Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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
S03H R2
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)
S03H
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.
-- 3 --
--- ~ HOE 74/'~ ~82
1059998
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
-- 4 --
HOE 74LF 382
1059998
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
-- 5 --
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
- 6 -
382
~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-
-- 7 --
HOE 74/F 382
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-
- 8 -
OE 74LF 382
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 _
HQE 74/F 382
~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
-- 10 --
~ - 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
