CA1073450A - 1:2-cobalt-complex azo dyestuffs, their preparation and their use - Google Patents

Abstract

Abstract of the Disclosure:
Water-soluble cobalt complex azc dyestuffs of the formula

Description

~ ~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 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~ , .
`
.

' `~.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 ' ' '' I

~. . - - .
.

HOE 7~ 071 .
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 - 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~

' -.''' ~
, ,, .. . .:

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 -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 - -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.

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Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A water-soluble 1:2-cobalt complex of a monoazo dyestuff of the for-mula (1) in which R1 is chlorine or nitro, R2 is methyl, ethyl, methoxy or ethoxy, and R3 is methoxy or ethoxy.

2. Process for the preparation of the 1:2-cobalt complex dyestuffs as claimed and defined in claim 1 which comprises diazotizing 4-chloro- or 4-ni-tro-2-aminophenol and coupling it with a compound of the formula in which R2 and R3 are defined as in claim 1 and metallizing at 90 to 130°C
with a cobalt yielding agent optionally in the presence of an acid-binding agent.

3. A process for printing or dyeing a fiber-material wherein a dyestuff according to claim 1 is used.

4. A process for dyeing natural or synthetic polyamide fibers or poly-urethane fibers wherein a 1:2 cobalt complex of a monoazo dyestuff according to claim 1 is used.

5. Fiber-material dyed or printed with a dyestuff according to claim 1.