CA1059998A - Water-soluble disazo dyestuffs, process for their preparation and their use - Google Patents

Abstract

WATER-SOLUBLE DISAZO DYESTUFFS, PROCESS FOR THEIR
PREPARATION AND THEIR USE
Abstract of the Disclosure:
New water-soluble disazodyestuffs of the formula

Description

105999~

The present invention concerns water-soluble disazo dyestuffs~ a process for their preparation and their use for dyeing synthetic polyamide fibers.
New water-soluble disazo dyestuffs were found~ which in the form of the free acid correspond to the general formula (1) 03 ~ N N ~ ~ N=N ~ NH-C0 ~ 3 (1) in which the radicals Rl and R2 are identical or different, each represent-ing a hydrogen atom, a methyl, ethyl or methoxy group, and the radical R3 stands for a hydrogen or chlorine atom, or an alkyl group of 1 to 4 carbon atoms, such as for example the methyl, iso-propyl or tert.~butyl group. The dyestuffs are preferably used in form of their sodium~ potassium or ammonium salts.
The present invention also provides a process for the preparation of a dyestuff of the general formula 3 ~ N=N ~ - N=~ ~ ~N-C0 ~

in which the radicals R1 and R2 are identical or different, and each is a hydrogen atom, a methyl, ethyl or methoxy group, and the radical R3 stands for a hydrogen or chlorine atom, a nitro group or an alkyl group of 1 to 4 carbon atoms; by coupling the diazo compound of 1 mol~of 4-amino-azobenzene-~OS9998 3~ 4'-disulfonic acid of the formula (2) 3 ~ ~ / ~ (2) with 1 mol of the following coupling components (3)~ (4) or (5) R2 2 ~

NH2 ~ 2 3 ~ H-S03H
R;i Ri Ri (3) (4) (5) to yield the disazo dyestuffs of the formulae (6), (7) or (8) -2a-HOE ?4!F ~82 105~998 ~0~ l2 ~sS ~ N===N ~ ~ N~2 (6) R~
~0~S ~ N===N ~ ~ N ~ NE-C~2-SOSH (7) ~SOs~ ~
~05S ~ N===N ~ N=~=N ~ N~-SO3E (8) then splitting off the sulfo or sulfomethylene group in the dyestuffs of formulae (7) and (8~ by acid or alkaline hydro-lysis to yield the dyestuffs of formula (6), and then reacting subsequently the dyestu~fs of the formula (6) with the acid chloridc o~ the formula (9) ~a~R5 Cl in the presence of an acid binding agent at a temperature of between O to 25C and at a pH in the range of 6.0 to 9.0, pre-ferably between pH 7.5 and 8.5.
As coupling components of the general formula (3), respec-tively the derivatives corresponding to the general formulae (4) or (5), the following ones are preferably used:
Aniline, 2- and 3-methylaniline, 2,5-dimethylaniline, 3-ethy].-29 aniline, 2- and 3-methoxyaniline.

--- ~ HOE 74/'~ ~82 Acid chlorides of the general formula 9 are, for example:
Benzoylchloride, 4-toluylchloride, 3- and 4-chlorobenzoyl-chloride, 3- and 4-nitrobenzoylchloride, 4-isopropyl-benzoyl-chi~fiue ~lu 4-~e.-b.-~utyl-be~ o-y ohlvrid~.
The present invention concerns furthermore the use of the new disazo dyestuffs for the dyeing of synthetic polyamide fibers, especially those of caprolactam of hexamethylendiamine and adipic acid or of polycondensation products obtair~able from W -amino-undecanoic acid.
The dyestuffs are used as free acids or as salts. They may also be used in mixture with other suitable dyestuffs ~or -dyeing synthetic polyamide fibers. The dyebaths contain per 1000 parts by weight of the dyebath 0.01 to 20 parts by weight ~5 of dyestuff, 0.05 to 10 parts by weight of usual dyeing auxil-iaries and 0.05 to 10 parts by weight of usual dispersants.
The batches are chosen in such a way that the dyeing bath is neutral or acid. By addition of 0.01 to 20 parts by weight of an acid, for example of formic acid or acetic acid or also of mineral acid, or alkali salts, as sodium salts, of the formic-or acetic acid to the dye-bath, dyeing can be carried out in a weak to strong acid but preferably in a weakly acid or neutral bath (pH 4 to 7) and advantageously at a temperature between~
80 and 105C, optionally between 90 and 105C.
For local dyeing by printing, aqueous printing pastes are used which contain per 1000 parts by weight generally 1 - 50 parts by weight of dyestuff, 250 to 700 parts by weight of a usual aqueous thic~ening such as~ for example, crystal gu~, 29 1 to 50 parts by weight of usual printing auxiliaries, 1 to 50 parts by weight o~ usual dispersants and 5 to 5G parts by weight of a salt of a weak base and a strong mineral acid or organic acid, for ex~mple, ammonium sulfate or ammonium tartrate, and water. The printed fabrics are dried and ~reated for a short time with hot air or steam.
According to this process applied on synthetic polyamide fibers~ yellow to yellow-bro~m shades with good to very good fastnesses to wet~ for example,.fastness to washing at 40C
and 60C, generally called washing test 1 and ~ in DIN 54 014 and DIN 54 010, to water under severe conditions (DIN 54 006), -~o alkaline and acid perspiratio~, to hypochlorite bleach mild (DIN 54 034) and to hypochlorite bleach severe (DIN 54 035), to chlorinated water, to rubbing in the dry or wet state~ to fulling in acid and alkaline medium, fastness to steaming, ~astness to alkali and to acid, to decatizing and to dry cleaning, as well as with excell~nt fastness properties to light in xenotest- and day-light were obtained.
The dyestuffs excell by a good built-up property and good properties to migration, thus permitting to obtain deep dyeings with good e~enn-ess.
Together with selected yellow, red and blue acid dyes, the new dyestuffs are very suitable for the dyeing of blended dye shades with excellent fastness properties to light.
The following examples illustrate the invention. Parts and percentages are by weightO
X X A M P L E 1:
35.7 parts of 4-aminoazobenzene-3,4'-disulfonic acid in form of the neutral alkali salt were stirred into 150 part.s of 29 water and added to ~,9 parts of sodium nitr.ite~ and the whole HOE 74/F ~2 ~OS9998 was poured slowly into a mixture of 100 parts of ice and 32 parts of ~ 31 % hydrochloric acid. For the decomposition of nitrous acid in excess, a small quantity of amido-sulfonic acid was added after 3 hours. The suspension of the diazo-salt was inen adjusted with wa~srfree æofiiu~ o~r'oon~
a pH value of 2.5 and brought to reaction with a solution of 20,1 parts of m-toluidine-N-methanesulfonic acid in 100 parts of water. The pH value was then adjusted to 4.5 with water-free sodium carbonate and kept until complete coupling.
Afterwards, 48 parts of a 31 % hydrochloric acid were added, and the whole was heated durin~ 2 hours under reflux. After cooling to room temperature, the product was filtered and washed with water. The moisty filter-cake was mixed with ~00 parts of water and diluted with-an aqueous 33 % solution f sodium hydroxide at pH 8.5. By a dropwise addition of ~5 parts of enzoylchloride while ~eeping at the same time the pH value at 8.0 - 8.5 by means of waterfree sodium carbonate, a yellow dyestuff of the following formula was obtained:
SO~H O
~O~S ~ N=_-N ~ N~
~5C

By adding sodium chloride, the partially crystallized dyestuff was completely precipitated and isolated by filtration.
DYein~ Example:
100 parts of a polycaprolactam ~abric were put into a bath having a temperature of 40C; the bath contained:
1.5 parts of the above mentioned dyestuff, 29 0.15 parts of the addition product of 12 mol of ethylenoxide ~5999~
on 1 mol of stearylamine, 0.40 parts of the condensation product of 1 mol cyanochloride (trichloro-s-triazine), ~ mol of aniline-~-sulfonic acid,

2.0 pa~t~ ul ~iUiUU~li-U~ ~cet~te ~,u 1.0 part of an aqueous 60 % by weight acetic acid and 3000 parts of water.
The temperature of the dyebath wa~ raised within 15 minutes up to 98 - 100C, and dyeing was continued for 60 minutes at 100C. After the usual finishing, a yellow dyeing with good to very good fastness to wet such as for example, fastness to water under severe conditions, to washing at 40C and 60C, fastness to perspiration in alkaline and acid medium, to steaming, to alkali and to acid, and with an excellent ~astness to xenotest- and to day-light was granted.
E X A M P L E 2:
.
3S.7 parts of 4-aminobenzene-3~4'-dis~lfo~ic acid in form of the neutral alkali salt were stirred into 150 parts of water.
The solution was added to 6.9 parts of sodium nitrite, and the whole poured slowly~whilst stirringlinto a mixture of 100 parts of ice and 32 parts of a 31% hydrochloric acid. For the decomposition of nitrous acid in excess, a small quantity of amidosulfonic acid was added after 3 hours. The suspension of diazo salt was then adjusted with waterfr~ sodium carbonate at a p~ value of 2.5 and brought to reaction with a solution of 21.7 parts of 2-methoxy-aniline-N-methansulfonic acid in 100 parts of water. The pX value was then ad~us~ed with water-free sodium carbonate ~o 3.~ - 4.0 an~ kept at this value 29 until complete coupling. Afterwards9 4~ parts of ~ 31% hydro-105~998 chloric acid were added, and the whole was heated under re-flux for 2 hours. After cooling to room-temperature, the dye-stuff was separated by f$1trati~ and washed with water.
~he moisty f~lter ca~e was stirred with 200 parts of w~ ~ù di~soived with an aqueDus 33~ by weight sod~um hy-droxide solution at a pH 8.5. By a dropwise addition of 20 parts of 4-chlorobenzoylchloride~while the pH was kept with waterfree sodium carbonate at 8.0 to 8.5, a dyestuff of the following formula was obtained:
SO~.~ ' OC~ ~s ~lo~s~ ===n~n-c~cl The d~estuff was separated by salting out with sodium chloride and i~olated by filtration.
~yein~ ExamPle:
A polycaprolactam fabric wa~ printed with an aqueous paste per 1 Ug. 10 parts of the above~entioned dyestuff, 30 parts of dibutylglycol, 250 parts of w~ter, 650 parts of an aqueous crystal gum thickener, 30 parts of nitro-benzene-3-sulfonic acid and 30 parts of ammoniumsulfate. The printed fabric was dried and steamed during ~0 minu~s at 100 - 102 C. After a subsequent rinsing and drying, ~inishing was e~fected as usual.
The golden-yellow print has an ex~-ellent fastness to llght and possesses good general fabricati~n fastnesses.
E X A ~ P ~ E 3: `
Dia~otation of the 4-aminoa~oben~ere-3,4'-disulfonic acid was effected as indicated in Example 1, a~d the diazo sus~en-2~ sion was brought ~ reactlon wlt~ solution of12.1 par~s of 295-1l~55~998 dimethylaniline and 15 parts of a 31% hydrochloric acid in 150 parts of water while the pH ~alue was kept with waterfree sodium carbonate at 2.8 - 3.2 until complete coupling. A dye-stuff was obtained, which, after reaction with 25 parts of 4-+ert.b--tylben~o~ h~^ri~e c~rrA~ d~D ~o EV9.~P1 e n+ ~ P~A
of 8.0 - 8.5, yielded a golden-yellow dyestuff of the follow-ing formula:

SOaH c~5 ~IO3 S ~N= ==~;3N= _ =N~ _ C ~3C ( C~5 ) 3 ~3d~ .

D~ein~ Example:
100 parts of a tufted carpe~ of polyamide fibres, pre-heated to 100C in saturated steam, run during 5 minutesthrough a hot solution of 100 - 102C, containing 15 parts of the abovementioned dyestuff, 0.3 parts of the additlon product of 12 mol of ethylenoxide on stearylamine, 2 parts of sodium acetate and 1 part of acetic acid per 1000 parts of water.
Subsequently it was rinsed and dried. An eve~ golden-yellow dyeing with excellent fastness to light and good general fast-nesses was obtained.
The same coloristic result was obtained with tufted felt carp~ts.
E X A M P ~ E 4:
To a suspension.of diazotized 4-aminoazobenzene-3,4'-di-sulfonic acid as prepared in Example 1, a solution of 17.3 parts of aniline-sulfamide acid in form of the ammoni~ salt in 100 29 part of water was added, and the pH value W8S adjusted with _ 9 _ ~059998 waterfree sodium carbonate at 3.5 - 4Ø After complete coupling, 48 parts of a ~1~ hydrochloric acid were added and the whole was heated during 3 hours under reflux. The preci-pitated dyestuff was separated by filtration and washed with water. The moisty filtercake was dissolveâ in ~uu parts oi water with an aqueous 3~% by weight sodium hydroxide solution at a pH of 8.5. The solution was then slowly brought to reac-tion with 25 parts of 3-~itrobenzoylchloride, whereby the pH
value was kept at the same time with waterfree sodium carbo-nate at 8.0 to 8.5. The dyestuff of the following formula was isolated by salting out with sodium chloride and separation by filtration:

, .
SO~H N02 ~OsS ~ l~-==N ~ ~===N ~ N-D~eirl~ Example:
A polyamide carpet yarn was treated with a padding liquor up to a liquor pick-up of 100% by weight, whereby 1000 parts of the padding liqour contained 10 parts of the dyestuff o~
the abo~e formula, 5 parts of a locust béan flour preparation, 4 parts of an addition product of 8 mol of ethylenoxide on 1 mol of iso-tridecyl alcohol and 15 parts of an aqueous 60~ by weight acetic acid. The padded yarn was subsequently steamed during 6 minutes at 100 - 120C and rinsed with cold water.
The dyeing possesses very good general fastnesses and an excel-lent fastness to light.
The following table containSfurther dyestuffs which were 29 prepared and dyed according to the a~ovementioYled examples and ~ - HOE 74/~ 382 ~059998 show good general fastnesses of the dyeings.

Example Shade on pol~-No. Formula amide ftbre Sû5--~5S~ =N~~ E(c~3 )2 yellow ~;~
SO~ 3 6 HO5$~=N~N=N~N-C~C~CH3 )5 golde~-yellow SO3 H CH3 Cl 7 HO5S ~ N=N ~ N=N ~ N-C ~ golden-yellow ~3 5~3 H CH;s 8 . H8 S~r~=N~N=N~N-C~No2 yellow ' S03~I
~03S ~ N=N ~ N=N ~ N-C ~ golden-yellow H3~0 S03 ~I , lûHb~S ~ N=N ~ Na~ ~ N- ~ C~3 yellow ~6 2 -SU5~ H yellow H~C2

Claims (5)

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

1. Water-soluble disazo dyestuffs, which, in form of the free acid, correspond to the general formula in which the radicals R1 and R2 are identical or different, and each is a hydrogen atom, a methyl, ethyl or methoxy group, and the radical R3 stands for a hydrogen or chlorine atom, or an alkyl group of 1 to 4 carbon atoms.

2. A process for the preparation of a dyestuff of the general formula in which the radicals R1 and R2 are identical or different, and each is a hydrogen atom, a methyl, ethyl or methoxy group, and the radical R3 stands for a hydrogen or chlorine atom, a nitro group or an alkyl group of 1 to 4 carbon atoms:
Wherein the diazo compound of the 4-aminoazobenzene-3, 4'-disulfonic acid of the formula is coupled with a coupling component of the general formula in which R1 and R2 are as defined above and T is a hydrogen atom, a sulfo group or the sulfomethylene radical, to yield a disazo-dyestuff of the general formula in which R1, R2 and T have the beforementioned significations, and said disazo dyestuff in which T stands for the sulfo group or for the sulfomethy-lene radical, is converted to said disazo dyestuff in which T is a hydrogen atom by splitting off these groups in acid or alkaline medium, and disazo dyestuff in which T is a hydrogen atom, is acylated with an acid chloride of the formula in which R3 is as defined above.

3. A process for dyeing synthetic polyamide fibers utilizing dyestuffs as defined in claim 1.

4. A process according to claim 3, characterized in that the dyeing of the polyamide fibres is effected in a neutral or weakly acid aqueous bath at 90 - 105°C.

5, A process according to claim 4, characterized in that a polyamide fabric is printed with a thickened dyestuff solution and then fixed by a steaming process after drying.