Note: Descriptions are shown in the official language in which they were submitted.
~ ~IOE_ 75/F 071
` ` ` 1073450
.
The present invention relates to 1:2-co~alt-complcx azo
dyestuffs, to a process for their-preparation and their use.
We have found new water-soluble 1:2-cobalt complex monoazo
dyestuffs of the general formula 1
~H3
Q~ o=C
so H
1 - ~ ~2
in which R1 is a chlorine atom or a nitro group, R2 is the
: - methyl, e~hyl, methoyy or ethoxy group, preferably t~e methyl
- or methoxy group and R3 is the methoxy or ethoxy group, pre- -
ferably the methoxy group.
The new dyestuffs can be prepared according to the invention
-~-15 by diazotiæing 4-chloro- or 4-nitro-2-aminophenol and coupli~g
- wlth a compound of the formula 2
~ . . .
co C~
l~2 l3 (2)
-- - - CO-hTH~ ~
20 ~ So3H
.~ .
-. in which R2 and R3 are~defined as above, at a p~ of fro~ 6.,
to 9, prefer-ably 7 to 8.5, and metallizing the azodyes~f~
obtained with cobalt-yielding agents, op~ionally in the
~2~ presence of acid-binding agents at a temperature of fro~ 90
to 105C under nor~al pressure or at a temperature o~ from
10~~ to 130C, for example 120 to 130~C, unaer pressure.
Cobalt-yielding agents are, for exanple, cobalt-carbonate.29 cobalt hydroxycarbonate, cobalt-acetate, co~alt s-llfate~ whieh
. - 2 ~
~ .
HOE ?5 jF 071
1073450
are used optionally in the presence o~ acid-binding agents, for
example sodium or potassium acetate, sodium or potassium
carbonate or alkali metal hydroxides, as potassium hydroxide.
- The dyestuffs are isolated from their preparation solutions
by salting out with sodium or potassium chloride or by spray
-~ drying.
- The 1:2-cobalt-complex azo dyestuffs according to the
invention are preferably in the form of their alkali metal
salts, preferably sodium, potassium or ammonium salts,and are
O also used in the form of these salts. They are suitable for
` dyeing polyurethane fibers or natural polyamide fibers, such
- as wool and silk, and synthetic polyamides, especially the
condensation products obtained from caprolactam, from hexa-
-. I
methylene diamine and adipic acid, or from ~-amino-undecylic
~5 acid. They are also especially suitable for dyeing the fibers
: ~ .
mentioned in mixture with other hydrophobic fibers, for
example wool and polyester fibers, the hydrophobic fiber -
portion being excellently reserved, and ha~e a high affinity
to the fiber and a good colour build-up, and dye the fib~r~
mentioned in level and constant shades, even at varying
p~-values.
The novel dyestuf~s can also be used in mixture with other
1:2-cobalt or chromium complex dyestuffs, which contaln one
to two sulfonic acid groups per dyestufI molecule. For the
dyeing from acid or neutral dyebaths, at a te~perature o~ from
90 to 105C, preferably at a pH in the range of from 4 to 6.~,
the usual dyeing auxiliaries are used, for example fatty amine
or fatty alcohol oxethylation products and usu21 bufler SUD-
stances to stabilize the p;l-~alue for dyeing. For ex~ple,
- T~ ,
.
`
.
HOE 75/F 071
' `~.1073450
the addition of an acid, for example formic acid or acetic
acid, or a mineral acid to the dyebath which contains alkali
metal salts of the formic acid or the acetic acid or of other
organic or inorganic acids, permits to adjust that pH-value
whicn is the best for dyeing in dependency ~n the dyestu~
concentration used and on the color intensity desired on th~
fiber. ~ -
Local dyeing by printing is effected with the use of
printing pastes ~thich contain the usual thickening agents and
~I printing auxiliaries, and a salt of a ~Jeak base and of a
.
`- strong mineral acid or an organic acid, for example ammonium
-~ sulfate or ammonium tartrate. The printed fabrics are driéd
- and treated with hot air or steam for a short time.
According to these processes, natural and synthetic poly-
amide fibers are dyed golden-yellow shades, they have good
.-. -
to very good fastness propertles to wet processing, for
<)~ example the fastness to washing at 40 and 60C, the fastness
`~ to water under se~rere conditions, the fastness to alkaline ard
- ~- acid perspiration, the fastness to acid and alkaline fulling,
~0~ the fastness to acid cross-dyeing, to steaming and to dec2-
tizing, and excellen~ fastness properties to the light in the
Xenotest and in the daylight.
:
~Comp~red to dyestuffs of similar strl~cture kno~m from the
- ~rench Patent Specification No. 1 Z72 729 the dyestuffs OT^ th~
~5 invention are distinguished by an improved affini~y and bw ld-
up property, an in-proved levelness of the dyeings, for example
woollen flocks, alone or in mixture with 1:2-metalcomplex
~ dyestuffs which contain t~to sulfonic acid groups, and an im-
'9 proved constance of the shades at varying pH values,~especially
- 4 -
' ' '' I
~. . - - .
.
HOE 7~ 071
- 1073450
.
when lo~rering the pH-values-w~icll can be done to improve the
ex~austion of the dyebath.
The following Examples illustrate the invention, the parts
and percentages being by weight.
E X A M P L E 1:
15.4 Parts of 4-nitro-2-aminophenol were dissolved with
25 parts of hydrochloric acid of 31 C6 strength in 150 parts
of water and diazotized, after adding 50 parts of ice, by intro-
ducing 17.3 parts of a 40 % sodium nitrite solution. A~ter
}O 30 minutes a small amount of amidosulfonic acid was added to
destroy excess nitric acid. 30.1 parts of N-acetoacetyl-
cresidin-sulfonic acid were added and the pH was adjusted to
8.5 to ~ with calcined sodium carbonate solution. Coupling
was finished at room temperature after 6 hours. The pH-value
~5 of the dyestuff suspension was adjusted at first to 7 by means
i;~-
` of hydrochloric acid of ~1 ~ strength, then to 6 by means of
acetic acid. 6.35 parts of cobalt hydroxycarbonate (havi~g
~ - a contsnt of 47 % of cobalt) were added and the mixture ~las
`~i heated under reflux ~or 4 hours. The 1:2-cobalt complex was
7 separated by salting out with sodium chloride or isolated by
` spray~drying. The dyestuff corresponds to the ~ormula
2 - - _
~N====N-C~C,~I~
~ o < ~ - C~3 --
- ~3C~ ~ / ,
-~0,5~ 0-- ~ :
H~Co H NO2
- - 5 -
- Ç
'
- ~.
1073450 HOE 75/F 0;1
in the form of the free acid.
` Dyeing Example
.
100 Parts of a woollen fabric ~lere introduced into a dye-
bath of 40C which contained 1 part of the dyestuff of Example 1,
0.15 par~ vl an a~dition produc~ of 12 m~l~ o~ e~hy ene o~id~
to 1 mol of stearyl amine, 2 parts of ammonium acetate and
2 parts of acetic acid of 60 % strength in 3.000 parts of
water. The temperature was raised to the boiling point within
` 30 minutes and dyeing foll~wed at 100C during 60 minutes.
;iO After the usual finish, a golden-yellow dyeing ~Jas obtained
having a good levelness and good ~o very good fastness proper--
ties to wet processing and an excellent fastness to light.
When the ~roollen fabric was replaced by 100 parts of a
fabric made of polycaprolactam, a dyeing was obtained which
-l5 had also good to very good processing properties and an ex-
,.;. - - .
` -cellent fastness to light.
_ X A M P L E 2: -
.~en in Example 1 the 4-nitro-2-aminophenol ;as replaced by
~ 14.4 parts of 4-chloro-2-aminoph~nol, the process being other-
'O wise effected as described therein, a dyestuff was obtained
which had ln the form of the free acid the formula
. ci ~ ~',
~=~~0~ ~q~O,~
o ~ I `
~0;, S~ C C-N=====_N~
- ~3 C ~ H Cl
- ~,
--- - r~
'
-
.''' ~
, ,, .. . .:
HOE 75/F 071
1 07345
Dyein~ Example:
100 Parts of a fabric made of polycaprolactam were intro-
duced into a bath o~ 40C which contained 1.5 parts of the
dyestuff of Example 2, 0~15 part of the addition product o~
~5 12 mols of ethyl~r.2 oxid~ to 1 mol o~ ~tearyl amine, ~ par's
of ammonium acetat.e and 2 parts of acetic acid of 60 ,' strength
in 3,000 parts of water. The ~mperature was raised to 98-100C
` within 15 minutes and dyeing follo~ed at 100C during 60 min-
- utes. After the usual finish, a golden-yellow dyeing was
~0 obtained which had good to very good fastness properties to wet
processing and an excellent fastness to light.
., .
When the polycaprolactam fabric was replaced by 100 parts
- .
of a wollen fabric, a dyeing was obtained which had also good
to very good processing properties and an excellent fastness
~5 to light.
E X A ~ P L E 3- -
;, . .
~ 15~4 Parts of 4-nitro-2-aminophenol were dissol~ed with
, ~1 ' _ .25 parts of hydrochloric acid of 31 % strength in 15~ parts of
water and diazotized, after the addition of 50 parts o~ ice,
~0 by introducing 17.3 parts of a 40 ,b dosium nitrite solution.
After 30 minutes, a small amount of amidosulfonic acid was
added to destroy excess nitric acid. 31.7 parts of ~-aceto~
acetyl-2-aminohydroquinone-dimethylether-5-sulfonic acid were
~ added and the pH was adjusted to about 8.5 by means of calcine~
2~ sodium carbonate solution. m e coupling was finished at room
temperature a~ter 6 hours. m e-pH-Yalue of the d~estuff sus-
pension was adjusted at first to 7 with hydrochloric acid of
~ 31 % strength, and then to 6 with acetic acid. 6.~5 parts of
29 cobalt hydroxyde-carbonate (content of cobalt 47 ~) were added,
~ - 7 -
,
~IOE 75/F 071 -
1073450
and the mixture was heated under reflux for 4 hours. The
1:2-cobalt complex was separated by salting out ~ith sodium
chloride or isolated by spray-drying. The dyestuff corre-
sponded in the form of the free acid to the formula
- ~2 _ _
- , , Ip ~ F . ~`so3
, ~ , -, --Co/ C~5, .
~3Co HSC C ~ ¦
~OsS~ ~C~}~ 3 ,..- .
- ~3CO - -
2
D~eing Example- -
Polyamide carpet yarn was treated with an aqueous padding
- liquor which contained 10 parts of the dyestuff of Example 3,
:`
- 5 parts of a locust bean flour preparation, 4 parts of &n
addition product of 8 mols of ethylene oxide to 1 mol of iso-
- tridecyl alcohol and 10 parts of acetic acid of-60 ~ strength
-20 in 1,00Q parts of the padding liquor, the liquor picl~.-up was
100 ~. The yarn was steamed at 100 - 102C for 6 minutes and
then rinsed with cold water in the usual ~nanner. The dyelng
had very good processing properties and an excellent fastness
to day light.
~25 ~
~en in Example ~ 4-nitro-2-aminophenol was replaced by
- - 14.4 parts of 4-chloro-2-aminophenol, and the process ~as
effected as described therein a dyestuff was obtained ~ich
29 corresponded in the form of the free acid to the formula
' ' 1
., ~
' ~073450 ~OE 75/F ~-1
- . ,
Cl
~ ~ ~5~3
`' ' ` ` ` ~ n ~ SO~F.
`~ ` ` o \~ o~C ~ C~I3 OCH3
`: 5 . Co~
-JIC)D5~3 ~~
,~ - ,. CC~ O Cl -, - .
~1 0 , . ~ - , , ,~ - D~eing Example:
100 Parts of woollen flocks were introduced in-c~ a dyebath
of 40C which contained 1 part of the dyestuff of Example 4,
0.15 part of the addition product of 12 mols of ethylene oxide
to 1 mol of stearyl amine, 2 parts of ammonium acetate and
`~, 2 parts of acetic acid of 60 % strength in ~,000 parts of water.
~ The temperature was raised to the Ooiling point within 30 min-
`;~- utes, and dyeing followed at 100C during 60 minutes. After
the usual finish, a level, golden-yellow dyeing was obtained
which had ~ery good fastness properties to wet processing and
an excellent fastness to light.
When the 100 parts of woollen flocks were replaced by the
same amount of ~oollen hank yarn, a good level dyeing ~Jas also
` obtained which had good to very good fastness properties to
wet processing and an excellent fastness to light.
"' ~ : ,. . .
.'
_ g _
. ~' . ' ' ' .
.: ~
-' ` ` ~
