Note: Descriptions are shown in the official language in which they were submitted.
~37~Z9
q'he present invention relates to a new class of sul~
phonated azoic dyestu~fs which are well suited for the direct
dyeing of cotton and other cellulosic fibers, such as flax,
- regenerated cellulose fibers, hemp and jute; natural and
æynthetlc polyamide ~ibers and blends thereof~ as ~lell as
leather and other similar materials.
The invention provides a new class of water-soluble
azoic dyestuffs having the ~ormula:
H~ - ~ N-N ~ CONH ~ N-N~A
COOH
wherein A i~: :
OH NH2
~=N ~ N2 ' :
H03S sa 3H
, ' ' .
NH2
N=N ~ SO~H
~2N
,.~
~3
- - Cu
' ~ N=~ - ~ , or
:.~ HO S03H
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. ~ ' . ~ : ,
`', '3 ~ ' . ~ '-
, ' ~ '
.
~C~3~7029
~ N~ ~ N-N ~ N=~ I~N ~ l-~-CO
S03H H2 ~ 1~2 ~ COOH
OH ~ N
~he~e direct dye~tuffs ha~e characteristics similar to
those of the conventlonal direct dye~tuffs of the benzidine
series, but the process for preparing them does not i~volve a~y
toxicologi¢al risksO A¢tually, benzidine and its derivatives, ~ -
which are used in preparing ¢onventional dyestuffs having
c`haracteristics which are similar to those according to the
invention, are dangerous substances, i.e.g they are carcinogenic
and, conse~uently, the use and preparation thereof are extremely
harmful to personnel handling them.
~he direct dyestuffs of the invention may be prepared
accoxding to methods known in the art.
These dyestuffs dge cellulosic fibers, aæotized fibers
and leather in dar~ shades ranging from green to brown.
Dyeing o~ ~ibers with the dyestuffs of the invention is
carried out using the same methods as are used~with conventional
direct benzidinic dyestuffs, i.e., at a te~perature generally
rangl~g between 50 and loooa., in ~ aqueous bath containi~g
~itable amounts~ eOgO from 0,01% ~ to 2-3% g or according to
~he u~er~s exigence, o~ dyestu~f and from 5 to 20~o ~with respect
.
to the ~iber weight) of anhydrous ~a2S04 or of NaCl.
he following examples are 8i~en to illustrate the
invention, all parts being understood as parts by weight unless ~;!
otherwise indicated.
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EXAMP~ 37029
19.6 parts of sulphanilic acid suspended in 170 parts
of water~ 16.7 parts o~ 20 Bé HCl~ and 100 part~ o~ ice were
diazotized at 0C. by pouring thereinto7 over a period of 20-
30 minutes9 7t8 parts of ~aN02 as a 20~o solut~on (parts/volu-
me). The mixture wa~ stirred ~or 2 hours and the exces~
nitrous acid was removed using sulphamic acid. The diazotiza~
tion mass was poured, o~er a pexiod of 15 minutes, onto a ~olu-
tion of 12.2 parts of m.toluylenediamine in 200 part~ of water,
~0 100 parts o~ ice and 22 parts of 20 ~é HCl.
`~ ~he pH value of the mixture was brought to 5.5 6 by
dxopping in o~er a period of 1 houx, a solution o~ 2007 g. of
NaHC03 in 200 parts of water, and stirring was continued o~er-
night. The n~xt morning, it was heated to 40~45C., and 140
parts of an aqueous solution of 10~ Na2C03 (parts/weight~ were
admixed there-to, the resulting pH value being 9-9.5. Once solu-
tion was completed, it was oooled to 10~. with ice and a diaæo-
monoazoio mass, separately prepared by coupling 474~-diamino
benzanilide with salicylio acid~ as hereinafter described, ~s
ad~ixed thereto. The temperature was 10C. and the pH ~alue
about 8. The reaction mixture was stirred overnight~ ~nd the
next morning it was heated to about 70C, aoidi~ied with 28
part~ of 20 Bé HCl and salted with ~00 parts of rock salt.
The product was filterod under vacuum and washed with a lO~o ~ ~ -
brine solution. I-t was then sgueezed dry. The product thus ;~
obtained7 a~ter being dried at 7Q-80C. ~or 24 hours, dyes
cellulose fibers in ~ellowish-brown shades. -
~he abore-mentioned diazo-monoazoic mass was prepared
as follows.
2?.7 parts of 4-4~-diaminobensanilide, suspended in
100 parts of water and 52 parts of 20 Bé hydroohloric acid axe
te~raazotized, after cooling with 100 parts of ice, by dropping
-3
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~ 37~2~
thereinto~ at o-5~a.5 a sol~ on ~3f ~4 parts o~ N~10~ in 60
parts of water. After stirring for 60 minutes, thé excess
nitrous acid was removed using s~lphamic acid.
15 parts o~ salicylic acid were dissolved in 150 parts
of H20 and 14.6 parts of 36 Bé NaOH. The resulting solution~
to which were added 5 par-ts of ~a2C03 as a 20~ solution (parts/
volume) and cooled to 0~20a. with 50 parts of ioe, was rapidly
admixed within about 2 minutes to the tetrazo-mass. 15 parts
of Na2C03 as a 20% solutio~ (parts/volume) were poured into the
reaction mixture over a period of 1 hourD ~he temperature was
kept at 0-2C. and -the pH value at about 9. ~inally~ the
produot was stirred for 2 hours to complete the ¢oupling.
~XAMP~E 2
18~9 parts of 2-amino-phenol-4 sulphonic acid suspended
in 150 parts o~ water and 10.5 parts of 20 ~é hydrochloric
acid were cooled with 10Q parts of ice and wexe diazotized, at ~
0-5C. by dropping thereinto, over 30 minutes, a solution of ~ -;
7 parts o~ ~aN02 in 30 parts of H20. After stirring ~or 60
minutes, the excess nitrous acid waæ removed using sulphamic
aoid.
11.6 parts o~ resor¢in were dissolved in 70 parts of
water and 13~3 parts of 36 Bé NaOH. The diazoti~ation mass
was poured over a 1 hour period onto the solution thus obtained,
~hile keeping the temperature at 0-5C. with 150 parts of ice
and maintaining a p~ ~alue of about ~ with 26.5 parts of ~6
~é NaOH. Stirxing wa carr~ed on for 1 hour to complete the --
~` ~ coupling, whereupon a æolution o~ 26 parts of CuS04.5H20 in 80
parts of H20 at 70~C. was admdxed thereto. ~he~ 8 parts of
.,
~ ~odium aoe~ate.3H20 were added to the mi~ture. ~he whole mass
wa~ ke2t for 3 hours at 35-40C., the pH ~alue being 5-5.50 It
,:
wa~ the~ salted with 45 parts o~ rock salt. The resulting
precipitate wa~ ~iltered undex ~acuum and sgueezed dry. The
. . . ..
- 4
. .
,, .'~
~3~25~;
cake was treated with 150 parts o~ water at 400a . and ~olubi-
lized by adding Q solution of 15 parts o~ Na2C03 in 70 parts
o~ H20, at a pH of about 9~ ~ile keeping the temperature at
10~15~o~ the solution was poured onto a diazo-monoazoic mass,
prepared separately by ¢oupling 474~- diaminoben2anilide with
ealicylic acid, as described in Example 1. The reaction mix-
ture was stirred overnight. ~he next morning it was heated to
60-70C. and slightly aoidified to Congo red with 20 Be hydro-
chloric acid~ It was filtered under vacuum and the resulting
cake was squeezed dr~.
The produot thus obtained, after being dried at 70-80C.,
~s useful in dyeing oMd printing on ¢ellulosic fi~ers9 providing
reddish brown shade~ exhibiting an excellent stability to mois-
ture and lighto
13.8 parts of p-nitroaniline were suspended in 50 parts
o~ H20 and 35 parts of 20 Be HCl. After addition o~ 100 parts
o~ ice it was diazotized by rapidly pouxing thereinto a 20% ~i
~olution (part~/volume) of 7 g. of ~a~02 `at a temperature of : :
?oC. Stirring was conducted for 30 minutes1 A solution of :~
39 parts of H acid in 150 parts o~ H20 and 14.6 parts of 36
. B~ NaOH was poured o~er 45 minutes at 0-5Co onto the clari~ied
diazo solution, the pH value being 0.8-1.1. It was stlrred :
o~ernight and the whole wa9 poured onto a diazo-monoazoic mass
~eparately prepared by coupling 4,4'-diaminobenzanilide with
salicylic acid, as described in Example 1. Thereafter, 50 parts
o~ ice were added and the pH value waa brought to 805-9 with 16
parts of Na2C03 dissolved i~ 70 parts of H20. It was stirred
overnightO The next morning after it was heated to 70~. and
f~ltered under ~acuum. ~he cake wàs squeezed out and then
dried at 80-90Co
. ~he re~ulting product dye~ ¢ellulosic and polyamide
. .
-5~
1~37Q;~9
fibers bluish green wi-th an excellent stability to moisture
and light.
~XAMP~E 4
20.4 parts o~ 4,4'-diaminobenzanilide, suspended in
45 parts of H20 and 52 par-ts of 20 Bé HFl, after cooling with
200 parts of ice, were tetraazotized by dropping therein-to at
0-50a. a solu-tion of 12~5 parts of Na~02 in 50 parts of H20.
It was stirred 1 hour at a p~ of 1-1.5. The exoes~ nitrous
acid was removed using sulphamio acid.
13.5 parts of salicyll¢ acid were dissol~ed in 180 parts
o~ H20 and 6~5 part~i of ~a2C03, the pH value being 7~5. After
addition of 100 part~ of ice, the whole was poured, in the form
o~ a flne streiam, onto the tetraazotization mass. The pH value
was brought to 9-9~5 by means of 29 parts of Na2C03~ Stirring
was carried on for 3 hours at 0-5Co and a solution consisti~g
of 17.2 parts of 1-naphthylamino-6- or -7 sulphonic acid dis-
solved in 270 parts of H20 at 40C. a2ld 9.3 parts of 36 Bé
NaOH and cooled with 100 parts of ice was admixed thereto. It
was stirred overnight. ~he next morning, the pH was brought
to 2.5 with 42 parts of 20 Bé HCl; after stirring for 15 minu-
tes the pH value was then raised to 8.5 with 22.5 parts of 36 ~;~
Bé NaOH to complete the coupling. ~he mas3 was mixed with 200
parts of ioe~ 60 parts o~ 60 ~é H2~04 and was diazotized by
gradually i~troducing a solution of 11.5 parts of NaN02 in 50
parts of H20. ~tirring ~as carried ~n until the next day,
whereupon the exoess nitrous acid was removed using sulphamic
acid. A su~pension, prepared as herei~after described was
admdxed thereto:
16.3 parts of m.phenylenediamine were dissolved in ~30
parts of water and brought to a pH of 5-5.5 with a 20 Bé HCl.
~70 parts of ice and 702 parts o~ sodium nitrite were added;
~ ~ùbsequently9 oYer 3 hours, 26.1 parts of 20 ~ HCl, diluted ~ --
.~....................... . .~
-6-
' ~
~ 0 ~7 ~ %9
with 26.~ parts of H20, were introducedO ~he mixture was
slightly aoid -to Congo red. Stirring was carried on at room
temperature until the next day.
The mass was salted with 135 parts rock salt; the
precipitated dyestuf~ was filtered under vacuum and squeezed
dryO ~he cake was suspended in 400 parts of H20 at 90~C. It
was then homogenized and cooled with 300 parts of iceO
~ he ooupling mass was brought to a pH of 7.5 with 120
parts of 36 Bé NaOH and was kept under stirring until the
next day~ It was heated to 700a~ and salted with 90 parts
of rock salt. It was ~iltered under vacuum and accurately
~ æquee~ed dryO It wa~ then dxied at 80Co The dyestu~ thus
obtained dyes cellulosic ~ibers with brown hues and good
stability characteri~ticæO
Variations can, of course, be made without departing
from the spirit and scope of the in~ention.
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