Note: Descriptions are shown in the official language in which they were submitted.
~7~)9~3
The prcsent lnvention relates to liquid preparatlons oE reactive
dy~estu~es.
More particularl~, the present invent:lon relates to liquid, aqueousd~eing preparations which contain one o~ the herelna~er mentioned reactlve
d~estuffs I OT II or III or I~ or ~ or ~I, which in the ~orm o~ the free acid
correspond either to formula ~I)
COOH
CH2-02S ~ NH-CO ~ ~ - _ N _ ~ ~ S03H
CIH2 OH
0S03
or to formula (II)
COOH
H03SO-CH2-CH2-02S 3 ~ :
OH
or to formula (III)
CH31 ~ N
H3S-CH2-CH2 2S ~ N=N ~ N _ ~ - SO H (III)
CH3 OH
Or to formula ~
HO ~H2
S2 ~ N N 1' ~r N~N ~ - 73 ~IV)
CIH2 H03S S03H I 2
H03SO-CH2 ' CH2-OS03H
" . 2
'
` 1~7~9~3
or to formula (~)
Cu
/ \ ~lOOC
~ N=N ~ ~J - N=N ~ V)
Ha3so~`cE~2-cH2-~;o2
~C~I H03S H0 ~ ~ :
or to formula (~I) S0 H
S03H ~ N
H03S / ~ - N~N ~ i (VI)
,, .'':
S02-CH2-CH2-OS03EI
These dyeing preparations are characterized by that they contain one of the
aforementioned dyestuffs, preferably in the form of their alkali metal salts,
in particular sodium salts, in aqueous solution in a concentration of 5 to 35%
by weight, preferabl~ 15 to 30% by weight, re~erred to the pure dyestuf~ of
the formula ~I) or (II) or ~III) or (IY) or CJ) or CVI) and havlng a pH-value
of between 3 and 7, preferably between 5.5 and 6.8~ and additionally contain-
ing 1 to 5% by weight of buf~er substances.
The dyestuff of the formula ~I) is described ln German Patent Speci-
fication DT-PS 1 206 107~ Example 1, the dyestuff of the formula ~II) is known
from German Patent Specification DT-PS 1 282 213, Example 1, the dystu~f of
the formula ~III) is known from German Patent DT-PS 1 150 163, Example 1, the
d~es!~u~ the~ormula CIV) is known from German Auslegschrift 1 619491,
Example 8, the dyestuff of the formula CV) is known from German O~enlegungs-
schrift 1 544 538, 1st Example of the Table on page 24, and the d~estu~f of
. _ 3 _
..... . ... .. . - - : ~ .................................. .
.
~37~903
the eormula ~I) is knol~ from German 0~eenlegungsschrift 1 80~ 524, Examples
4 c~nd 5.
After their synthesis, water-soluble s~eactive dyestuffs are commonly
isolated in such a way that they are salted out from the aqueous reaction
solution, that the precipitated salt-dyestuff mixture is suction-filtered and
the press cake obtained is driecl. Another technically common method to isolate
the dissolved dyestuff, which is usually easy to dissolve in water, frwn the
synthesis solution, is the direct drying, for example the spray drying, of the
preparation solution.
For the desired dyeing purpose, the salt-containing dyestuf powder
is usually ad~usted, after the drying process, to a determined dyestuf~ con-
tent by the admixture of n0utral inorganic salts, ~or example sodium sulfate.
However, these common powder formulations of reactive dyestuffs have
several drawbacks which are due particularly to the dust formation of these
pulverulent dyeing preparations when they are being handled, or example during
emptying or re-filling weighing and measuring, or in the preparation of the
dyebaths or prin~ing pastes. In this connection, this dust formation not only
represents an annoyance for the workers in the manufacturing plant or the ap-
plication unit, but in the dyeing or printing processes it may also lead to `~
unpleasant specks of undyed or already dyed merchandise, due to the settling
of the dyestuff dust. On the other hand, the dust removal of pulverulent d~e-
stuffs by means o~ the common dust removing agents on the basis of mineral oil
alwa~s involves the risk of oily deposits in the dyeing and printing opera-
tions, which leads to stained, and thus useless, dyeings and printings. More-
overJ these pulverulent dyestuffs often prevent the application o:~ measures
of rationalization which are technically desirable, such as, or example, con-
tinuous d~eing processes or automatic measuring and weighing de~ices.
These drawbacks which are equally true ~or the pulverulent d~estu$~s
~70~903
of the ~ormulae (I), ~II), (III), (IV), (V) and (VI) are completelr avoided
by the liquid pr~parations of the inventlon of the respective dyestuffs. -
Moreover, the novel preparations have the advantage, both for the dyestuff
producers and those who use them, in comparison with the pulverulent dyestuff
formulations, that the salt charge of the waste water is considerably reduced.
The novel liquid dyeing preparations of the dyestu~fs of the formula
(I), (II), (III), (IV), CV) or ~I) are prepared in such a way - in accordance
with the invention - that the clarified dyestuff solution obtained by the syn~
thesis is used directly and is optionally, i.e. advantageously, adjusted to the
desired higher dyestuff content, either by concentration7 for example~ by re-
moval by distillation of a part of the water in vacuo, or advantageously by
adding a dried, for example spray-dried, proportion o the same clari~ied dye~
stuff solution obtained in the synthesis in which process buf~er substances
are also added to this dyestuff solution in all cases.
For the preparation of these dyeing compositlons according to the
inventi~n which have up to 35% by weight of dyestuff, it is advantageou~ to
use aqueous clarified dyestuff solutions as starting compounds, which have a
content of inert salts, such as sodium sulfate or sodium chlorideJ that is as
low as possible and is less than ~0~ ~y weight of the dyestuf~ content of
these dyestuff solutions obtained in the synthesis. ~or the preparation of
dyeing compositions having a lower dyestuff content, such as those containing
up to 15% by weight of dyestuEf, the content of inert salt of the starting
solution should be lower than their dyestuff content. As a rule, the content
of inert salt of the aqueous dyestuff solutions obtained in the synthesis is
below these limits. In order to keep the content of inert salts below these
limits, also for solutions of ~he reactive dyestuff with the ~-sulfa~oeth~l-
sulfonyl group which has been obtained by esterification of the ~ hydro~y-
ethylsulfonyl group with concentrated sul~uric acid, the excess sul~uric ~cid
_
..
: `, .
.
: .
.
~7(~g~33
necessary or ~he formation o~ this sulfuric acid semi-ester group cannot be
neutralized with soclium hydroxide solution or other reagents which lead to
easily soluble inert salts. It is recommended, rathe~r, to neutralize the ex-
cess sulfuric acid l~ith calcium carbonate and to scpclrate the dyestuf solu~
tion from the sparingly soluble calcium sulfate by way of iltration. This
process has been described, inter alia, in German O~enlegungsschriften No.
1.955.849, Example l; No. 2.049.664, Example 1, and No. 2.06~.081, Example 2.
The solutions of the dyestuff of the formula ~I), ~II), (III), ~IV),
~V) or ~VI) obtained by the synthesis contain from 5 to 15% by weight o dye-
stuff and may be adjusted to a dyestuff content of from about 30 to 35% by
weight by the addition of dried dyestuff or by removal o~ water ~y distilla-
tion under reduced pressure.
For the dyestuff producer, there is no need anymore or the mothe*
liquors which have a very high content o salt and which are partially satu-
rated with salt, and also for those who use the dyestuf~s, the salt content
of the waste water is considerably reduced, since the amounts of salt used for
the adjustment of the dyestuff powders are no longer required ;n the prepara-
tion of the liquid formulations according to the invention.
For the dyeing preparations of the invention, all buf~er substances
~Q are suitable that are unable to react chemically with the ~-sulfatoethylsul-
fonyl group, or its ~inylsulfonyl analog, which would lead to a reduced dye-
stuf yield, such as sodium and potassium acetate, sodium and potasslum oxa-
late, the acid sodium and potassium salts o~ phosphoric acid, mixtures of the
different sodiu~l or potassium salts o~ phosphoric acid, as well as sodium
borate. There are preferred sodium borate and disodium-hydrogenophosphate
as well as sodium-dihydroge~ophosphate.
The mechanlsm of the reaction of reacti~e dyestu~$s of t~e
above type ~ith cellulose fibers is generally known. Thus, the ~ormation o$
- 6 -
- ~ .
.
:, . . ~ ~ ,".,, ., ., ' ' , ~ , ,
,
,,
76~;)3
the covalent bond bet~een the ~i~er substrate and the dyestuff molecule ac-
cording to the reaction (4) o~ the scheme shown below, after conversion of
the ~-sulfato-ethyl-sulfonyl group into the vinyl-sulfone group, in the pres-
ence of agents having an alkaline action in accordance with reaction ~1), leads
to the known good fastness properties of dyeings with these reactive dyestuff.
Furthermore, it has been known from the use of the reactive dyestufs
with the ~-sulfatoethyl-sulfonyl group, that this reactive group, also in the
form of its vinyl-sulfonyl group, with water shows a reaction - not only in
the presence of alkalies, but also in the acid range - that is concurrent with
the dyeing reaction (4) itself, according to reactions ~2) or ~3) of the
scheme, and results in the S-hydroxyethyl-sulfonyl group which is but slow to
react with the fiber substrate.
F-SO2-CH2-CH2-O-cell.
~4) ~ ~cell.-OH
~1) I .
F-S02- H2 C~12-0-S03~ F-S02-CH=C~ 2
'H20 ~2) ~3) -'H20
-~l2so4
~ F-S02-CH2-CH2-oH <
wherein F respresents the radical of the d~estuff molecule and m has the
above meaning, and cell.-OH stands for the cellulose.
The hydrolysis ~2) and the addition of water ~3) are practically
irreversible under dyeing conditions and thus reduce the dyestuff yield.
For this reason, in the manufacture o~ water~soluble reactive dye-
stuffs, the above-mentioned separationanddr~ing o~ the reactive dyestuf~s
2Q ~rom the synthesis solution is in general also carried out, with regard to
~ 7 --
,
" ' ~ ~:' ' : '
~L~7~9~3
time, too, directly after the s~lthesis in order to a~oid losses of the tinc-
torial strength.
Thus, it w~s the more surprising to find that neutral to weakly
acidic aqueous buffered solutions, which contain one of the reactive dyestuffs
~I~ or ~II) or (III) or ~IV) or ~) or (VI), can be stored over a fairly long
period of time without reduction of their tinctorial strength. Aqueous solu-
tions of the dyestuff of the formula (i) or (II) or (III) or (I~) or ~V) or ~ -
IVI) according to the invention yield dyeings and prints unaltered intensity
of shade, even after a storage of several months, for example 6 months, at
room temperature or after storage o several weeks, for example 8 weeks, at
50C.
The dyeing preparations of the invention are suitable for the dye-
ing and printing of fibrous materials of wool, silk, polyamide and natural or
regenerated cellulose, or of fiber mixtures containing one or several of the
types of fibers mentioned, according to the methods usually employed and well
known in the dyeing with reactive dyestuffs, after dilution with water and,
optionally, after addition of the usual dyeing auxiliary agents or, in cor-
responding manner, after addition of the thickeners usually employed in print-
ing and, optionally, of printing auxiliary agents.
The following Examples illustrate the invention.
EXAMPLE l:
150 Parts by weight o~ an aqueous clarified dyestuf~ solution o the
dyestuff of the following formula (known from German Offenlegungsschrift No.
1.544.538, 1st Example of the Table given on page 24)
.' ','
':
1C~7~3
Cu \ ~IOOC
~Io3so-C}l~-c~l2-o2s ~ 3 \
CH3
~03H
ha~ing a pH value of 5.8 and a d~estuf content of 15% by ~e:ight, which solu~
tion had been obtained in usual manner in the synthesis o~ the dyestuf~ by
diazotizing and coupling corresponding starting compounds and b~ way of the
complex formation, were mixed, while stirring, with 36 parts by weight of a
dry dyestuff powder having a dyestuf content o~ 70% by weight, the powder
having been obtained by spray drying another part of the same clarified dye.
stuff solution. The 186 parts by weight thus obtained of an aqueous solution
containing 25.7% by weight of pure dyestuff yielded, a~ter the addition o~
5 parts by weight of disodiumhydrogenophosphate, 191 parts ~y weight of an
aqueous dyeing preparation having a content of pure dyestuff of 25% by weight
and a pH value of 6.2.
Using 2 parts by weight of this solution, dye baths, paddlng liquors
and printing pastes were prepared each time according to known and common pro~
cesses which - when applied onto cotton and fixed according to methods common
for reactive dyestuffs - yielded black or grey dyeings and prints which had
the same întensity of shade as those prepared while using accordingly dye
baths, padding liquors or printing pastes of the same concentration, with 1
part by weight of a powder formulation containing 50% by weight of pure dye~ ;
stuf~.
~ 9 ~ .
~ . .
'
'
~7~903
This intensity o~ shade of the pTints and d~eings was maintained un-
altered ~hen the novel aqueous preparation mentioned above was stored at 50C
for ~ weeks in a closed vessel.
EXAMPLE 2:
.
200 Parts b~ weight of an aqueous clari~ied dyestufe solution of the
dyestuff mentioned in Example 1 having a pH value of 5.7 and a dyestuff con-
tent of about 11% by weight, which solution had been obtained in usual manner
in the synthesis of ~he dyestuff by dia70tizing and coupling corresponding
starting compounds and by way of the complex formation, were mixed, while
stirring, with 48 parts by weight of a dry d~estuff powder having a dyestuff
content of 60% by weight, the powder having been obtained by spray drying
another part of the same clarified dyestuff solution. The 248 parts by weight
thus obtained of an aqueous solution containing 20.5% by weight o~ pure dye-
stuff yielded - after the addition of 6 parts b~ weight of disodiumhydrogeno-
phosphate - 254 parts by weight of an aqueous dyeing preparation having a con-
tent of pure dyestuff of 20% by weight and a pH value o~ 6Ø
Using 5 parts by weight of this solution, dye baths, padding liquors
and printing pastes were prepared each time according to known and common pro-
cesses which - when applied onto cotton and fixed according to methods common
Eor reactive dyestuffs - yielded black or grey dyeings and prints which had
the same tinctorial strength as those prepared while using accordingly dye
baths, padding liquors or printing pastes of the same concentration, with 2
parts by weight of a powder formulation containing 50% by weight of pure dye-
stuff.
This tinctorial strength of the prints and d~eings was maintained
unaltered when the novel aqueous preparation mentioned above was stored at
20C for 3 months in a closed vessel.
~ ~ 10 -
.: ~
~0~9~3
EXAMPLE 3:
150 Parts by weight of an aqueous clarified dyestuff solution of the
dyestu~f mentioned in Example 1 having a pH value of 5.8 and a dyestuff con-
tent of 15% by weight, which solution had been obtained in usual manner in the
synthesis of the dyestuff by diazotizing and coupling corresponding starting
compounds and by way of the complex formation, were mixed with 5 parts by
weight of disodiumhydrogenophosphate. Of this dyestuff solution, 65 parts by
weight of water were distilled off, while stirring at 60C and under a vacuum
of 18 Torr. 90 Parts by weight of an aqueous dyeing preparation were obtained
which had a content of pure dyestuff of 25% by weight and a pH value of 6.4
at 20C.
Using 2 parts by weight of this solution, dye baths, padding liquors
and printing pastes were prepared each time according to known and common pro~
cesses which - when applied onto cotton and fixed according to methods common
for reactive dyestuffs - yielded black or grey dyeings and prints which had
the same intensity of shade as ~hose prepared while using accordingly dye
baths, padding liquors or printing pastes of the same concentrationJ with 1
part by weight of a powder formulation containing 50% by weight of pure dye
stuff.
~lis lntensity of shade of the prints and dyeings was maintained
unaltered when the novel aqueous preparation mentioned above was stored at
50C for 6 weeks in a closed vessel.
EXAMPLE 4:
200 Parts by weight of an aqueous clarified dyestuff solution of
the dyestuff mentioned in Example 1 having a pH value of 5.7 and a dyestuff
content of 11% by weight, which solution had been obtained in usual mamler in
the synthesis of the dyestuff by diazotizing and coupling corresponding start-
ing compounds and by way of the complex formation, were mixed, while stirring,
~L~7~D03
wlth 48 parts by tYeight o~ a clr~ d~estu~e powder havillg a dy0stuf~ content
of 60% by wei~ht, the pol~der ha~ing been obtained by spray drying another part
of the same clarified dyestuf~ solution. The 248 parts by weight thus ob-
tained of an aqueous solution containing 20.5% by weight of pure dyestuff
yielded - ater the addition of 6 parts by weight of sodium borate - 254 parts
b~ weight of an aqueous dyeing preparation having a content of pure dyestuff
of 20% by weight and a pH value of 5.9.
Using 5 parts by weight of this solution, dye baths, padding liquors
and printing pastes were prepared each time according to known and common pro-
cesses which - when applied onto cotton and fixed according to methods common
for reactive dyestuffs - yielded black or grey dyeings and prints which had
the same intensity of shade as those prepared while using accordingly dye
baths, padding liquors or printing pastes of the same concentration, with 2
parts by weight of a powder formulation containing 50% by weight of pure dye~
stuff.
This intensity of shade of the prints and dyeings was maintained
unaltered, when the novel aqueous preparation mentioned above was stored at ;~
20C for 3 months in a closed vessel.
EXAMPLE 5:
200 Parts by weight of an aqueous clarified dyestuff solution of
the dyestuf corresponding to the ~ormula
H0 NH2
H03S ~' ~ SO;H S02 CH2 H2 S03H
~which had ~een known from German Auslegeschrift No. 1.619.491~ Example 8)
and having a pH value of 6.0 and a dyestu~f content of 15% ~ ~e~ght, which
solution had ~een obtained in usual manner in the synthesis o~ the dyestuff
r 12 ~
" ' ' - . ''' ' ,.
-
.: .
~7~9C~3
by diazotlzing and coupling corresponding starting compounds, were mixed,
while stirring, with 37 parts by weight of a dry dyestuff powder having a
dyestuff content of 67% by weight~ the powder having been obtained by spray
drying another part of the same clarified dyestuff solution. The 237 parts by
weight thus obtained o an aqueous solution containing 23.1% by weight of pure
dystuff and having a pH value of 6.0 yielded - after the addition of 6 parts
by weight of disodiumhydrogenophosphate - an aqueous clyeing preparation having
a content of pure dyestuff of 22.5% by weight and a pH value of 6.2.
Using 2 parts by weight of this pH-stabilized solution, dye baths~
padding liquors and printing pastes were prepared each time according to known
and common processes which - when applied onto cotton and fixed according to
methods common for reactive dyestuffs - yielded black or grey dyeings and
prints which had the same intensity of shade as those prepared while using
accordingly dye baths, padding liquors or printing pastes of the same concen~
tration, with 1 part by weight of a powder formulation containing 45% by weight
of pure dyestuff.
This intensity of shade of the prints and dyeings was maintained un-
altered, when the novel aqueous preparation mentioned above was stored at
50C for 6 weeks in a closed vessel.
EXAMPLE 6:
200 Parts by weight of an aqueous clarified dyestuff solution o~
the dyestuff mentioned in Example 5 having a p~l value of 5.5 and a dyestuff
content of about 14.5% by weight, which solution had been obtained in usual
manner in the synth~sis of the dyestuff by diazotizing and coupling correspond-
ing starting compounds, were mixed, while stirring, with 45 parts by weight of
a dry dyestuff powder having a dyestuff content of 64% by weight, the powder
having been obtained by spray drying another part of the same clari~ied dye-
stuff solution. The 245 parts by weight thus obtained of an aqueous solution
~; - 13 -
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"
~07~13
containing 23.6% by weight of pure dyestuf~ yielded - after the addition of
12 parts by weight o~ disodi~hydrogenophosphate - 257 parts by weight of an
aqueous dyeing preparation having a content of pure dyestuf~ of 22.5% by
weight and a pil value of 6.2.
Using 2 parts by weight of this pH-stabilized solution, dye baths,
padding liquors and printing pastes were prepared each time according to known
and common processes which - when applied onto cotton and fixed according to
methods common for reactive dyestuffs - yielded black or grey dyeings and
prints which had the same intensity of shade as those prepared while using
accordingly dye baths, padding liquors or printing pastes of the same concen-
tration, with 1 part by weight of a powder formulation containing 45% by weight
of pure dyestuff.
This intensity of shade of the prints and dyeings was maintained un-
altered, when the novel aqueous preparation mentioned above was stored at
20C for 4 months in a closed vessel.
EXAMPLE 7:
200 Parts by weight of an aqueous clarified dyestuff solution of
the dyestuff men~ioned in Example 5 having a pH value of 5.5 and a dyestuff
content of 14.5% by weight, which solution had been obtained in usual manner
in the synthesis of the dyestuff by diazotizing and coupling corresponding
starting compounds, were mixed with 12 parts by weight of disodiumhydrogeno-
phosphate. Of this dyestuff solution, 83 parts by weight of water were dis~
tilled of~, while stirring at 60C and under a vacuum of 18 Torr. 129 Parts
by weight of an aqueous dyeing preparation were obtained which had a content
of pure dyestuff of 22.5% by weight and a p~ value of 6.5 at 20C.
Using 2 parts by weight of this solution, dye baths, padding liquors
and printing pastes were prepar~d each time according to known and common pro-
cesses which - when applied onto cotton and ~ixed according to methods common
- 14 ~
:
.. ~
" :'
~7~9~3
~or reactive dyestuf~s ~ yielded black or grcy d~eings and prlnts which had
the same intensi-ty of shade as those prepared while using accordingly dye
~aths, padding liquors or printing pastes of the same concentration, with 1
part by weight of a powder formulation containing 45% by weight of pure dye-
stuff.
This intensity of shade of the prints and dyeings was maintained un-
altered, when the novel aqueous preparation mentioned above was stored at
50C for 6 weeks in a closed vessel.
EXAMPLE 8:
200 Parts by weight of an aqueous clarified dyestuff solution of
the dyestu~f mentioned in Example 5 having a pH value of 6.0 and a dyestuff
content of 12% by weight, which solution had been obtained in usual manner in
the synthesis of the dyestuff by diazotizing and coupling corresponding start-
lng compounds, were mixed, while stirring, with 14 parts by weight of a dry
dyestufE powder having a dyestuf content of 67% by weight, the powder having
been obtained by spray drying another part of the same clarified dyestuff
solution. The 214 parts by weight thus obtained of an aqueous solution con-
taining 15.6% by weight of pure dyestuff and having a pH value of 6.0 yielded
- after the addition of 8 parts by weight of sodium borate - an aqueous dye-
Z ing preparation having a content of pure dyestuff of 15% by weight and a pH
value of 6.2.
. Using 3 parts by weight of this pH-stabilized solution, dye baths,
padding liquors and printing pastes were prepared each time according to known
and common processes which - when applied onto cotton and fixed according to
methods common for reactive dyestuffs - yielded black or grey dyeings and
prints which had the same intensity of shade as those prepared while using
accordingly dye baths, padding liquors or printing pastes of the same concen-
tration, with 1 part by weight of a powder formulation containing 45% by weight
.. - 15 -
~7~ 3
of pure dyestuff.
This intensit~ o~ shade of the prints and dyeings was maintained
unaltered, when the novel aqueous preparation mentioned above was stored at
20C for 4 months in a closed vessel.
EXAMPI.E ~:
100 ~arts by weight of an aqueous clari~ied dyestuff solution of
the dyestuff corresponding to the formula
H3C
SO3H / _ N
N=N ~
S2 -C~12 -C112-OS03~1
(which has been known from German Offlengungsschrlft No. 1.804.524, Examples
4 and 5) and having a pH value of 6.0 and a dyestuf~ content of 15% by weight,
which solution had been obtained in usual manner in the synthesis of the dye-
stuff by diazotizing and coupling corresponding starting compounds9 were mixed,
while stirring, with 24.5 parts by weight of a dry dyestuff powder having a
dyestuff content of 67% by weight, the powder having been obtained by~spray
drying another part of the same clarified dyestuff solution. The 124.5 parts
by weight thus obtained of an aqueous solution containing 25.3% by~weight o~
pure dyestuff and having a pH value of 6 yielded - after the addition of 2
parts by weight of disodiumhydrogenophosphate - an aqueous dyeing preparati~n
having a content of pure dyestuff o~ 25% by weight and again a pH value of
6Ø
Using 2 parts by weight of this pH-stabilized solution, dye baths,
padding liquors and printing pastes were prepared each time according to known
- - 16 -
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~LID7~9(~
and common processes ~hich - when applied onto cotton and fixed according to
methods common ~or reactive dycstuffs - yielded yellow dyeings and prints
~hich had the same intensity Oe shade as those prepared while using according-
ly dye baths, padding liquors or printing pastes of the same concentration,
~ith 1 ~art by weight of a powder formulation contain.Lng 50% by weight of pure
dyestu~f.
This intensity of shade of the prints and dyeings was maintained un-
altered, when the novel aqueous preparation mentioned above was stored at
50C for 6 weeks in a closed vessel.
EXAMPLE 10:
200 Parts by weight of an aqueous clarified dyestuff solution of
the dyestuff mentioned in Example 9 having a pll value of 5.8 and a dyestuff
content of about 13% by weight, which solution had been obtained in usual
manner in the synthesis of the dyestuff by diazotizing and coupling correspond-
ing starting compounds, were mixed, while stirring, with 34 parts by weight
of a dry dyestuff powder having a dyestuff content of 65% by weight, the
powder having been obtained by spray drying another part of the same clari~ied
dyestuff solution. The 234 parts by weight thus obtained of an aqueous solu-
~ion containing 20.5% by weight of pure dyestuff yielded - after the addition
of 6 parts by weight of disodiumhydrogenophosphate - an aqueous dyeing pre-
paration having a content of pure dyestuff of 20% by weight and a pH value of
6.1.
Using 5 parts by weight o~ this pH-stabilized solution, dye baths,
padding liquors and printing pastes were prepared each time according to known
and common processes which - when applied onto cotton and fixed according to
methods common for rea~tive dyestuffs - yielded yellow dyeings and prints
which had the same intensity of shade as those prepared while using according-
ly dye baths, padding liquors or printing pastes of the same concentration,
- 17 -
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:
~ 7~9~3
with 2 p~rts by~weight o~ a powder ~ormulation containing 50% by weight of
pure dyestuff.
This intensity of shade of the prints and dyeings was maintained un-
altered, when the novel aqueous preparation mentioned above was stored at
20C for 3 months in a closed vessel.
EXAMP~E 11:
200 Parts by weight of an aqueous clarified d~estuff solution of
the dyestuff mentioned in Example 9 having a pH value of 6 and a dyestuff con-
tent of 13% by weight, which solution had been obtained in usual manner in the
synthesis of the dyestuff by diazotizing and coupling corresponding starting
compounds, were mixed with 3 parts by weight of disodiumhydrogenophosphate.
Of this dyestuff solution~ 73 parts by weight of water were distilled off,
while stirring at 60C and under a vacuum of 18 Torr. 130 Parts by weight of
an aqueous dyeing preparation were obtained which had a content of pure dye-
stu~ of 20% by weight and a pH value of 6.1 at 20C.
Using 5 parts by weight of this pH-stabilized solution, dye ~aths,
padding liquors and printing pastes were prepared each time according to known
and common processes which - when applied onto cotton and ~ixed according to
methods common for reactive dyestuffs - yielded yellow dyein~s and prints
which had the same intensity of shade as those prepared while using according-
ly dye baths, padding liquors or printing pastes of the same concentration,
with 2 parts by weight of a powder formulation containing 50% by weight of
pure dyestuff.
This intensity of shade of the prints and dyeings was maintained
unaltered when the novel aqueous preparation mentioned above was stored at
2QC for 3 months in a closed vessel.
EXAMP~E 12:
:::
100 Parts by weight of an aqueous clari~ied dyestuf~ solution o~
., . ,: . . ~ .
- ' . .' ': .. ,: . , :...................................... .
:. ,: ~ :
~7~gC~3
the dyestu mentioned in Example 9 having a pH value of 6 and a dyestu~ con-
tent o 15% by weight, which solution had been obtained in usual manner in
the synthesis of the dyestu~f by diazotizlng and coupling corresponding start-
ing compounds, were mixed, while stirring, with 27 parts by weight of a dry
dyestuff powder having a dyestu content of 67% by weight, the powder having
been obtained by spray drying another part of the same clarified dyestuff
solution. The 127 parts by weight thus obtained of an aqueous solution con-
taining 26.1% by weight of pure dyestuff yielded - after the addition of 8
parts by weight of sodium borate - an aqueous dyeing preparation having a con
tent o pure dyestuff of 20% by weight and again a pH value of 6.
Using 2 parts by weight o this pH-stabilized solution, dye baths,
padding liquors and printing pastes were prepared each time according to known
and common processes which - when applied onto cotton and fixed according to
methods common for reactive dyestufs - yielded yellow dyeings and prints
which had the same intensity o~ shade as those prepared while using according-
ly dye baths, padding liquors or printing pastes of the same concentration,
with 1 part by weight o a powder formulation containing 50% by weight o pure
dyestuE.
This intensity of shade of the prints and dyeings was maintained
unaltered, when the novel aqueous preparation mentioned above was stored at
50C for 6 weeks in a closed vessel.
EXAMPLE 13:
100 Parts by weight of an aqueous clari~ied solution o~ the dyestuf$
o~ the above ~`ormula ~I) having a pH-value o 5.8 and a dyestuf content o
about 15% by weight, which solution had been obtained in the usual manner ln
the synthesis o~ the dyestuff by diazotization and coupling o corresponding
starting compounds, were combined, while stirring, with 19 parts by weight o~
a dry dyestuff powder having a d~estu~ content o 67% by weight and which
- 19 _
: ~ .
9~3
had been obtained by spray-dr~ing o~ another part o~ the same clarified dye-
stuff solution. The 119 parts by weight of an aqueous solution containing
23.3% by ~eight o pure d~estu~ and having a pll-value of 5.8 yielded, ater
addition of 4 parts by wei~ht of disodium-hydrogenophosphate, an aqueous dye-
ing preparation having a content of pure dyestu~f o~ 22.5% by weight and a
p}l-value of 6Ø
Using 2 parts by weight o~ this pH-stabilized solution, dyebaths,
padding li~uors and printing pastes were prepared in known and usual manner,
which when applied and fixed on cotton according to the methods usually em-
ployed for reactive dyestuffs, yielded yellow dyeings and prints which had
the same depth of shade as those prepared using dyebaths, padding liquors or
printing pastes of the same concentration and that had been prepared with 1
part by weight of a powder formulation containing 45% by weight o~ pure dye-
stuEf.
This intensity of shade of the prints and dyeings was unaltered
even if the novel aqueous preparation mentioned above had been stored for 6
weeks at 50C in a closed vessel.
EXAMPL~ 14:
100 Parts by weight of an aqueous clari$ied dyestuff solution of
the dyestuf of the above formula ~I) having a pH-value of 5.8 and a dyestuff
content of about 13% by weight, which solution had been obtained in the usual
manner by the synthesis of the dyestuff by diazotization and coupling of cor-
responding starting substances, were mixed, while stirring, with 17 parts by~ -
we~ght of a dry dyestuff powd0r having a dyestuff content of 65~ by weight
and which had been o~tained by spray-drying of another part of the same clari~
fied dyestu~f solution. The 117 parts by weight so obtained o~ the aqueous
solution containing 20.5 parts by~weight of pure dyestu$f y~ielded, after addi~
tion of 3 parts by ~eight of sodium bicar~onate, an aqueous d~eing preparation
- 20 -
: . . .. . . . .
.
, ' "'~ ' ' : :
--. . , , ', . .
~L~7~
having a content of pure dyestu~f o~ 20.0% by weight and a pH-value of 6.1.
Using 5 parts by weight of this pH-stabili~ed solution, dyebaths,
padding liquors and printing pastes were prepared in known and usual manner,
which when applied and fixed on cotton according to the methods usually em-
ployed for reactive dyestuffs, yielded yellow dyeings and prints which had
the same depth of shade as those prepared using dyebaths, padding liquors and
printing pastes of the same concentration and that had been prepared with 2
parts by weight of a powder formulation containing 50% by weight of pure dye-
stuff.
This shade intensity of the prints and dyeings was unaltered even
if the novel aqueous preparation mentioned above had been stored ~or 3 months
at 20C in a closed vessel.
EXAMPLE 15:
200 Parts by weight of an aqueous clarified drestuff solution of
the dyestuff of the above formula ~I) having a pH-value of 6.0 and a dyestuff
content of 12% by weight, which solution had been obtained in the usual manner
by the synthesis by diazotization and coupling of corresponding starting sub~
stances, were mixed with 3 parts by weight of disodium~hydrogeno-phosphate.
96.5 Parts by weight of water were removed ~rom this dyestuf~ solution by~ dis-
tillation, while stirring, at 60C and under a reduced pressure of 18 Torr.
106.5 Parts by weight o~ an aqueous dyeing preparation were obtained which had
a content of pure dyestwff of 22.5% by weight and a pH-value of 6.1 at 20C.
Using 2 parts by weight of this solution, dyebaths, padding liquors
and printing pastes were prepared in the usual and known manner, which when
applied and fixed on cotton according to the methods usually employed for re-
active dyestuffs, yielded yellow dyeings and prints which had the same depth
of shade as those produced using dyebaths, padding liquors and printing pastes
of the same concentration and that had been prepared with l part by weight of
21
'
903
a powder ~ormulation containirlg 45% by welght o~ pure dyestuff.
lhis intensitr o~ shade of the dyeings and prints was obtained with
unaltered ~uality when the above-indica~ed novel aqueous preparation had been
stored for 3 months at 20C in a closed vessel.
EXA~PLE 16:
100 Parts by weight of an aqueous clarified d~estu~f solution of
the dyestuff of the above formula ~I) having a pH-value of 6.0 and a dyestuff
content of 13% by weightJ and which had been obtained in the usual manner in
the synthesis of the dyestuff by dia~otizing and coupling corresponding start-
ing substances, were mixed, while stirring, with 25 parts by weight of a dry
dyestuff powder which had a dyestuff content o~ 65% by weight and had been 7
obtained by spray-drying of another part o the same clarified dyestuff solu-
tion. The 125 parts by weight so obtained of an aqueous solution containing
23.4% by weight of pure dyestuff yielded, after addition o~ 5 parts by welght
of sodium borate, an aqueous dyeing preparation which showed a content o~ pure
dyestuff of 22.5% by weight and a pH-value of 6Ø
Using 2 parts by weight of this pH-stabilized solution, dyebaths9 ~-
padding liquors and printing pastes were prepared which, when applied and
~ixed on cotton according to the methods usually employed for reactive dye~
stuffs, yielded yellow dyeings and prints which had the same depth of shade
as those produced with dyebaths, padding liquors and printing pastes of the
same concentration bu~ had been prepared with 1 part by weight o~ a powder
formulation containing 45% by weight of pure dyestuff.
This intensity of shade of the dyeings and prints was obtained with
unaltered quality, when the above-indicated novel aqueous preparation had ~een
stored for 6 weeks a~ 50C in a closed vessel.
EX~MPLE 17:
100 Parts by weight o~ an aqueous, clari~ied dyestu~f solution o~
. :~'
~L071~g~3
the dyestu~ of the above ~ormula (I) havin~ a pH-value o~ 6.0 and a dyestu~f
content of 13% by welght, and which had been obtalned in the ~Isual malmer in
the synthesis of the dyestu~f hy diazotizing and coupling corresponding start-
ing substances, were mixed, while stirring, with 12 parts by weight of a dry
dyestuff powder which had a dyestuff content of 60% by weight and which had
been obtained by spray-drying of another par~ of the same clarifled dyestuff
solution. The 112 parts by weight so obtained of an aqueous solution contaln-
ing 18% by weight of pure dyestuff and having a pH-value of 6.0 yielded, a$ter
addition of 4 parts by weight of disodium-hydrogenophosphate, an aqueous dye-
ing preparation whlch had a content of pure dyestuff of 17~5% b~ weight and a
pH-value of 6.3.
Using 2 parts b~ weight of this pH-stabilized solution, dyebaths,
padding liquors and printing pastes were prepared in the usual and known man-
ner, which when applied and fixed on cotton according to the methods usually
employed for reactive dyestuffs yielded yellow dyeings and prints which had
the sa~e depth of shade as those produced with dyebaths, padding liquors and
printing pastes o~ the same concentration but which had been prepared with 1
part by weight of a powder formulation containing 35% of pure dyestuff.
This intensit~ of shade of the dyeings and prints was obtained with
unaltered quality when the above-indicated novel aqueous preparation had been
stored for 6 weeks at 50C in a closed vessel.
EXAMPLE 18:
200 Parts by weight of an aqueous9 clarified dyestuff solution of
the dyestuff of the above formula (II) having a pH-value of 5.8 and a dyestuf$
content of about 13% by weight, and which had been obtained in the usual man-
ner in the synthesis of the dyestuff by diazotizing and coupling of coTrespond-
lng starting substances, were mixed, while stirring, with 44 parts by weight
of a dr~ dyestuff powder having a dyestuff content o~ 54% b~ weight and ~hich
23 -
. : ' '
~C~7~3
had been obtained b~ spray-dr~ing o~ another part of the same clarified dye-
stuff solution. The 2~4 parts by weight so obtained of an aqueous solution
containing 20.4% by weight o~ pure dyestuff yielded, a~ter addition o~ 5 parts
by weight of disodium-hydrogenophosphate, an aqueous dyelng preparation which
had a content o~ pure dyestuff of 20.0% by weight and a pH-value of 6.1.
Using 2 parts by weight of this pH-s~abillzed solution, dyebaths,
padding liquors and printing pastes were prepared which, when applied and
fixed on cotton according to the~methods usuall~ employed for reactive dye-
stuffs yielded yellow dyeings and prints which had the s<~me depth of shade as
those produced with dyebaths, padding liquors and printing pastes of the same
concentration but which had been prepared with 1 part by weight of a powder
formulation containing 40% of pure dyestuff.
This intensit~ o~ shade of the dyeings and prints was obtained in
unaltered quality when the above-indicated novel aqueous preparation had been
stored for 3 months at 20C in a closed vessel.
EXAMPLE 19:
200 Parts by weight of an aqueous, clarified dyestufE solution of
the dyestuff of the above ~ormula ~II) having a pH-value of 6.0 and a dye- ;
stuff content of 15% by weight, which had been obtained in the usual manner ~ ~ -
in the synthesis of the dyestuff by diazotizing and coupling correspondlng
starting compounds, were mixed with 5 parts by weight of disodium-hydrogeno-
phosphate. 55 Parts by weight of water were eliminated Erom this dyestuff
solution by distillation, while stirring, at 60C and under a reduced pressure
of 18 Torr. 150 Parts by weight of an aqueous dyeing preparation were ob-
tained, ~hich had a content of pure dyestuff of 20% by weight and a pH-value
of 6.3 at 20C.
Using 2 parts by weight of this solution, dyebaths, padding liquo~s
and printing pastes were prepared in the known and usual manner, which when
- 24 -
,.. . :~
~' ' ' ,
.
~7~03
applied and ~ixed on cotton in the manner usually employed ~or reactive dye-
stuffs, yielded yellow dyeings and prints which had the same depth o~ shade
as those produced wlth d~ebaths, padding liqucrs and printing pastes of the
same concentration ~ut which had beenprepared with 1 part by weight of a pow-
der ormulation containing ~0% of pure dyestuff.
This intensity of shade of the dyeings and prints was obtained with
unaltered quality when the above-indicated novel aqueous preparation had been
stored for 3 months at 20C in a closed vessel.
EXAMPLE 20:
100 Parts by weight of an aqueous, clarified dyestuff solution of
the dyestuff of the above formula (II) having a pH-value of 6.0 and a dyestuff
content of 15% by weight, which had been prepared in the usual manner in the
synthesis of the dyestuff by diazotization and coupling of the corresponding
starting substances, were mixed, while stirring, with 15 parts by weight o~
a dry dyestuff powder having a dyestuff content of 60% by weight and prepared
by spray-drying of another part of the sam0 clarified dyestuff solution. Ihe
115 parts by weight so obtained of an aqueous solution containing 20.8% by
weight of pure dyestuff yielded, after addition of 5 parts by weight o~ sodium
borate, an aqueous dyeing preparation which had a content of pure dyestuff
of 20% by weight and a pH-value of 6Ø
Using 2 parts by weight of this pH-stabilized solution, dyebaths,
padding liquors and printing pastes were prepared in the known and usual man-
ner, which, when applied and fixed on cotton in ~he manner usually employed
for reactive dyestuffs, yielded yellow dyeings and prints which had the same
depth of shade as those produced with dyebaths, padding liquors or printing
pastes of the same concentration but which had been prepared with 1 part by
weight of a powder formulation cGntaining ~0% by weight of pure dyestuff.
This intensity of shade of the prints and dyeings was obtained with
- ~5 -
.~ `
~7~3
unaltered quality ~hen the above-indicated novel aqueous preparation had been
stored for 6 weeks at 50C ln a closed vessel.
EXAMPLE 2_:
100 Parts by weight o~ an aqueous clari~ied dyestuff solution of the
dyestu~f of the above formula (III) having a pH-value of 5.7 and a dyestuff
content of 12% by weight, which had been obtained in the usual manner in the
synthesis of the dyestuff by diazotization and coupling of the corresponding ~`
starting substances, were mixed, while stirring, with 24.5 parts by weight of
a dry dyestuff powder having a dyestuff content of 70% by weight and which had
been obtained by spray-drying of another part of the same clarified dyestùff
solution. The 124.5 parts by weight so obtained o an aqueous solution con-
taining 23.4% by weight of pure dyestuff and having a p~l-value of 5.7, yielded
after addition of 5 parts by weight of disodium-hydrogenophosphate an aqueous
dyeing preparation which had a content of pure dyestuff of 22.5% by weight and
a p~l-value of 6Ø
Using 2 parts by weight of this pH-stabilized solution, dyebaths,
padding liquors and printing pastes were prepared in the known and usual manner,
whlch, when applied and fixed on cotton according to the methods usually em-
ployed br reactive dyestuffs, yielded yellow dyeings and prints which had the
same depth of shade as those produced with dyebaths, padding liquors or printing
pastes of the same concentration but which had been prepared with 1 part by
welght of powder formulation containing 45% by weight of pure dyestuff.
This lntensity of shade of the dyeings and print was obtalned wlth
unaltered ~uality when the above-indicated novel aqueous preparation had been
stored for 6 weeks at 50C in a closed vessel.
BXAMPLE 22:
200 Parts by weight of an aqueous, clarified d~estuf~ solution o~
the dyestu~f of the above formula ~III) having a pH-value of 5.8 and a dyestu~f
- 26 -
., .
.. .
content of about 13% by weight, which had been obtained ln the usual manner
in the syn~hesis of the dyestuff by diazotiæation and coupling of correspond-
ing starting compounds, were mi~ed~ while stirring, with 3~ parts by weight
of a dry dyestuff powder having a dyestu-ff content of 6~% by weight and pre-
pared by spray-drying of another part of the same clarified dyestuff solution.
The 234 parts by weight so obtained of an aqueous solution containing 20.4%
by weight o pure dyestuff yielded, after addition of 5 parts by weight of
disodiumhydrogenophosphate, an aqueous dyeing preparation which had a content
of pure dyestuff of 20.0% by weight and a pH-value of 6.1.
Using 5 parts by weight of this p~l-stabilized solution, dyebaths,
padding liquors and printing pastes were prepared in known and usual manner
which, when applied and fixed on cotton according to the methods usually em-
ployed for reactive dyestuffs, yielded yellow dyeings and prints which had
the sanle depth of shade as those produced with dyebaths, padding liquors or
printlng pastes of the same concentration but which had been prepared wlth 2
parts by weight of a powder formulation containing 50% of pure dyestuff.
This intensi~y of shade of the prints and dyeings was obtainedwith
unaltered quality, when the above-indicated novel aqueous preparation had been
stored for 3 months at 20C in a closed vessel.
EXAMPLE 23:
200 Parts by weight of an aqueous clarified dyestu~f solution of
the dyestiff of the above formula ~III) having a pH-value of 6.0 and a dye-
stuff content of 13% by weight, which had been obtained in the usual manner
in the synthesis of the dyestuff by diazotization and coupling of correspond-
ing startingsubstances, were mixed with 3 parts by weight o~ disodium-
hydrogenophosphate. 87.5 Parts by weight of water were eliminated from this
dyestuff solution by distillation, while stirring, at 60C and under a reduced
pressu~e o~ 18 Torr. 115.5 Parts by weight of an aqueous dyelng preparation
~ 27 ~
,
,'
903
were o~tained ~hich had a contcnt of pure d~estufe o~ 22.5% by weight and a
pll-value o~ 6.1 at 20C.
Using 2 Parts by ~elght of this solution, dyebaths, padding liquors
and printing pas~es were prepared in known and usual manner and yielded, when
applied and fi~ed on cotton according to the methods usually employed for re-
active dyestuffs, yellow prints and dyeings which had the same depth of shade
as those produced with dyebathsl padding liquors or printing pastes of the
same concentration, but which had been prepared with 1 part by weight of a pow-
der formulation containing ~5% by weight of pure dyestuf.
This intensity of shade o the prints and dyeings was obtained with
unaltered quality when the abo~e-indicated aqueous preparation had been stored
for 3 months at 20C in a closed vessel.
E~AMPLE 24:
100 Parts by weight of an aqueous, clarified dyestuff solution of
the dyestuff of the above formula (III) having a pH-value of 6.0 and a dye-
stuff content of 12% by weight, which had been obtained in the usual manner
in the synthesis of the dyestuff by diazotization and coupling of correspond-
ing starting compounds, were mixed, while stirring, with 25 parts by weight
of a dry dyestuff powder having a dyestuff content of 70% by weight and ob-
tained by spray-drying of another part of the same clarified dyestuff solution.
The 125 parts by weight so obtained of an aqueous solution containing 23.9%
by weight of pure dyestuff yielded, after addition of 6 parts by weight of
sodium borate, an aqueous dyeing preparation which had a content of pure dye-
stuff of 22.5% by weight and a pH-value of 6Ø
Using 2 parts by weight o~ this pH-stabilized solution, dyebaths~
~adding liquors and printlng pastes were prepared in known and usual manner~
which, when applied and ~ixed on cotton according to the methods usually~ em~
ployed ~or reactive dyestu~fs, yielded yellow dyeings and prints which had
28 -
: ' ' , -
. ' ' .
the same depth of shade as those produced with dyebaths, padding liquors or
printing pastes of the same concentration, but which had been prepared with
1 part by weight of a powder formulation containing 45% by weight of pure dye-
stuf~.
This intensity of shade o~ the prints and dyeings was obtained with
unaltered quality, when the above~indicated novel aqueous preparation had been
stored for 6 weeks at 50C in a closed vessel.
- 29 - .
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'
