Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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~
OR1
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 $s for
,
.. ... . , , . , , . , ~ ................... . . . . .
.. ; . . . . .. . , -. , .. .- . . -
OE 74/F 381
example
~ and - ~ ~
or with 1 mol o~ a mixture of the~e ~-oup].ing compo~ents, in a
temperature range o~ O - 30C a~d i~ a pEI ran~e 8 - 12~pre~er-
ably at a pH ~alue betwee~ 10 - i2; subsequently, the ~ree
hydroxy group is reacted optionally in presence o~ water, and
an acld binding agent with an alkylation agentS A~ a:L~ylat~n
agent~ there ca~ be cited :
dimethylsul~ate, diethylsul~ate, methylbro~ide~ eth~lbromide
or ethylchloride, ethylen~chlorhydrine or ethyle~ox~de,
B-chloro-propionitrile or acrylo~trile.
The present invention concerns furthermore the use o~
the dis~zo dyes of the invention and ~heir mixtures ~or the
dyelng of natural polyamide fibres, such a~ wvol and silk~ and
synthetlc polyam~des~ particularly those of caprolactam 5 of
hexamethglenediamine a~d adipic acid or o~ polycondensation pro-
ducts obtainable ~rom ~r-ami~o-undecan~ic acid.
The dyestu~fs are used as free acids or as salts. They
may alsc be used i~ mixture with other sultable dyestuf~s f'or
dyelng of the aboYementioned, pre~erably synthetic9 textile
materials. The dyebat~ contain 0.01 t~ 20 parts b~ weight of
dyestu~, O.Q5 to 10 parts by weigh~ o~ u~ual dye auxiliair~es
a~d 0.05 to 10 parts bg w~ight of usual dispersants per 1000
parts by weight of d~ebath. The admixture~ are chose~ in such
a way, so that the dyeing bath i~ ~eutr~l or acid. Also d~eing
can be carried out i~ a weak to strong acid bath by addition of
~ 3 --
-- .. . .
.. i,, . ,, " , ....... .. . ..... .. .. ... . . . ..
0~01 to 20 parts by weight of an acid, for example of form$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
-- 4 --
.~ .
... : . . . , . ... - . -;, .: .. ,, : , .. .
.. : .. . : . .. .. . . . . . . - .
~ . .
: .. : . .. .. : , . - . ... , . , - . :
: ., ~ . ~ . .. . . . . -
. . : -: -,
: ~ . . . ... .. .
OE 74LF 381
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
- 5 -
.. .
- ,.: . ... ~ , .: , ,. . . ~, ,
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
- 7 -
'
~ , , ,, , . . .: . . . -
:: - ., .... .. . . , . . 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
:: :
.
10 -
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 ' . . ' ' ' ' ' ' . ' .'.' '. . .' ' .' . . .'
