Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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Description
Deep Navy Dye Mixtures of Fiber-Reactive Azo Dyes and A Method for their
Preparation and A Process for Dyeing Hydroxy and/or Carboxamido Containing
Fibers
The present invention relates to the field of fiber-reactive dyes.
io
Navy-dyeing mixtures of fiber-reactive dyes are known from European Patent
Applications EP-A 0588257, EP-A 0668328, EP-A 0127456. However these dye
mixtures have still some deficiencies, such as, for ex., when applied to
substrates
other than cellulose, for example wool. Deep navy shades on carboxamido
is containing fibers are usually achieved by the application of mordant dyes.
Mordant
dyes are well known for their good fastness - and dyeing properties. However
they
have ecological disadvantages, so that alternative reactive dye mixtures are
desirable.
2o With the present invention, deep navy-dyeing reactive dye mixtures have
been found
which unexpectedly and surprisingly have improved properties, such as improved
resistance to ammonium aftertreatment and levelness in regard to the dyeing of
wool. The present invention discloses dye mixtures comprising one or more,
such as
one, two or three, disazo dyes conforming to the general formula (1 )
H2 H
R~ R3
Y~ - 02S \ N = N / I \ N = N I S02 - Y2
R ~ MO3S \ ~ SO3M R4 (1 )
2
one or more, such as one, two, three or four, monoazo dyes conforming to the
general formula (2),
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2
X~
R5
i~ ~N
(Ya'SOZ)n D~N ~N~Xz
Rs~ O H H N
(2)
M03S ~ ~ S03M
in which:
R' is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
s methoxy or hydrogen and in particular hydrogen;
R2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
hydrogen;
R3 has one of the meanings of R1
R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
io hydrogen;
R5 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
methoxy, sulfo or hydrogen and in particular sulfo;
R6 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
methoxy, sulfo or hydrogen and in particular sulfo;
is D is a benzene or naphthalene radical;
n is0or1
X' is a fluoro, chloro, cyanamido, or morpholino group or a group of the
following
formulae; NR7R$ or OR9 or
wherein R»
zo
12
*~
N SOZ Ys
Rio
R' is hydrogen, methyl, ethyl, hydroxyethyl, methoxyethyl, ethoxyethyl, or
2s sulfoethyl, preferably ethyl, methoxyethyl, sulfoethyl
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3
R8 has one of the meanings
of R';
R9 has one of the meanings
of R7;
R' has one of the meanings
of R';
R" is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
s methoxy or hydrogen and in particular hydrogen;
R'2 is hydrogen, methyl, ethyl, methoxy, ethoxy, sulfo or carboxy, preferably
methoxy or hydrogen and in particular hydrogen;
X2 has one of the meanings of X';
Y' is vinyl, or is ethyl substituted in the ~i-position by a substituent which
is
io 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, and Y' is preferably
vinyl,
f3-chloroethyl, f3-thiosulfatoethyl or f3-sulfatoethyl and is in particular
preferably
vinyl or ~i-sulfatoethyl;
is Y2 has one of the meanings
of Y';
Y3 has one of the meanings
of Y';
Y4 has one of the meanings
of Y';
M denotes hydrogen or an alkali metal such as lithium, sodium and potassium.
Both in the formulae mentioned above and in those below, the individual
formula
members, both with different and with the same designation within a formula or
the
various formulae, can within the scope of their definitions have meanings
which are
the same as or different from one another.
The groups "sulfo", "thiosulfato", "carboxy", "phosphato" and "sulfato"
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 , carboxy groups are groups of the formula -COOM , phosphato groups
are groups of the formula -OP03M2 and sulfato groups are groups of the formula
-OS03M , in which M is defined as above.
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4
The dye, respectively dyes, of the general formula (1 ) are present in the
mixtures in
an amount of from 70 to 95% by weight, preferably of from 75 to 90 % by
weight, and
the dye, respectively dyes of the general formula (2) are present in the
mixtures in an
s amount of from 5 to 30% by weight, preferably of from 10 to 25 % by weight.
The dye mixtures of the invention may optionally contain one, two or three
dyestuffs
corresponding to the general formula (3a) or (3b) or both
R~
\ N=N
Y~ - S02
z
R M03; M
(3 a)
R3 HO NH2
Y2 - SOZ \ N N / \
,/
Ra \ ( /
M03S S03M
(3b)
in which R', R2, R3, R4, M, Y' and Y2 are defined as above. These two monoazo
is dyestuffs may be already formed during the synthesis of the disazo dye of
formula
(1 ) when coupling reactions of the starting compounds are incomplete.
If the dye mixture of the instant invention contains, as a further component,
a
monoazo dyestuff of formula (3a) or of formula (3b) or both, the dye or dyes
of
2o formula (3a) or of formula (3b) or of both are present in the dye mixture
of the dyes
of formula (1 ) and (2) in the range of 0.01 to 8 % by weight, calculated on
the 100
dye mixture of the dyes (1 ) and (2).
The dyes of the general formulae (1 ), (2), (3a) and (3b), in particular if
those
2s corresponding to the same general formula have the same chromophore, can
have,
within the meaning of their Y-moiety, structurally different fiber-reactive
groups
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corresponding to their -SOz-Y-moiety. In particular, the dye mixture can
contain
dyes of the same chromophore conforming to the formula (1 ) and/or dyes of the
same chromophore conforming to formula (2), optionally likewise of the general
formula (3a) or (3b) or both in which the fiber-reactive groups of the
corresponding
s -SOz-Y-moiety are partly vinylsulfonyl groups and partly groups in which the
Y-moiety is a ~i-ethyl substituted group as defined above, such as
f3-chloroethylsufonyl, f5-thiosulfatoethylsulfonyl or, preferably, f3-
sulfatoethylsulfonyl
groups. If the dye mixtures contain the respective dye components in the form
of a
vinylsulfonyl dye, the proportion of the respective vinylsulfonyl dye to the
respective
io dye with a Y-moiety being a ~3-ethyl substituted group as defined above,
such as a (3-
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-
substituted
ethylsulfonyl dye, such as f3-sulfatoethylsulfonyl dye, is in terms of the
molar ratio
is between 2 : 98 and 30 : 70.
Radicals of the formulae (4), (5) and (6)
R~ s
Y~.OzS . v ~ Y~02S
(4) ( 5 )
Rz Ra
R5
(Y4 SOz) ~D~*
R/s
in the dyes of formulae (1), (2) for n=1, (3a) and (3b) are, for example,
2s 2-(~3-sulfatoethylsulfonyl)phenyl, 3-(~3-sulfatoethylsulfonyl)phenyl, 3- or
4-vinylsulfonylphenyl, 4-(~3-sulfatoethylsulfonyl)phenyl, 2-carboxy-5-(~3-
sulfatoethylsulfonyl)phenyl, 4-methoxy-3-(~3-sulfatoethylsulfonyl)-phenyl,
2-ethoxy-4- or -5-(~3-sulfatoethylsulfonyl)phenyl, 2-methyl-4-((3-
sulfatoethylsulfonyl)-
phenyl, 2-methoxy-5- or -4-(~3-sulfatoethylsulfonyl)phenyl, 2,4-diethoxy-5-((3-
sulfato-
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6
ethylsulfonyl)phenyl, 2,4-dimethoxy-5-(~3-sulfatoethylsulfonyl)phenyl, 2,5-
dimethoxy-
4-(~-sulfatoethylsulfonyl)phenyl, 2-methoxy-5-methyl-4-(~i-sulfatoethyl-
sulfonyl)phenyl, 2- or 3- or 4-(~3-thiosulfatoethylsulfonyl)phenyl, 2-methoxy-
5-(~3-thio-
sulfatoethylsulfonyl)phenyl, 2-sulfo-4-(~3-phosphatoethylsulfonyl)phenyl, 2-
sulfo-4-
s vinylsulfonylphenyl and 3- or 4-(~3-acetoxyethylsulfonyl)phenyl and their
corresponding vinylsulfonyl derivatives.
Radicals of the formula (6)
R5
(Ya'SOz) / D-* (6)
to
Rs
for n=0 in the dyes of formula (2) are, for example 4-methyl-2-sulfophenyl, 4-
methoxy-2-sulfophenyl, 4-sulfophenyl, 3-sulfophenyl, 2-sulfophenyl, 4-methoxy-
2,5-
disulfophenyl, 4-methyl-2,5-disulfophenyl, 1,5-disulfonaphthyl or 1-
sulfonaphthyl.
is
Preference is given to dye mixtures according to the invention, in which
D is the radical of 1,5-disulfonaphthyl
R' is methoxy or hydrogen,
R2 is hydrogen,
2o R3 is methoxy or hydrogen,
R4 is hydrogen,
X' is chlorine
XZ is the radical 4-(f3-sulfatoethylsulfonyl)phenyl
and R', R2, R3 and R4 are in particular preferred each hydrogen and the Y-
moieties
2s are each preferable, independently of the other one vinyl or ~i-
sulfatoethyl.
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
3o 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
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bicarbonate, 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.
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 substances in a
total
io 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
solutions 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 abovementioned buffer substances in
an
is amount of up to 5 % by weight, preferably up to 2 % by weight.
The dye mixtures of the invention are preparable in a conventional manner, as
by
mechanically mixing the individual dyes in the necessary proportions, whether
in the
form of their dye powders or granules or their synthesis solution or of
aqueous
solutions of the individual dyes in general, which may still include customary
2o auxiliaries.
The dyes according to the general formula (1 ) are known from the U.S. Patents
Nos.
2,657,205, 3,387,914, 4,072,463 and 4,257,770 or from one of the above-
mentioned publications, and the dyes of the general formula (2) are known from
the
2s European Patent Application EP-A 534 342 and from the European Patent
Application EP A 177 449.
The dye mixtures of the instant invention are well suitable for dyeing (which
includes
printing) hydroxy- andlor carboxamido-containing fiber materials by the
application
and fixing methods numerously described in the art for fiber-reactive dyes, in
deep
3o navy shades with good color build-up and good wash-off in respect of
unfixed dye
portions.
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The present invention therefore also provides for use of the novel dye
mixtures for
dyeing (including printing) hydroxy- and/or carboxamido-containing fiber
materials
and processes for dyeing such 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 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
io 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.
is 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.
Furthermore, the dye mixtures of the invention can also be used for the fiber-
reactive
dyeing of wool. Moreover, wool which has been given a nonfelting or low-
felting
2o finish (cf. H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd
Edition (1972), p.
295-299, especially the finish by the so-called Hercosett process (p. 298); J.
Soc.
Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good
fastness properties.
2s 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 may 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 on the basis of a reaction product of
cyanuric
so chloride with 3 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 of the
invention is
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preferably subjected to the exhaustion 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 perhaps 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 of 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
io polyurethanes. In general, the material to be dyed is introduced into the
bath at a
temperature of about 40°C, agitated therein for some time, the dyebath
is then
adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and
the
actual dyeing is carried out at a temperature between 60 and 98°C.
However, the
dyeings can also be carried out at the boil or in sealed dyeing apparatus at
is temperatures of up to 106°C. Since the water solubility of the dye
mixtures of the
invention is very good, they can also be used with advantage in customary
continuous dyeing processes. The color strength of the dye mixtures of the
invention
is very high.
2o Application of the dye mixtures of the invention 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
advantageously useful in exhaust dyeing processes. Applied in this way for
example
2s 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 or sodium
sulfate, they produce dyeings in very good color yields with excellent color
build-up
3o 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
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exhaustion of the dyes can also if desired not be added to the bath until the
actual
dyeing temperature has been reached.
Similarly, the conventional printing processes for cellulose fibers, which can
either be
s 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
to alkaline bath or by overpadding with an alkaline electrolyte-containing
padding
liquour and subsequent hatching of this treated material or subsequent
steaming or
subsequent treatment with dry heat, produce 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
Is 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.
2o 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
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
2s 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
3o agents with or without heating bonds the dyes chemically to the cellulose
fiber;
especially the dyeings on cellulose, after they have been given the usual
aftertreatment of rinsing to remove unfixed dye portions, show excellent wet
fastness
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11
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
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 aminobenzenesulfonic
to 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 out at temperature between 60 and
98°C.
is 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 precentages are
by
weight, unless otherwise stated. The parts by weight bear the same relation to
parts
2o by volume as the kilogram to the liter.
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Example 1
A dye mixture according to the invention is prepared by mechanically mixing
150
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A)
H03SOCHZCH202S (A)
/ / SOZCHZCH20S03H
\ I OH NHZ
N=N / \ N=N
I
H03S \ / S03H
with 33.3 parts of a red electrolyte-salt containing powder with a content of
60% of a
dye of formula (B)
/ S02CH2CH20S03H
is I (B)
HN \
N i 'N
OH HN~N~CI
%Y\
\ t /
H03S S03H
with 10 parts of a red electrolyte-salt containing powder with a content of
50% of a
dye of formula (C)
/ SOZCH2CHzOS03H
OH NHZ
N=N \
/ \ (C
I
H03S \ / S03H
3o The resulting mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye
(B) and
5% (w/w) of dye (C) and dyes wool in navy-blue shades. The dye mixture
exhibits
excellent dyestuff properties (i.e. lightfastness and washfastness).
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Example 2
A dye mixture according to the invention is prepared by mechanically mixing
155
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 33.3 parts of a red electrolyte-salt containing powder
with a
content of 60% of a dye of formula (B) with 5.0 parts of a red electrolyte-
salt
containing powder with a content of 50% of a dye of formula (C). The resulting
mixture contains 77.5% (w/w) of dye (A) and 20% (w/w) of dye (B) and 2.5%
(w/w) of
dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent
to dyestuff properties (i.e. lightfastness and washfastness).
Example 3
A dye mixture according to the invention is prepared by mechanically mixing
160
is parts of a navy-blue electrolyte-salt containing powder with a content of
50% of a dye
of formula (A) with 25 parts of a red electrolyte-salt containing powder with
a content
of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-salt
containing
powder with a content of 50% of a dye of formula (C). The resulting mixture
contains
80% (w/w) of dye (A) and 15% (w/w) of dye (B) and 5% (w/w) of dye (C) and dyes
2o wool in navy-blue shades. The dye mixture exhibits excellent dyestuff
properties (i.e.
lightfastness and washfastness).
Example 4
2s A dye mixture according to the invention is prepared by mechanically mixing
170
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 16.6 parts of a red electrolyte-salt containing powder
with a
content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-
salt
containing powder with a content of 50% of a dye of formula (C). The resulting
3o mixture contains 85% (w/w) of dye (A) and 10% (w/w) of dye (B) and 5% (w/w)
of
dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent
dyestuff properties (i.e. lightfastness and washfastness~.
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Example 5
A dye mixture according to the invention is prepared by mechanically mixing
150
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 16.6 parts of a red electrolyte-salt containing powder
with a
content of 60% of a dye of formula (B) with 10.0 parts of a red electrolyte-
salt
containing powder with a content of 50% of a dye of formula (C) with 20.0
parts of a
red electrolyte-salt containing powder with a content of 50% of a dye of
formula (D).
The resulting mixture contains 75% (w/w) of dye (A) and 10% (w/w) of dye (B)
and
l0 5% (w/w) of dye (C) and 10% (w/w) of dye (D) and dyes wool in navy-blue
shades.
The dye mixture exhibits excellent dyestuff properties (i.e. lightfastness and
washfastness).
/ SOZCHZCHzOS03H
(D)
HN \
is
H03SOCHzCH20zS N i _N
I \ OH HN~N~CI
N-N / I \
H03S \ / S03H
2o Example 6
A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 16.6 parts of a red electrolyte-salt containing powder
with a
2s content of 60% of a dye of formula (B) and with 20.0 parts of a red
electrolyte-salt
containing powder with a content of 50% of a dye of formula (D). The resulting
mixture contains 80% (wlw) of dye (A) and 10% (w/w) of dye (B) and 10% (w/w)
of
dye (D) and dyes wool in navy-blue shades. The dye mixture exhibits excellent
dyestuff properties (i.e. lightfastness and washfastness).
Example 7
A dye mixture according to the invention is prepared by mechanically mixing
150
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
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of formula (A) with 28.5 parts of a red electrolyte-salt containing powder
with a
content of 70% of a dye of formula (E) and with 10.0 parts of a red
electrolyte-salt
containing powder with a content of 50% of a dye of formula (C). The resulting
mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (E) and 5% (w/w) of
dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent
dyestuff properties (i.e. lightfastness and washfastness).
(E)
/ I
H~ \ SOzCH2CH20S03H
l0 S03H
N~ N
\ \ 1' l
I / / OH HN'\\N/\CI
N-N / I \
S03H
H03S \ / S03H
is Example 8
A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 21.5 parts of a red electrolyte-salt containing powder
with a
2o content of 70% of a dye of formula (E) and with 10.0 parts of a red
electrolyte-salt
containing powder with a content of 50% of a dye of formula (C). The resulting
mixture contains 80% (w/w) of dye (A) and 15% (w/w) of dye (E) and 5% (w/w) of
dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent
dyestuff properties (i.e. lightfastness and washfastness).
Example 9
A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 23 parts of a red electrolyte-salt containing powder with
a content
of 65% of a dye of formula (F) and with 10.0 parts of a red electrolyte-salt
containing
powder with a content of 50% of a dye of formula (C). The resulting mixture
contains
80% (w/w) of dye (A) and 15% (w/w) of dye (F) and 5% (w/w) of dye (C) and dyes
SUBSTITUTE SHEET (RULE 26)
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WO 00/63298 PCT/EP00/03150
16
wool in navy-blue shades. The dye mixture exhibits excellent dyestuff
properties (i.e.
lightfastness and washfastness).
O
c~
N
N i 'N
\ \ ~ ~ (F)
OH HN N F
/ / N=N
/ ( \
S03H
H03S \ / S03H
Example 10
A dye mixture according to the invention is prepared by mechanically mixing
170
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
is of formula (A) with 23 parts of a red electrolyte-salt containing powder
with a content
of 65% of a dye of formula (F). The resulting mixture contains 85% (w/w) of
dye (A)
and 15% (w/w) of dye (F) and dyes wool in navy-blue shades. The dye mixture
exhibits excellent dyestuff properties (i.e. lightfastness and washfastness).
2o Example 11
A dye mixture according to the invention is prepared by mechanically mixing
150
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 30.7 parts of a red electrolyte-salt containing powder
with a
2s content of 65% of a dye of formula (G) and with 10.0 parts of a red
electrolyte-salt
containing powder with a content of 50% of a dye of formula (C). The resulting
mixture contains 75% (w/w) of dye (A) and 20% (w/w) of dye (G) and 5% (w/w) of
dye (C) and dyes wool in navy-blue shades. The dye mixture exhibits excellent
dyestuff properties (i.e. lightfastness and washfastness).
(G)
N ~ N / SOZCH2CHZOS03H
\ \
OH HN N N
/ / N=N H
S03H
_ \ / __ __
SUBSTITUTE SHEET (RULE 26)
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Example 12
A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 23 parts of a red electrolyte-salt containing powder with
a content
of 65% of a dye of formula (G) and with 10.0 parts of a red electrolyte-salt
containing
powder with a content of 50% of a dye of formula (C). The resulting mixture
contains
80% (w/w) of dye (A) and 15% (w/w) of dye (G) and 5% (w/w) of dye (C) and dyes
wool in navy-blue shades. The dye mixture exhibits excellent dyestuff
properties (i.e.
to lightfastness and washfastness).
Example 13
is A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 30 parts of a red electrolyte-salt containing powder with
a content
of 50% of a dye of formula (H) and with 10.0 parts of a red electrolyte-salt
containing
powder with a content of 50% of a dye of formula (C). The resulting mixture
contains
20 80% (w/w) of dye (A) and 15% (w/w) of dye (H) and 5% (w/w) of dye (C) and
dyes
wool in navy-blue shades. The dye mixture exhibits excellent dyestuff
properties (i.e.
lightfastness and washfastness).
2s CI (H)
N i 'N / SO2CH2CHZOS03H
HsC O \
OH HN N N
/ N-N H
3o S03H
H03S \ / S03H
SUBSTITUTE SHEET (RULE 26)
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WO 00/63298 PCT/EP00/03150
18
Example 14
A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 30 parts of a red electrolyte-salt containing powder with
a content
of 50% of a dye of formula (I) and with 10.0 parts of a red electrolyte-salt
containing
powder with a content of 50% of a dye of formula (C). The resulting mixture
contains
80% (w/w) of dye (A) and 15% (w/w) of dye (I) and 5% (w/w) of dye (C) and dyes
wool in navy-blue shades. The dye mixture exhibits excellent dyestuff
properties (i.e.
to lightfastness and washfastness).
NHCN
N i _N / S02CH2CH20S03H
H3C'O \ ~ ~ \ I
is I / OH HN N H
N=N / I \
S03H
H03S \ / S03H
Example 15
2o A dye mixture according to the invention is prepared by mechanically mixing
160
parts of a navy-blue electrolyte-salt containing powder with a content of 50%
of a dye
of formula (A) with 30 parts of a red electrolyte-salt containing powder with
a content
of 50% of a dye of formula (J) and with 10.0 parts of a red electrolyte-salt
containing
powder with a content of 50% of a dye of formula (C). The resulting mixture
contains
2s 80% (w/w) of dye (A) and 15% (w/w) of dye (J) and 5% (w/w) of dye (C) and
dyes
wool in navy-blue shades. The dye mixture exhibits excellent dyestuff
properties (i.e.
lightfastness and washfastness).
(J)
NHCN
30 ~ S02CH2CH20S03H
N~N
HsC \
OH HN N N
N-N H
I\
S03H
H03S ~ ~ S03H
SUBSTITUTE SHEET (RULE 26)
