 carbon atoms or
alkoxy having 1 to 4 carbon atoms; R7 is hydrogen, alkyl having 1 to 4 carbon
atoms, alkoxy having 1 to 4 carbon atoms or sulfa; R is hydrogen or alkyl having
1 to 4 carbon atoms; Y1 is vinyl, -sulfatoethyl, -thiosulfatoethyl or -chloroethyl;
Y2 has one of the meanings of Y1; Y3 has one of the meanings of Y1; X1 is
fluorine, bromine or chlorine; X2 has one of the meanings of X1; and the groups -
SO2-Y1, -SO2-Y2 and -SO2-Y3 are in the meta- or para-position relative to the
azo group on the benzene nucleus of D1 and D2 or are bonded in the meta- or
para-position relative to the amino group.