Note: Descriptions are shown in the official language in which they were submitted.
HOE 7~F _177
13V5~
The present invention relates to liquid compositions of
fiber-reactive azo dyes.
After having been synthetiæed,water-soluble reactive dyes
are generally isolated by salting them out from the aqueous
.eac'~vl~ svl~tiv-, suv'ion~ i ter~ng the precipitated sal'~dJ~e-
stu~f mixture and drying the fi:Lter cake obtained. Another
method used i~ industry for iso:Lating the dissolved, generally
readily water-soluble dyestuff from the solution is by drying
it directly~ ~or example by spray-~ying the solution.
For the dyeing purpose intended, the salt~ containing dye-
stu~f powder is then generally standardized to a determined
dyestuf~ content, ~ollowing the drying operation, by admixing
neutral inorgi~nic salts, for exi~mple sodium sulfate.
These con~ent~onal powder brands of reactive dyesl how-
ever, have a number o~ drawbacks resulting from the formation
of dust of these pulverulent dyestuf~ compositions when hand-
- ling them, for example when filling or refilling them in con-
tainers, weighing and dosing them or using them to prepare
dyeing liquors or printing pastes. This dust formation not
only inconveniences the operating per~onel but may also, whe~
the dust settles down, lead to unpleasant dotty coloration of
undyed or already dyed material in the dyeing or printing
shops. Alternatively, dust prevention on dyestuff powders
using the conventional dust-preventing agents on a mineral oil
basis always involves the risk o~ oily deposits in dyeing and
printing, which result in spotty and there~ore useless dyeings
and prints. Moreover, in many cases, these dyestuff powders
constitute an ~bstacle in indu6try to desira~le rationali-
29 zation measures such as, ~or example continuous dyeing process
- 2 -
~q~
.
.
1~9~VS5
or automatically operated dosing and weighing devices,
These drawbacks are fully overcome according to the present
~nvention, as far as azo dyes are concerneld.
We have now found liquid, aqueous compositions of fiber-reactive
aza dyes which in the form of the free acild correspond to the formula (I)
QH3S~m - F ~n ~I)
in which
F represents the chromophoric residue of a monazo, disazo, or trisazo
dyestuff;
Z represents a fiber~reactive group;
m represents an integer of from 1 to 8; and
n represents an integer of from 1 to 3,
These dyestuff compositions comprise one or more, e.g two, three
o~ our, of these dyestuffs of formula (I), preferably the alkali metal
salts, especially sodium salts thereof~ in an aqueous solution in a con~
centration of from 5 to 45% by weight, preferably from 15 to 40% by weight,
more preferably from 15 to 30% by weight, calculated on the pure dyestuff
o formula CI~, and have a pH value of from 3 to 7, advantageously 5.5 to
6~8 and additionally contain one or more, e.g. 2, 3 or 4, buffer substances,
preferably l to lO, more preferably 1 to 6% by weight thereof.
To all conce m ed in the production and handling of the dyes,
the novel co~positions m4reover give a fair advantage over dyestuff powder
firands, inas~ar as they substantially reduce the waste water pollution
with salts.
.
- " : . .
. : , . '. ' . ' . ' ' ': . . ' '
' : . ., ' . ' " . : " " '
" . : . .' . . ' ~ . '. ~ '
. . , ' ' .. ..
~,- , ' . ' ' : ' . :' ' . . : ' : .
~,. . : . ~ . . .:, ' '
' . . ' ' ' . . '
HOE 75lF 177
9005S
According to this i~vention, -the ~ew liquid dyestuff com-
positions of ~ormula I are prepared by starting directly from
a dyestuff solution optionally clarified, or ~rom a dyestuff
suspension which are obtained by a new, hereina~ter specified
ayl.'hasl~ mathcd; ~hê~ . ûr exampla, ~he sû'~t vrl is s~allu~rd-
~zed where desired - since this is advantageous - tû the de-
sired higher dyestuff content either by concentration, for ex-
ample by separation of part of the water by distillation in
vacuo, or advantageously by addition of a dried, for example
spray-dried, portion of the same cl~rified dyestuff solution
obtained by this synthesis, or water is added to the suspension
for dissolving the dyestuff to a highly concentrated solution,
- and finally, at any event, buffer substances are added to this
dyestuff solution.
15- The conventiû~al synthesis method ~or water-soluble a~o
dyes~ including a diazotizatiûn with at least 2 mols o a mine-
; ral acid per each mol o~ diazotizable amine, always results in
dyestuffs co~taining ~nert salts. This generally prevents the
preparation of liquid concentrated compûsitiûns of fiber-re--
act~ve azo dyes containing only one sulfo group with a dyestuff
content that~is interesting for industrial use. These industrial-
ly interesting, liquid composltions of reactive dyes should
pos~ibly have half the tinctorial strength of the conventional
powder brands, which means a content o~ pure dyestuff in the
liquid composltion of frûm about 15 to 30~ by weight.
Such a dyestuff content may, however, also not be achieved
for azo dyes containing 2 or more S03H~groups; ~or the solubili-
ty of a dyestuff substantially~ but not exclusively, depends
29 on the number o~ SO~H--groups, but also ûn the molecule size,
-- 4 --
.
1090U~
on the arrangement of the S03~.groups in the molecule and on the presence
- of further substituents. Thus, for example, an S03H-group linked in ortho
position with regard to the azo group brings about a poorer solubility than
a S03H-group being farth~r away from the azo group.
In contradistinction to the known methods) the novel pTocess for
the prepasation of azo dyes, which i~proves the above-mentioned preparation
of the dyestuff compositions of the inventionl permits a reaction of stoi~
chiometrical amounts of an aromatic amine and a coupling component having
at least one free acid group in one of the two components, with the stoi-
10 chiometrical amount of a nitrite in water and/or an organic solvent, but
without addition of an acid, while the pH of the reaction mixture, if
required, is adjusted, to the optimum ~or the coupling reaction by means
o~ acid-binding inorganic compounds or buffer substances during or after
the addition of the nitrite. This process is disclosed in detail in our
copending Canadian patent application Serial No. 244,529 (issued as Canadian
Patent 1,063,5~8).
The solvents used do not contain groups having an acid or basic
effect, are miscible with or soluble in water and show a pH of from 6 to 8,
preferably from 6,5 to 7.5, in an aqueous solution at 20C. These solvents
20 include, for example, lower aliphatic alcohols, as alkanols, e.g~ methanol,
ethanol, n hutanol; lower aliphatîc or cycloaliphatic ketones, as alkanones
; c~ cycloalkanones, e.g. dîethyl-ketone, acetone, butanone-~2), cyclohexanone;
dimethylformamide, N methyl~pyrrolidone, N-methyl-
~ 5-
... .:i~ .
.
.~ . . . : :
: . .
...
: , . . '
: ' ' ,' . ~ :,
.. . . . ..
HOE 7~/F 177
3~ V ~5 ~
acetamide, dimethylacetamide~ dimethylsulfoxide, dioxan, ethy-
lene-glycol monome~h~l ether and phosphoric acid tr~s-(~-di-
methyl)-amide as well as -caprolactam.
The diazotization and coupling reactions according to
this novel process may be carried ou~ in di~ e an~ oon5Pn-trat
ed9 aqueous, aqueous-organic or organic solutions with organic
solvents of the above type. It is, however, advantageous to
choose a reaction medium in which the reaction components are
present ln a highly concentrated form, especially as a suspen~
sion in the solvent used, in which part of the two coupllng
reactio~ components should be in a dissolved stateO
Water is the preferred solvent.
This novel process is most advantageously carried out by
preparing a paste of the diazotizable aromatic-amine or the
coupling component, or the two together, in stoichiometrical
amounts, preferably in a finely divided form, with a small
amount of water or in another of the solvents or mixtures of
solvents, and if required, then adding the other component in
astoichiometrical amount, and finally admixing the calculat-
ed equivalent amount of a salt of the nitrous acid~ preferably
an alkali metal nitrite, for example sodium nitrlte, in a
solid, advantageously finely divided form. The nitrite may be
added in one single portion but advantageously it is added in
several portions, since this enables a better temperature
check. The temperature for the diaæotization and coupling re-
actions may ra~ge from -10C to ~50C, preferabl~ from 0C to
30C
Hence~ this invention preferably relates to compositions
29 comprising dyestuffs of formula (I) of the above-said consti-
- 6 -
''~ ' .
F 177
~ 3 ~ ~5 ~
tutlons, which contain one or more dyestuffs of formula (I)
prepared acoording to the above-described new process.
The aqueous dyestuff solutions or suspensions obtained
according to the novel process are directly used~ optionally
a4tel additior. Ol ~UULlel sub3tances; lOr~ th~ ~rep~ OI
the dyeing compositions of the invention. The dyestuff solu~
tions or suspensions obtained by this process, which contain
; organic solvents only or other solvents, too, are freed from
the organic solvents, ~or example by heating them in vacuo or,
10 if required or des$red, they are spray-dried.
Organic solvents may advantageously be used for the syn-
thesis, for example if the diazotizable organic amine or the
coupling component is too sparingly soluble in water only, and
speedy and complete diazotization and coupling reactions o~ly
take place in the presence o~ an organic solvent.
The solutions or suspensions of the dyestuf~s of formula
(I) obtained by this synthesis contain from 10 to 80% by weight
of dyestuff but they do not contain any inorganic saltsg un-
less such inorganic salts are already contained in the start-
ing products. The suspension may be diluted with water to suchan extent that the solutions obtained there~rom have a dyestuff
content of from 10 to 45~ by weight. Solutions having a dye-
stuff content less than 45% can be concentrated to reach a con-
tent of 45% by adding dry dyestufP obtained by drying part of
the same solution or suspension or by distilling o~f water and/
or solvents in vacuo. The highly concentrated compositions
may, of course, also be prepared by dissolving the dyestuff
pvwder, that has been obtained by drying this solution or sus-
29 pension, to provide a correspondingly highly concentrated a~ue-
-- 7 --
.. . . . . ..
. ~ . ' .
, ' ~': ' ;' . .
.
~ 90V~ HOE 7~ ~ 177
ous dyestuff solutlon and then adding buffer substances thereto.
Since the dyestuffs co~tained in the compositions of the
invention need not be isolated by salting out9 there is no pro-
duction of mother liquors which have a very high content of
salis or even are saturaled witn sa;~s. Ai~o, wi b~i t~le 3- lt
content of the compositions being nil or very low and no need
for salts to standardize the dyestuff powders, the salt con-
tent of the waste waters coming from the dyestuff user i~ con-
siderably reduced.
Hence, the advantage of the dyestu~ compositions of the
invention is that they contain no salt coming from the synthe-
sis. The salt content merely depends on the purity of the
starting components. Another advantage is the mild manufac-
turing conditions using no excess acid, which is particularly
useful with components containing such kind o~ reactive groups
which are sensitive to acids. Difficulties are only liable to
arise if complete diazotization and coupling reactions;require
wor~ing in a pH-range which also accelerates the reaction speeds
o~ possibie side reactions, ~uch as the hydrolysis o~~chlorine
linked to he-terocycles or the reaction of reactive groups with
the dia~oti~able amine. ~onetheless, in most of these special
cases, a careful c~ecking of the temperature and/or an alter-
natingly portionwise addition o~ one or both compdnents and
o~ the sodium ~itrite will result in satisfactory yields.
The reactive group Z is understood to contain one or more
reactive groups or substituents capable o~ being split o~
under the reaction while forming covale~t bonds, with tne hy
droxy groups of the cellulose when applying the dyes onto
29 cellulosic material in the presence of acid-binding agents and,
-- 8 --
- HOE_75/F 177
()0~ 5
optionally, under the action of heat, or 7 when applying tne
dyes onto natural or synthetic polyamide fibers7 with the NH-
groups of these fibers. These fiber-reactive groupings are
known in the art in a great variety~
Reaciive groups o~ this type are, for example, he~ero-
cyclic radicals including 2 or 3 nitrogen atoms in the hetero-
cycle, which carry at least one reactive substituent, such as
a halogen atom, linked to a carbon atom, as for example of the
halogenotriazinyl, halogenoquinoxaline, halogeno-pyridazine and
- halogeno-pyrimidine series, the acyl radicals of halogenated
aliphatic carboxylic acids and unsaturated carboxylic acids~
especially the reactive groups of the vinylsulfone series and
the sulfamide derivatives thereof.
Dyestuff compositions of the invention containing one or
more dyestuffs having a vinylsulfony~, B-sulfatoethylsulfonyl7
B-thiosulfatoethylsulfonyl or ~-acetoxyethylsul~onyl-group,
are preferred.
Examples of important reactive groups of the vinylsulfone
series are, in addition to the vinylsulfone group ~tself, ali-
~0 phatic sulfone groups containing, in the B-position with re-
gard to the sulfone group, a group which can be split off by
alkali, for example a halogen atom or an ester radical of an
acid, such as the B-chloroethyl-sulfonyl, B-acetoxyethylsulfo-
nyl, B-(3-sulfobenzoyloxy)-ethyl-sulfonyl,~ sulfatoethylsul~o-
nyl, ~-thiosulfatoethyl-sulfonyl, ~-phosphatoethylsulfonyl and
B-sulfatoethylsulfonylmethylamino groups, or the vinylsulfonyl-
methylamino group. Further important reactive radicals o~ the
~ above-mentioned series are, ~or example, acyl groups of acry
2g lic acid7 of B-bromopropionic acid and of ~ dibromo propio~
_ g ~
. . . .
-
: ., . , ' ' '
'`.. .', . , : . . '
' ' . . .' , . ' ,:
- , :
- HOE 7~1F- 177
nic acid; the 3,6-dichloropyridazin-4-carbonyl, 2,3-dichloro-
quinoxalin-5- or -~-carbonyl, 2,4-dichloropyrimidin-5-carbonyl,
5-chloro-2-methylsulIonyl-6-met:hyl-pyrimid-4-yl, 2,4-difluoro-
5-chloro-pyrimid-6-yl or 9 especially s-triazin-2-yl- and pyri-
5 rn~-lln-2-yl ~r -~-yl groups7 l.rhich cor.ta~r a bromin^ ^~ p.afer- !
ably chlorlne atom or a sulfonic acid group in at least one of
the remaining 2-, 4- or 6-position. If the triazine or pyrimi-
dine ring carries only one of these reactive substituent3, the
remaining cyclic carbon atoms may carry non-reactive substitu-
10 ents. Examples OI these non-reactive substituents are the hy-
droxy group, etherified hydroxy groups, primary amino groups
and mono- or disubstituted amino groups, such as mono- and di-
alkylamlno groups having up to 4 carbon atoms in the alkyl
moiety, which may carry further substituents, such as hydroxy
15 or alko~y groups, or phenylamino groups which may preferably
carry sulIonic acid groups and further substituents linked to
the aromatic nucleus, for example the carboxy group. Etheri--
fied hydroxy groups are preferably the alkoxy groups having
up to 4 c rbon atoms. Specific examples of all these classes
20 of non-reactive substituents are methylamino, ethylamino, di-
methylamino, phenylamino, o-, m- and p-sulfophenylamino, the
~arious disulfophenylamino and m- and p-carboxyphenylamino
groups.
Fiber-reactive azo dyestu~fs OI formula (I~, which are
25 suitable for liquid dyestuff compositions of this type, accord-
ing to the invention are known for example from the following
publications:
German Offenlegungsschriften Nos.:
29 1 ,544,499;1 ,544,512; 1 ,544,517; i 754495~8; 1 ,544,542;
- 10 -
'~
.
`
,~, '
, ' ', ' '
HOE 75LF 177
.~ VVS~
1,544,547; 1,619,491; 1,769,091; 1,793,301; 1,7959086;
1,804,524; 1,619~519;
German Auslegeschriften Nos.:
1,109,807; 1,156,914; 1,186,160; 1~204,762; 1,232,294;
1,~ A ~ 76 A; 1,~Q9,~
German Patent.Specifications Nos.:
436,179; 1,0629~67; 1,103,483; 1,206,107; 1,248,188;
1,282,213; 1,150,163; 1,256j622;
Belgian Patent Specifications Nos.:
572,491; 578,742; 578,933; 592,213; 590,519; 597,730;
598,831; 609,091; 673,572; 673,573;
French Patent Specifications ~os.:
1,512,646; 19160,909;
Swiss Patent Specification No.:
. 15 466,455.
Suitable for the compositions of the ~nvention are all
the buffer substances which are not capable of a chemical re-
action, that would reduce the color yield, with the fiber-re-
active group Z 9 such as with the B-sul~atoethylsulfonyl group
or the vinylsulfonyl analog there~f, for example sodium and
potassium acetate, sodium and potassium oxalate, the acid so-
dium and potassium salts of phosphoric acid, mixtures of the
various sodium or potassium salts of phosphoric acid, and so-
dium borate, among which sodium borate and disodium hydrogeno-
phosphate and sodiumdihydrogenophosphate are preferred.
The mechanism of the react~on of reactive dyes with cellu-
lose~ fibers is generally known. Thus, for example, in the
reactive dyes of the vinyl-sulfone type, the formation of the
29 covalent bond between the fiber substrate and the dyestuff
. ~. .
,:. ' - . ' :
. . .
., . ., ' ' ' .
, ~, . ' .
.. . . . .
HOE 75/F 17'j
J~ O~S
molecule according to the reaction (4) of the below-mentioned
scheme 1 - after conversion of the ~-sulfatoethylsulfonyl group
into the vinylsulfonyl group in the presence of alkaline agents
- according to reaction (1) - brings about the known good fast-
r.eQs propert~ e9 of th~ dyein~s proAuceA with thess reacti ~.re
dyes.
The same applies, for example9 to reactive dyes havin.g
a halogeno~triazinyl gr~p, in which the covalent bond with
the f$ber is caused according to reaction (6) of the scheme 2.
Scheme 1: -
'
(so3H)m-F-so2-cH2-cH2-o-ce
J ~
(4) + Cell.-OH
(1 )
F-S02-CH2-CH2-o-so3H ~ So2 CH=CH2
(S03H)~ (S03H)m
~ H~O . ~
- H2S4 (2) ~3) + H20
. ~ ~-CH2-~2-~
(S03~)m
- 12 -
.
- :- - . . - . .
. . . . . .
; .: .. ,; '~. , ' , , ' ', , , ': ' ' , ' , ' . .
. . .. . . .
: : . , .:. :
.
. .
~ F~ 7
1~)9~
Scheme 2:
.
Cl
/ OH
, (HO~,S)
NH2 ~ HCl (SO H) \N
(6) ~ Cell.-OH
- HCl O-Cell.
. N ~
: ~~~~~ (H3S)m~ F - NH ~ //N
~.
NH2
.
r
in which schemes F stands for the rest of the dyestuff mole-
cule and m is defined as above, and Cell A -OH stands ~or cellu-
lose.
For example, when using the reacti~e dyes havi~g a ~-sul-
fato-ethylsulfonyl group, it is however known that this re-
active group, as does the ~inylsul~onyl ~orm with water, reacts
not only in -the presence of alkaline agents but also in an
acid medium in a reaction according to (2) or (3) of the
scheme, running concurrently with the dyeing reaction ~4) it-
sel~, to pro~ide the B-hydroxyethylsulfonyl group which is
only sparingly reacting wlth the fiber substrate.
The hydrolysis (2) and the addition o~ water t3) are prac-
tically not reversible under the dyeing conditions and there-
~ore~Feduce the color yield-
13
s
, ~ . , :
., , , , ~,, ...
.
.. ...
. .
~0~05 S
For this reason, water-soluble reactive dyes are generally
prepared in such a manner that the above-mentioned separation
and drying of the reactive dyes from the reaction solution
immediately follows the synthesis in order to avoid loss in
ctv al str~r.gth ~or tha abûva reasûns.
It was the more surprising to find that neutral to weak-
ly acid aqueous bu~fered solutions of reactive dyes of ~ormula
(I) are stable over a prolonged period of time without loss
in tinctorial strength. Even after storage for se~eral mon-ths,
for example for 6 months at room temperature, or for several
weeks, for example for 8 weeks, at 50UC, the aqueous solutions
~ the dyestuffs of formula (I) obtained according to the in-
vention provide dyeings and prints of unaltered color inten-
sity.
- After having been diluted with water and optionally after
addition of the current dyeing auxiliaries or accordingly of
thickening agents and optionally printing auxiliaries usual
in pri~ting, the dyeing compositions of the invention are
suitable, in a manner usual and generally known for reactive
dyes~ for the dyeing and printing of fibrous materials made
~f wool, silk, polyamide fibers, and natural or regenerated
cellulose or of fiber blends containing one or more of the
said fibers types.
The following Examples illustrate the invention, the
parts and percentages being by wei~ht unless stated otherwise.
E X A M P ~ E 1:
32.5 Parts of 2-methoxy-4-(B-sulfatoethylsul~onyl)--5-
methyl-aniline and 31.8 parts of 1-acetoacetylamino-2-methoxy-
29 5-methyl-benzene-4-sulfonate of ammonia were introduced wh.ile
.... . . . . . . . . ... . . .
;: : ' : .~ .
.
.. . ............................................ . .
.
' , . .
~iLF 1 7~Z
stirring into 140 parts of water of 5C. The addition of 17.3
parts of 40% sodium nitrite solution immediately resulted in
a quantitative yield of the dyestuff which, in the form of
the free acid, corresponds to the formula (II)
~.... .
C ~ CO-C~3 ~ S2-C~2-C~2_o_So3H
~03S OCH3 3~C
(II)
- - . .
The pH-value of the solution rose from 2.8 to 5.5. The
addition o~ 5 parts of disodium hydrogeno phosphate and 28
parts of water resulted in 262 parts of a composition contain-
~ng 25% of the dyestuff of formula (II) and having a pH o~
.3.
2 Parts each of thls pH-stabilized solution were used to
prepare a dyebath, a padding liquor or a printing pas~e in
~ the known and usual manner, which was then applied and fixed
on cotton in the manner usual for reactive dyes to provide yel-
low dyeings and prints that had the same color intensity as
those produced with equally concentrated dyebaths,padding li-
- quors or printing pastes prepared with 1 part of a .powder
brand co~tain.ing 50~ of the dyestuf~.
This color intensity of the prints and dyeings was un-
changed eYen a.~ter the abo~e-said novel aqueous composition
. had been stored ~or 6 weeks at 50C in a closed container.
E X A M P ~_E 2:
34.1 Parts of 2~amino-5-(B-sul~atoethylsulfonyl)-hydro-
quinone dimethyl ether and 25.4 parts of 1-(49-sulfophenyl)-
3-methyl-5-hydroxy-pyrazole were su,spended in 14.1.5 parts o~
:, . - 15 -
.
~....... . . , : . ,
. . . .
. : . . :
,. ' ' . ' : ~ ' '' ' '
:. . . '. :
. . .
~ 9 ~ 79~
water of 20C while stirring. The pH of the suspension was
adjusted to 4.5 by dropwise adding 30 parts by ~olume ~25.5
parts) of 5N sodium hydroxide solution. The addition of 6.9
parts of sodium nitrite raised the pH only slightly so that
the pu w~s at 5 At th~ end of the couplin~ rescti^n. 233.~
Parts of a solution of the dyestuff were obtained which, in
the form of the free acid, corresponds to the formula (III)
H03S-0-c~2-c~2-s02 ~ N ~ S05
~C
.
(III)
After addition of 9 parts o~ sodium acetate, the solution
contained 25% of dyestuff and had a pH of 5.5.
- 2 Parts of this pH-stabilized solution were each used -
to prepare a dyebath, a padding liquor or a printing paste in
the known and usual manner, which was then applied and fixed
on cotton in the manner usual for reactive dyes to provide
yellow dyeings and prints which had the same color intensity
as those produced with equally concentrated dyebaths, padding
llquors or printing pastes prepared with 1 part of a powder
brand containing 50% of the dyestuff.
This color intensity o~ the prints and dyeings was un-
changed even after the above-said novel aqueous composition
had been stored ~or 6 weeks at 50C in a closed container.
E X A M P ~ E 3:
28.1 Parts of 4-aminophenyl-B-phosphatoethylsulfone and
28.1 parts of 2-acetylamino-8-naphthol~6~sulfonic acid were
stirred in 150 parts of water of 10~C9 and 6.9 parts of sodium
- 16 -
-...... . . .
:. : . , .
.. . . . .
; ~ . . , : .
.. . . . . . . . .
.
:. :: '' ' ' '
. HOE 7 ~
~ 3~3~S5
nitrite were added portionwise thereto, while the pH rose from
3.2 to 5.2 and the reaction temperature to 22C. The addition
of 7 parts of disodium hydrogenophosphate resulted in 220
parts of a solu"tion containing 26%.of the dyestuff which in
thc ~Ol~ o the lree acid co.~r~spu~lds t~ -the for~uia ~IV)
-O-C~2-C~2_So2 ~ ~~ N OE
. ~03S ~ ~ NH-CO~H5 (IV)
and which had a pH o~ 6.2.
2 Parts each of this pH`stabilized solution were used to
prepare a dyebath, a padding liquor or a printing paste in the
known and usual manner, which was then applied and fixed on
cotton in the manner usual ~or reactive dyes to provide ora~ge
dyeings and prints which had the same color intensity as those
produced with equally concentrated dye~aths,` paddlng~liquors -
or printing pastes prepared with 1 part of a pwoder brand con-
tai~ng 52% of the dyestuff.
This color int.ensity of the prints and dgeings was un-
changed even after the above-said novel aqueous composition
had been stored for 6 weeks at 50C ln a closed container.
E X A M P ~ E 4:
40 Parts of 3-(4'-aminoben~oylamino)-B-sulfatoethylsulfonyl-
benzene and 40.5 parts of 1-acetylamino-~-naphtol-3,6-sulfonic-
acid (disodium salt) were stirred at 20C in 1.85 parts of
water, and 6.9 parts of sodium nitrite were added. After
stirring had been continued for 1 hour, 20 parts by volume
(17 parts) o~ 5N sodium hydroxide solution were added so as to
-. carry out the coupling reactiQn at a pH of about 4. Stirring
: - 17 -
~.. - -- - . . - . . .
. ~ . . . .. . .
.
:.: ' , . , ~ . ' :
.
.. :,..... , . ' " '. ' . '
. .... ~ ' ' ~. ~, ' ' . :
: . . . . ~ .
~ 77
S~
was continued for 15 minutes and the pH was adjusted to 6.~
by adding ~ parts of sodium borate. The addition of 12 parts
of water resulted in 309.4 parts of a solution containing
25% of the dyestuff o~ the formula (V)
~ . , . . _ _ . . .
~Q ~E-C0-C~3
-~E-C0 ~ N=--~N
E2-c~2-so2 EO~S s~
.. , , . .............. . ~
2 Parts each of this pH-stabilized solution were used to
prepare a dyebath, a padding liquor or a printing paste in the
known and usual manner, which was then applied and fixed on
cotton in the usual manner to provide red dyeings and prints
which had the same color intensity as those produced with
equall~ concentrated dyebaths, padding liquors or printing
pastes obtained w$th 1 part of a powder bra~d containing 50%
of the dyestuf~. -
This color intensity of the prints and dyeings was un-
changed even a~ter t~e above-said novel aqueous composition
had been stored for 6 weeks at 50C in a closed container~
.
E X A M P ~ E 5:
29.7 Parts of 2-amino-4-~sul~atoethylsul~onyl-phenol
and 4005 parts o~ the disodium salt of 1-acetylamino-8-naph-
thol-3,6-disulfonic acid were stirred in ~00 parts of water at .
15C, and 6.9 parts of sodium nitrite were added. Stirring
was continued for several hours until no more diazonium com-
pound could be established; the pH re~ained almost unchanged
a-t about 5. 25 Parts o~ copper sul~ate and 10 parts of di-
sodium hydrogenophosphate and 8 parts of sodium dihydrogeno-
- 18 ~
- ~ .. - . . . ~ ~,. .
.~ ' ' ' ~, " ~ ' ,, ,' ', , ; ' ' '
., , ' , . . . . ~
'' . ' ' ' ' ' ,' , ' '
OE 75/F~
~9~0~ X
phosphate were then introduced into the reaction mixture. The
complex compound formed at once, while the temperature rose
by about 5C. The addition of further 65.9 parts o~ water re-
sulted in 486 parts of a solution contalning 15% of the dye-
~tuff o4 th~ formu'~ r)
Cll
-- , `p ~-~O-CHS
~ EO3S ~ 05~ (VI) ~-
EO5S-O-CE2-C~2-s02
and having a pH value of 5.4.
3 Parts of this p~-stabilized solution were used to pre-
pare a dyebath, a padding liquor or a printing paste in the
known and usual ma~ner, which was then applied and fixed on
cotton in the manner usual for reactive dyes to provide red
violet dyeings and prints which had the same color intensity
as those produced wlth equally concentrated dyebaths,padding
liquors or printing pastes obtained with 1 part of a powder
brand containing 45% of the dyestuff.
This color intensity of the prints and dyeings was un-
changed even after the above-said novel aqueous composition
had been stored for 6 weeks at 50C in a closed container.
E X A M P ~ E 6-
28.1 Parts of 4-aminophenyl-B-sulfatoethylsulfone and
28.4 parts of 1-(4'-sulfopllenyl) ~-carboxy-5-hydroxy-pyrazole
were introduced while stirring into 200 parts of water of 20~C.
After addition of 6 parts of sodium carbonate and 8 parts of
disodium hydrogenophosphate~ 17.3 parts of a 40% sodivrll nitrite
;- - 1g
. .
. ' ' .
. .
'
~90 ~5 5 ~OE l5 ~
solution were added dropwise while stirring within 10 minutes
at a pH of 4.6. At 20C, stirr:ing was continued for 1 hour,
further 8 parts of disodium hydrogenophosphate were added,
and the mixture was diluted with 33.2 parts of water.
~29 Paris OI a soluiion were obtained whlch contained
17.5% of the dyestuff of the formula (YII~ and had a pH of
6.5.
HOOC
liO; S_O-CHz-C~8-SO~ =2-N;~l!r (VII)
2 Parts each of this pH-stabilized solution were used to
prepare a dyebath9 a padding liquor or a printing paste in the
known and usual manner which was then applied and fixed o~ cot-
ton in the manner usual for reactive dyes to pro~ide yellow
dyeings and prints which had the same color intensity as those
produced with equally concentrated dyeing baths~ padding li-
quors or printing pastes obtained with 1 part of a powder braIld
containing ~5% of the dyestuff.
This color intensity of the prints and dyeings was un
changed even after the above-said novel aqueous composition
had been stored for 6 weeks at 50C in a closed container.
E X ~ M P ~ E 7
.
40 Parts of ~-(4'-aminobenzoylamino)-4-sulfatoethylsul-
fonyl-ben~ene and 28.4 parts of 1-(4'-sulfophenyl)-3 carboxy-
5-hydroxy-pyrazole were introduced while stirring into 200
parts o~ water of 20C, and after addition of 12.1 parts of
33% sodium hydroxide solution and 8 parts of disodium hydro-
' . ' ' '
"'. ' . ' ' . ' ' ` '
~, .
.,
'. , : , . :
HOE 75/E' 177
~ 05 S
genophosphate, 17.3 parts of 40~ sodium nitrite solution were
added dropwise. The mixture was stirred for 1 hour at 20 -
25C, while the pH remained practically unchanged at about 5.
Further 6 parts of disodium hydrogenophosphate and 65.2 parts
U1 Wa~,er We- e the11 added i,V ~1~O-ViUi:! 328 lp~rt~ OI a ~ e~;tuîl
solution containi.ng 21.3% of the dyestuff o~ the formula (VIII)
' ~OOG~
~NEI-CO~N=a=~_~G 7
HO5S-O-C~2-CH2 S
~VIII)
and having a p~ of 5.5.
- . 2 Parts each of this pH-stabilized solution were used
to prepare a dyebath~ a padding liquor or a printing paste
in the known and usual manner, which was then applied and fix-
ed on cotto~ in the manner usual for reactive dyes to provide
yellow dyeings and prints that had the same color intensity
as those produced with equally concentrated dyebaths, padding
liquors and printing pastes obtained with 1 part of a powder
brand containing 43% of the dyestuff.
This color intensity of the ~rints and dyeings was un-
changed even after the above-sa~d novel aqueous composition
had been storecl for 6 weeks at 50C in a closed container.
E X A M P ~ E ~8
25.4 Parts of 1-(4'--sulfophenyl)-3-methyl-5-hydroxy-pyra-
~ole were int~oduced into 150 parts of water of 25C and dis-
sol~ed by adding 5.5 parts of sod.~um carbonate, whereupon a
pH of 5.4 was reached. After addition o~ 32.5 p~rts of 2-
methoxy-4-(~--sulfatQethyl-sulfonyl)-5--methyl~aniline and 4
- 21 -
. , :
: .
'~ .
... ;............ . .. . . . . ...
. .
~ 3~ ~ ~ F 1I7
parts of. disodium hydrogeno-phosphate, the solution was cooled
to 10C`. Within 10 minutes,20 parts by volume (17 parts) of
5N sodium nitrite solution were added dropwise. The diazoti-
~ation and coupling reactions were complete immediately after
additivr. o~ sodiwm r.itriteS ~hi'a the pX Or th~i ~olutior. wa~
4.g. The addition of 3.8 parts of disodium hydrogenophosphate
resulted in 236 parts of a dyestuf~ composition containing
25~ of the dyestuff of the ~ormula (IX) and having a pH of 6~4.
. OCH3 ~5~
l10~5-O-C2~ ;02~N===d~N, (~
,
2 Parts each of this pH-stabilized solution were used to
prepare a dyebath, a padding liquor or a printing paste in
the known and usual manner, whlch was then applied and fixed
on cotton in the manner usual for reactive dyes to provide
yellow dyeings and prints which had the same color intensity
as those produced with equally concentrated dyebaths, padding
liquors or printing pastes obtai~ed with1 part of a powder
brand containing 50% o~ the dyestuff.
This color intensity of the prints and dyeings was un-
changed even after the above-said novel aqueous composition
had been stored for 6 weeks at 50C in a closed container.
E X A M P ~ E~
50.8 Parts (0.2 mol) of 1-(4'-sul~ophenyl)-3-methyl-pyra-
zolone-(5) ~ere dissolved in a mixture of 123 parts of water
and 53 parts of -caprolactam at room temperature by adding
10.6 parts of a.nhydrous sodium carbonate, while a pH of 5.4
- 22 -
. ,, . , ~ , . . ~ . .
, ... .
'~ . . . i' '' .'` ;"', ' '' ' ' . , ~
. . , ................. , : . .
. .
:, ' ,' '', ' '. ". '.
' ,: . ': ., ,
~77
.~ 3Vi3~ii5
was reached. Then,32.5 parts (0.1 mol) of 1-amino-2-methox~-
5-methyl-benzene-4-B-sulfatoethyl-sulfone and 34.1 parts (0.1
mol) of 1-amino-2,5-dimethoxy-benzene-4-B-sulfatoethylsulfone
were added and the mixture was cooled to 10C by external cool-
i~g ThR ?.f~rli+.~ nn nf 2; p~ts Of diSodi~lm h"rdro"9r!~phosph~te
adjusted the pH to 4.4. Then 15.8 parts of sodium nitrite
were added within 10 - 15 minutes ? which resulted in a yellow
dyestuff solution. The pH rose to 5.0, and coupling was com-
plete immediately after the addition of sodium nitrite. 298
Parts of a dyestuff solution were obtained, which contained
19.7% of the dyestuff of the formula (X)
~o; SO-CH2 -C~2-02 S ~ ~ ~ (X3
CE~ -
and 20.3% of the dyestuff of the formula (XI)
C0 h
~-==N
~IOS SO-C~2 -CH2-02 S
OC~,
in the form of their sodium salts.
1 Part of this pH-stabilized solution was used to pre-
pare, in the known and usual manner, a dyebath, padding li-
quor or printing paste which was then applied and fixed on
cotton in a manner usual for reactive dyes to provide yellow
dyeings and prints. These had the same good color intensity
as those produced with equally concentrated dyeba~, padding
liquors or printing pastes prepared with 1 part of a powder
brand cont.aining also 19.7% of the dyestuff (X) and 20.3% Of
., ', ~ - .,, ......................... '
:
.. ' .
'''-'` .1 q~9~)V~
the dyestuff (XI).
This color intensity of the prints and dyeings was un-
charged even after the above-said no~el aqueous composition
had been stored for 3 months at 20C in a closed container.
. ~ a M P T. ~. 1n-
38.8 Parts (0.1 mol) of a coupling component of the for-
mula (XII)
(XII)
~0 ~H-CO
Cl
in the form of its disodium salt and 17.3 parts (0.1 mol) of
ortho-anilic acid and 4 parts of disodium hydrogeno-phosphate
were introduced into a mixture of 85~8 parts of water and 28.3
parts of -caprolactam, and the mixt-lre was cooled to 5C.
6.9 Parts of ground sodium nitrite were slowly added while
, stirring to yield immediately a yellow dyestuff solution; the
pH-value rose to 5. After coupling was complete, another 3
parts of disodium hydrogenophosphate were added, whereupon
the pH rose ~o 6.2.
191 Parts of a dyestuff solution were obtained which con-
tained 30% of the dyestuff of the formula (XIII)
. ~SO3H EOOC
Wl`N===N~ ,¢~ (XIII)
N~-CO
.. ~1
in the form of its sodium salt.
3 Parts of this pH-stabil~zed solution were used to pre-
24 -
. ' .
; - . . ., . . . . . , . : , ,
. . .
- ~ ~ - . .. .
.
' . ' '
' ~ : i' . . ' ,. . : ,
5 ~
pare, in the known and usual manner, a dyebath, a padding li-
quor or a printing paste which was then applied and fixed on
cotton in a manner usual Eor reactiYe dyes to provide yellow
dyeings and prints. These had the.same good color intensity
as tl.ose prûu-~c~u wi Lil eq-Ually- ~o~i~en~cL;~ ~a uye~aths, padding
liquors or printing pastes prepared with 2 parts oE a powder
brand containing 45% of the dyestuff (XIII~.
This color intensity of the prints and dyeings was unl
changed even after the above-said no~el aqueous composition
had been st~red for 3 months at 20C in a closed conta~ner.
E X A M P ~ ~ 1?:
Following the procedure of Example 10 but using a mixture
o~ 85.8 parts of water with 28.3 parts of tetramethyl-urea re-
sulted in an equally concentrated solution of the dyestufE of
Eormula (XIII) which had the same properties.
E X A M P ~ E 12-
~.
A mixture of 206 parts oE water and 70 parts of hexamethyl-
phosphoric acid triamide was cooled to 10C and blended while
stirring with 47.25 parts (0.1 mol) o~ 2-amino-4-~4'-chloro-
6'-(31'-sulfophenylamino)-s-triazin-2-y ~-benzene-sulfonic acid
in the form of its sodium salt and 28.4 parts (0.1 mol) of 1-
(4'-sulfo~henyl)-pyrazolone-(5)-3-carboxylic acid. After addi-
tion of 4 parts oE disodium hydrogeno-phosphate, 17.25 parts
of an aqueous 40% solution oE sodium nitrite were slowly added
dropwise while Eurther stirring to yield a yellow dyestuEf so
lution whose pH rose to 5.2 during the addition of nitrite.
AEter couplîng was complete, another 4 parts o~ disodium hy-
drogenophosphate were added to adJust the p~ to 6.3.
29 384 Parts of a dyestuff solution were ohtained which con
- 25 -
HOE 75 ~ 7
~ 90(~ 5
tai~ed 20% of the dyestuff of the formula (XIV)
SO~E HOOC
N ~ SO3H (XIV)
. ~
,
in the ~orm of its tetrasodium ~alt.
2 Parts-each of this pH-stabiliæed solution were used to
prepare, in the known and usual manner, a dyebath, a padding
l~quor or a printing paste which was then applied and fixed
on cotton in a manner usual for reactive dyes to provide yel-
low dyeings and prints. These had the same good color inten-
sity as those obtained with equally concen-trated dyebaths, pad-
ding liquors or printing pastes obtained with 1 part of a pow-
der brand ~ontaining 40% of the dyestuff of ~ormula (XIY)o
This color intensity of the prints and dyeings was,un-
changed even after the above-said novel aqueous composition
had been stored for 3 months at 20C in a closed container,
E X A M P ~ E 13:
,
17.3-Parts of sulfanilic acid were introduced into a so-
lution of 57 parts of the disodium salt o~ 1-hydroxy-8-N-(2'-
methylsulfonyl-5'-chloro-6'-methyl-pyrimid-4l-yl)-amino-naph
thalene-3,6~disulfonic acid in 250 parts of water. After cool-
ing to O - 5C9 6.9 par-ts of sodium nitri-te were added while
stirring, whereupon the pH rose from 2.6 to 5Ø Then, 4
parts o~ sodium dihydrogenophosphate, 8 parts of disodium hy-
drogenophosphate and another 11 parts of water were added-to
yield 35~ parts of a solution containing 20% of the dyestuff
- 26 -
HOE 75/F 1
~9 0
of the formula (XV)
,, ' ~sO2-C~
~03 S~3N_-=N ~ C:L C~l (XV) '
.,, ~ ~OoH
and having a pH of 6.1.
2 Parts each of this pH-stabilized solution were used to
prepare, in the known and usual manner, a dyebath~ a padding
liquor or a printing paste which was then applied and fixed
on cotton in a manner usual for reactive dyes to provide red
dyeings and prints~ These had the same good color ~ntensity
as those produced with equally concentrated dyebath~ padding
liquors or printing pastes prepared with 1 part o~ a powder
brand containing 40% of the dyestuff.
This color intensity of the prints and dyeings was un-
changed even after the above-said ~ovel aqueous composition
had been stored for 3 months at 20C in à closed container.
E E 1~:
25~.3 Parts of 1-aminobenzene-2,4-disulfonic acid were
introduced into a solution of 63.6 parts of the sodiumi salt
of 1-hydroxy~B-m-(2',4',5'-trichloropyrimid-6'-ylamino)-benzoyl-
amino-naphthalene-3,6-disulfonic acid in 250 parts of water.
After addition of 5.3 parts of sodiumi carbonate, 6.9 parts
of sodiumi nitrite were added while stirring at 5C and at a
pH of ~Ø While the dyestuff formed speedily,the pH rose to
4.8. The addition of 10 par-ts of disodiumi hydrogenophospha-te
and another 12 parts of water resul-ted in 363 parts of a dye
-- stuff solution which contained 25% of the dyestuff of the for-
~, - 27 -
'
.
.
~ .:
HOE 751~ ,77
109~(P55
mula (XVI)
~s ~ N====N ~ ~ ~ ~
SO~N HO5 O~H . ~ (XVI)
c:~ a
and had a pH of 6.3.
2 Parts of this pH~stabilized solution were used to pre-
pare~ in the know~ and usual ma~ner, a dyebath, a padding li
quor or a printing paste which was then applied and ~ixed on
cotton in a manner usual for reactive dyes to pro~ide red
dyeings and prints. These had the same good color intensity
as those produced with equally concentrated dyebaths, padding
liquors or printing pastes prepared with 1 part of a powder
brand containing 50% of the dyestuff.
This color intensity of the prints and dyeings was un-
changed even after the above-said novel aqueous composition
had been stored for 3 months at 20~C in a closed container.
E X A M P ~ E _17:
31.3 Parts of 2-naphthylamino-6,8-disulfonic acid and 8.4
parts of sodium hydrogenocarbonate were introduced into a so-
lution of 38.4 parts of the sodium salt of 1-4'~ sulfato-
ethyl-sulfonyl)-phenyl-3-methyl-5-hydroxy-pyra~ole in 85 parts
of water and 26 parts of -caprolactam. At 10C, 2 parts
of disodium hydrogenophosphate were added to raise the pH to
4.6. Then 6.9 parts of sodium nitrite were stirred into this
mixture. The dyestuff formed speedlly with the pH hardly
rising. 188 Parts of a solution were obtained which contain-
ed 40~0 of the dyestuff of the formula (XVII)
- 28 ~
.
, . ' ' ' :' ' ~ :
.
~IOE 7~F ~77
g~5~ ,
H03S ~13C
I ~ N
N=N ~ I (XVII)
~ l-/
b,~ SO~-CH2-CH2-0-So3
,
and had a pH of 4.9.
? Part o~ this pH-stabilized solution were used to pre-
pare, in the known and usual manner, a dyebath, a padding li-
quor or a printing paste which was then applied and fixed on
cotton in a manner usual for reactive dyes to provide yellow
dyeings and prints. These had the same good color intensi~y
as those produced with equally conoentrated dyebaths, padding
liquors or printing pastes prepared with 1 part o~ a powder
brand containing 40~ of the dyestuf~.
This color intensity of the prints and dyeings was un-
changed even af-ter the above-said novel aqueous composition
had been stored ~or 3 months at 20C in a closed container.
In the same analogous manner as disclosed in the preced-
ing Examples~ dyeing compositions of the invention can be pre-
pared using the dyestuffs known from German Of~enlegungsschri~t
No. 1,150,163; Fx. 1, German Offenlegungsschrift No. 1,804,524;
Ex. 4 and ~, German Of~enlegungsschri~t No. 1,769,091; Ex. 6,
German Patent No. 1,248,188; Ex. 1, German Patent No.
1,289,930; Ex. 19, US~Patent No. 3,419,541; Table-Ex. 11
German Patent No. 1,204,762; Ex. 38, German Patent No.
960~534; Table-~xl 8,on page 9, and Belgian Patent No.
598,831; Ex. 4, and starting from the diazo and coupling com-
ponents to be seen from the azo dyes.
- 29 -
'
' ' '
'
