CA1064022A - Water-soluble disazo dyestuffs, a process for their preparation and their use for dyeing synthetic and natural polyamides - Google Patents

Abstract

Abstract of the Disclosure:
New water-soluble disazodyestuffs of the formula

Description

HOE 74~F 381 L~ ,J ,~
The present invention concerns watsr-soluble di~azo-dye-stu~f~, a proce~s for their preparation and their use ~or dyei~g synthetic and natural polya~ides.
N~w water-soluble disazo dyestu~ were found, which, in t~e ~or~ o~ 'he ree a~id, cor~espond tD ~ha general ~ormula (1) ~03S~ =N~

in which R1 represents the ~ethyl, ethyl~ ~-hydroxyethyl ~
B-cya~oethyl group and R2 stands for a phenyl radicalv where-by the radical -OR1 stands in ri~.g A in 2~ or in 4 positlo~.
to the azo group. These new dyestuffs of the formula (1) can 15 al50 be present as mixtures. Preference is given to thei.r sodium9 potassium and ammonia salts.
The n~w dyestuffs are prepared, accordi~g to the inven-tion9 by coupling the dia~o compound of 1 mol of 4~am~no-azo ben~ene-4'-sul~o~$c acid of the ~ormula ~2 ~03~ ~ -N~ NH~ (2) with 1 mol of a coupling compo~ent of the fvr~ula ~4) or (5 .
25: EO

R2 R~

.

Z9 R2 hav~ng the above mentioned signifieatio~9 su~h $s for , .. ... . , , . , , . , ~ ................... . . . . .
.. ; . . . . .. . , -. , .. .- . . -example ~ and - ~ ~

or with 1 mol o~ a mixture of the~e ~-oup].ing compo~ents, in a temperature range o~ O - 30C a~d i~ a pEI ran~e 8 - 12~pre~er-ably at a pH ~alue betwee~ 10 - i2; subsequently, the ~ree hydroxy group is reacted optionally in presence o~ water, and an acld binding agent with an alkylation agentS A~ a:L~ylat~n agent~ there ca~ be cited :
dimethylsul~ate, diethylsul~ate, methylbro~ide~ eth~lbromide or ethylchloride, ethylen~chlorhydrine or ethyle~ox~de, B-chloro-propionitrile or acrylo~trile.
The present invention concerns furthermore the use o~
the dis~zo dyes of the invention and ~heir mixtures ~or the dyelng of natural polyamide fibres, such a~ wvol and silk~ and synthetlc polyam~des~ particularly those of caprolactam 5 of hexamethglenediamine a~d adipic acid or o~ polycondensation pro-ducts obtainable ~rom ~r-ami~o-undecan~ic acid.
The dyestu~fs are used as free acids or as salts. They may alsc be used i~ mixture with other sultable dyestuf~s f'or dyelng of the aboYementioned, pre~erably synthetic9 textile materials. The dyebat~ contain 0.01 t~ 20 parts b~ weight of dyestu~, O.Q5 to 10 parts by weigh~ o~ u~ual dye auxiliair~es a~d 0.05 to 10 parts bg w~ight of usual dispersants per 1000 parts by weight of d~ebath. The admixture~ are chose~ in such a way, so that the dyeing bath i~ ~eutr~l or acid. Also d~eing can be carried out i~ a weak to strong acid bath by addition of ~ 3 ---- .. . .

.. i,, . ,, " , ....... .. . ..... .. .. ... . . . ..

0~01 to 20 parts by weight of an acid, for example of form$c acid or acetic acid or also of a mineral acl~ or of alkali ~lts of the formic or acetic acid, to that neutral dye-bath, but preferably dyeing is carried out ln a we~ly acid or neu-tr~l bath (r~ A - 7), and ad~a~'~g~^u~ly æt a tempe~at~e be-tween 80 and 105C, preferably betwee~ 90 and 105C.
For local dyeing by printing 9 printiLng paste~ are used which contain per 1000 parts by ~eight generally I to 50 part~
by wei~ht ~f dyestuff, 250 to 650 parts b~ weight of a usu~l thickener such as, for 0xample, crystal gum, 1 to 50 parts by weight of a usual printiIlg auxiliairy) 1 to 50 parts by weig~t G~ a u.sual dispersa~t and 5 to 50 parts by weight o~ a salt o~ a weak base and a strong mineral ac~d or o~ an organic, for example, ammonium sulfate or a~mo~ium tartrate. For the ob-tention o~ 1000 parts by weight o~ the prlnting pasteD water or thickener~ are added adequately. The printed ~abrlrs are dr~ed and treated for a short time wlth hot air or steam.
According to thi~ process applied on natural or syntheti~
polyamide fibres, golde~ yellow to ora~ge shades with good to ver~ good ~astnesses to wet, for exampl~ ~astne~s to washl~g at 40C and at 60C, generally called washing test 1 and 3 in DI~ 54 ~14 and DIN 54 010, to water uJlder severe con~itlons ~DIN 54 ~06), to alkaline and acid perspirationg to hypo-chlorite ~each mild (DI~ 54 034) a~d to h~pochlorite bleach severe (DIN 54 35)1 to chlorinated water to rubbin~ ln the dry or wet state, to ~ullin~ in acid and alkaline med~um9 fas~--ness to steaming, fastnes~ to alkali 9 to aold9 to decatlzing and to dr~ cleani~g as well as with ~ery good to excelle~t

2~ .~as~ness propertie~ to light in xe~o-test a~d da~-light were .~ .

... : . . . , . ... - . -;, .: .. ,, : , .. .
.. : .. . : . .. .. . . . . . . - .
~ . .
: .. : . .. .. : , . - . ... , . , - . :
: ., ~ . ~ . .. . . . . -. . : -: -, : ~ . . . ... .. .

obtained.
The dyestu~fs e~cell b~ a good built~up property and good properties to migration, thus permitting to obtain deep clyeings with good eve~ness. Particularly1 polyamide flbres oan well e~ual be dyed in spite of their steady mvietie3.
Furthermore, together wlth well cho~en yellow, red and blue acid dyes, the new d~estuffs are ~er~ suitable Xor the dyeing of blended dye shades with very good fastness proper ties to lighto The ~ollowing examples illustrate th~ invention~ Parts and percentages are by weight.
E X A M P ~ E 1:
, . .
a) 27.7 Parts of 4-aminoa~obenzene 4' sul~onic acld were ~tirred in form o~ the sodium salt into 150 parts of water, 6.9 parts o~ sodium nitrite were added alld the wh~le wa~
~lowly poured~ whilst stirr~g,i~to a mixture o~ 100 parts o~ ice and 25 parts o~ a 31% hydrochloric acid. For the deco~position of nitrous acid ~n ~xcess3 a small amount o~
amidosulfonie a id was added a~ter 3 hours 4 The suspen-sion of the dia~o salt was the~ ad~usted with calcined so~
dium carbonate at a pH value o~ 6~5 to 7~0 a~d poured whils~
stirring, into a salution of 14.6 parts of 2-phenylphenol and 13 parts o~ an aqueous 3~ by weight sodium hydroxide ~olution $n 250 parts of water a~d 250 parts of ice. The coupling was effected ~ter 15 minutes. By a pH ad~ustmen~
at 6.0 with diluted hydrochloric ac~d, the d~estuff pre~l pitated. It was then filtered off ~d washed with a ~% so~
diwm chloride solution, 29 b) 45.8 Parts of the dyestuf~ prepared accordin~ to a~ were .. .
- ,.: . ... ~ , .: , ,. . . ~, , dissol~ed in a mixture of 400 parts o~ water and 350 part~
o~ aceto~e with an aqueous 33% by weight sodium hydroxide solutlon at pH 12.0; a solution o~ 32 psrts of ethyleneoxide in 150 parts o~ water were added, a~d the whole was stirred a..;,0C. T~e et.heriîica~i~n was firlisned aI~er ~ hours at; .
p~ 12,0. The solvent was separated by distillation and tha dyestuff was precipita~ed from the aqueous solution by adding ~odium chloride. A~ter filtration and dryi~g, a dyestuf~
was obtained, which corresponds as ~ree acid to the formula . ; :
~OD S~N-==N~N==-~O-C~2 -CEI2 ~H

. ~ ', '' ~ ~ , Dn~lNG EXD~P5E:
100 Parts o~ a polycaprolactam fabric were put into a bath ha~ng a temperature o~ 40C and co~taining 1.5 parts of .
the d~estuff of Example 1b), 0O15 parts of an addition product of 12 mol of ethylene oxid~ 1 mol of stearylamins, 0.40 parts of the condensation product o~ 1 mol of cyanurochloride (trichloro-s-triazine3 with 3 mol o~ an~line-3 sul~o~ic acid9 2.0 parts o~ ammonium acetate and 1.Q part o~ a 60% acetic acid in 3000 parts o~ water.
The temperature o~ the dye bath was raised within 15 minutss up to 98 - 100C, and dyeing was co~ti~ued for 50 ~inu- .
tes at 100&. After the usual finishing, a golden-~ellow dye-~ng with good to very good fastness t~ wa~hing at 40C a~d 6~C9 to water (severe), to chlorlnate~ bath-water, to ~cid a~d alkali~e perspiratio~J to mild a~d se~ere hypo~hlor~te 6 - :

... . . . . . . .... .., ., ~ . . . ~ . . .

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

~OE 74/F 381 bleach~ to ~ulllng ~n alkaline and ~cid medium, to decatizing and steaming, to acid and alkali as wel:L as to xeno--test and day-light were obtained.
When the caprolactam fabric was replaced by 100 parts o~ woal, dyeings wlth simllar gOOd general ~ast~ess properties to use and processing and an excellent fastness to light were obtained.
E X A M P ~,E 2:
45.~ Parts o~ the dyestuf~ o~ Example la) were dissolved in 500 parts of water together with an aqueous sodlum hydroxide solution at p~ 12.0; whllst ~igourosly stirring~ 25 parts o~
dim~thylsulfate were added dropwise, while the pH was ~ept at -11.5 - 12.0 with the aid o~ a~ aqueous 33% sodium hydroxide solution. The methylation was finished after 4 hours. The reaction product prec~pitated partially; precipitatio~ is finally achieved by addition of sodium chloride~ A~ter ~ ra~
tion9 a dyestuff was obtained~ which, ln th~ ~orm o~ the fre~ :
~cld, correspond~ to the ~ollowing formula:
. , ~
~ ~OoS ~ N===N ~ N===~ ~ OCH3 .
~E!~C ~AIII'DI~
: ~ h polycaprolactam fabric was printed with a paste cDn ~ Qlstlng o~ 10 parts of the dyestuff o~ Example 2, 30 parts : of dibutylglycol9 250 parts of water, 650 parts o~ a çry~tal :: gum thickening, 30 parts o~ ~itrobenze~e-3-sul~onic ~cld and : . 30 parts of ammonium sul~ate. The printed fabric was drled : ~ u~id steamed at 100 - 10?~C during 3~ minutes. The ~ln{~h~ng ' ~ , , ,, , . . .: . . . -:: - ., .... .. . . , . . i ... ~ : .

HOE ~

is ~ffected, ~s usual, after subsequent rin~ing and dr~ing.
The golden-yellow printing obtained, possesses a very good fastness to light beside very good general fastness to use and processing.
E X A M P ~ E ,3:
45.8 Parts of the d~estuff o~ Example 1a) were dissol~ed in a m~xture o~ 300 parts of water and 350 parts of aoetone with an ~queous 33% hydroxide solution at p~ 10.5; 12.5 parts of acrylo~itrile were added dropwise, at room temperature.
The al~lation was finished after 5 hours. ~he solvent was distilled off, the aque~us dyestuff solution was diluted w~th 200 parts of water and filtered until clear at 6G~C. The dye-~tuff was salted out from the solution by addition of sodium chloride. It corresponds in the f~rm o~ the free acid to the following formula:
.
~03S ~ N~ ~ N~ ~ O CH2-CE2-C~
.' ' ' ~
`, ~ -'. .
D~n~o ~
100 Parts of a tufted carpet of polyamide ~ibres, pre~ :
heated in ~aturated steam to 100C) run during 5 minute~
through a hot aqueous solution of 10~ - 102C, containing t5 parts of the dyestuf~ o~ Example 3~ 0.3 parts of an add~
tion product of 12 mol of ethylenoxide to 1 mol stearylaminet , 2 parts of sodium acetate and 1 part of acetic acidr Subse~ :
quently the dyed carpe~ was ri~sed a~ dried~ An even gol~e~
yellowp even dyeing with ~xcellent fa~t~ess to lig~ and g~oo~
general fast~es~ to use was achieY~d.
:i - 8 -' ~~OE 7$/F 381 .r ~

The same coloristic result was o~tained with tufted felt carpets.
E X A M P ~ E 4:
a) 27~7 Parts ~f 4-aminoaæobenzene-4'-sulfonic ac~d were stirred in the form of the sodium salt into 150 parts of water, 6.9 parts of sodium nitr~.te were added, and the whole was poured slowl~, whilst stirring into a m~xtur~ of 100 parts of ice and 25 parts of a ~ hydroohloric acidO After ~ hours, a small am~unt of amidosulfonic acid was added in order to 'decompose th~ nitrous acid in excess. The suspe~sion o~ the dia~o salt was ad~usted with sodium carbonate to a pll of 6,5 t~ 7.0 a~d the~ poured, whilst s~irri.~g9 into a solutlon of 14.6 part~ of 4-phenylphenol and 13 parts of an aqu~ous ~3%
sodlum hydroxide solution in 250 parts of water and 250 parts of ice. Coupling was complete after 15 minutes~ T~ ~
dyestuff precipitated after a pH ad~ustme~t at 6.0 with di~ -luted hydrochloric acid. It was then filtered and washed with a 1% sQdium chlor~de solution.
b) 45.8 Parts o~ the dyestu~f prepared accordi~g to ~xample a~
were dissolved in a mixture of 400 parts of water and 350 parts of acetone with an aqueous 33% ~odium hydroxide solu-tion at pH 12,0; 20 parts of ethylenechlorhydri~e were added~
By a dropwi~e addition of said c~ncentrated sodi ~ hydrox~de solution, the pH Yalue was kept at 11.5 to 12.~. The re-~25 action was complete after 6 hour~. The sol~ent ~as ad,~usted : . with hydrochloric aoid at 6:.0 9 and th~ dyestuf~ was salted ~:: out with ~he aid of sodium chloride. After ~iltration a~d drying, a dyestuff was obtained which correspo~ds in the 29 f orm of free acld to the following form~la: -: - _ g _ ,. ., .. , .. . ~-~: .. :, . . . . . - -,, - : , . ; ,: . . . ~ ., -...... , . ".. .--. ~, .. ~ . , ... ,. - . ., ~ . .
- . .. . : . .i,. . . ~ .. . :. : . . . :, . .. .
- . ., -, ~ - , . . ,. ~ . , ~ .
. . . .. , ~ . , . ~ .

~L~

I~&~ f~

~0-H~C~ C-0 ROa S~3N~ N~63NGlG~sN~?

. ' ',J ~

n~ G E~ s:
~ pol~amide carpet garn was treated wi-th a padding li~uor up to a li~uor plck-up of 100~ by wei~ht. The paddin~ liqour cont~$ned per 1 litre 10 part~ of ~he dyestuff of Exa~ple 3 5 parts of a locust bean flour preparationg 4 parts of an addi-tion product of 8 mnl o~ ethyl~noxide to 1 ~ol of lso~ritlecyl alcohol and 15 parts o~ a 60% acetic a¢id. The padded.y~rn was subsequently steamed duri~g 6 minutes at 100 - 120~C and then rinsed with cold water~ The dyeing p:ossess~s ~ery good general fastness to u~e and a very good to ex~elle~t fastnes~
to day-light. .
The following table contains further dyestu~s which were prepared and dyed according to the abo~eme~tio~ed Examples9 presenting good general ~astnes~ to use and pr~cessing.
.~ . ' : .
Example Formula Shade on p ly~

~(~
~;o~s~3N=N~3N=N~ ~ golden-~el~ ow . H~C20 ~ 6~ ~ss ~ N=N ~ N=N ~ golden~yellow :: :
.

OE 74lF 381 .

... .. . . ...
E~ample F'ormula Shade o:~ poly-7 ~0~5~ N=N~3N~N~oc2~6 golden yellow ~ . . .

B lsl - Mixture composed of ~s S~N--N~N- aN~OC~3 ~ .
-aDd ~ ~ golden~yello~ -. ~1~0 -.. ~ IIO"S~3~1=ll~ll_W~

J ~ .

1~1 - Mlxtur~ composed of 9 ' ~OoS~N~N~Ns N~OCH2-C~2-O~

and ~ 3 golde~-y~ll ow o~ 2 c- q {02~ S~_N~N=~
' ~ : ~

: ~ . :, :

,, .': ` ' ' ' ' ' : . ': . . . ' . . ' . `. . ~ " . . I ' . . ' ' ' ' ' ' . ' .'.' '. . .' ' .' . . .'

Claims (4)

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

1. A water-soluble disazo dyestuff which corresponds in the form of the free acid to the formula in which R1 is methyl, ethyl, .beta.-hydroxyethyl or .beta.-cyano ethyl, R2 is phenyl whereby -OR1 stands in ring A in 2- or 4-position to the azo group.

2. A process for colouring natural or synthetic polyamide fibres which comprises applying to the fibres a dyestuff as claimed in claim 1 and fixing the dyestuff.

3. A process as claimed in claim 2 wherein polyamide fibres are dyed in a neutral or weakly acid aqueous bath at 90 - 105°C.

4. A process as claimed in claim 2 wherein polyamide fabric is padded or printed with a dyestuff solution, thickened with a thickener, and fixed by steaming after drying.