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Патент USA US2135433

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Patented Nov. 1, 1938
2,135,433
UNITED STATES PATENT OFFICE
2,135,433
AZO DYESTUFFS
Detlef Dell's, Leverkusen, Helmut Kleiner,
Cologne-Muhlheim, and Theodor Kollmami,
Leverlmsen, Germany, assignors to General
Aniline Works, Inc., New York, N. Y.,' a corpo
ration of Delaware
No Drawing. Application September 16, 1936,
Serial No. 101,078. In Germany October 28,
1935
20 Claims.
The present invention relates to water insoluble
azodyestuifs and to printing preparations suit
able for the manufacture of the said dyestuffs by
(Cl; 8-42)
a printing process, more particularly our inven
1,874,524; 1,867,088; 1,871,850; 1,879,424; 1,882,
560; 1,882,562; 1,979,327; 1,982,681), and by de
6 tion relates to water-insoluble azodyestu?s which
may be represented by the general formula:
R—N=N—-R'—N=N—R"
X-Me-O
In the said formula R. stands for an aromatic
radical which may bear further azo groups, for
example for the radical of the benzene series, of
the naphthalene series, of the diphenyl series and
the like, R’ stands for a radical of the benzene
series capable of coupling twice, which is sub
stituted in a position meta to O by a hydroxy
group. R" stands for the radical of a diazotized
aromatic amine of the kind generally used in the
manufacture of ice colors, X stands for an oxygen
atom or the group COO, Me stands for a metallic
atom, capable of yielding azodyestu? complex
compounds and wherein the bridge X—Me-—O is
attached to the nuclei in positions ortho to the
azo bridge, it being selfunderstood that groups in
aromatic, secondary alphatic, aromatic or hetero
cyclic bases or cyanamide or cyanamide car
boxylic acid (compare U. S. Patents 1,858,623;
veloping the dyestu? in the customary manner,
e. g. by hanging, steaming or treating with dilute ,
acids or steam containing an acid. (Compare
U. S. Patents 1,880,522; 1,882,556; 1,893,991;
2,035,518). In this manner in general brown
shades of good fastness properties are obtained.
According to a further feature of the invention
for producing the newv waterinsoluble azodye
stu?s by a printing process preparations consist
ing of the above-named azodyestu?‘s and arylni
trosamines or aryldiazoamino--or -imino-com
pounds, soluble in water or an alkaline medium,
have proved particularly suited.
v the azodyestuffs from resorcinol or its homo
logues, capable of coupling twice, and ortho-hy-'
droxy- or ortho-carboxydiazo compounds, the 9.20
dyestuffs containing no further solubilizing
groups, with diazo compounds suitable for-the
manufacture of ice colors. The process may be
effected in the manner generally used in the man
15
(Compare U. S.
Patents 1,882,561; 1,915,734).
-
The invention is illustrated by the following ex
amples:
20
Example 1
A cotton tissue is printed with a printing color,
ducing solubility in water, such as the sulfonic , containing in 1000 grams:
acid group and the carboxylic acid group, are ex
cluded as substituents.
28 grams of the diazoimino compound from di
The process of manufacture of the dyestuffs
azotized 4-chloro-2-anisidine and sarcosine,
according to the invention is by coupling, espe
cially on the ?ber, metal complex compounds of
10'
25
35 grams of the copper complex compound of the
monoazodyestu? from 4-chloro-2-diazophenol 30
and resorcinol,
30 grams of aqueous caustic soda lye 38° Bé.,
50 grams of glycolmonoethylether,
500 grams of a neutral starch tragacanth thick
35
ener, the remainder being water;
then the cotton is dried, steamed for ?ve minutes,
ufacture of ice colors by impregnating the ?ber in steam containing acetic acid and/or formic
with the azodyestuffs containing metal referred
to above and further developing the dyeing with ' acid, rinsed, boiled, again rinsed and dried. A 40
full dark brown is obtained.
suitable diazo compounds.
'
The dyestuff» corresponds to the following for
A particular method of effecting the process is
V
by bringing the said coupling component on the mula:
OCH:
,5 fiber together with an arylnitrosamine suitable
for the manufacture of ice colors (compare U. S.
Patent 1,915,734) or a suitable aryldiazo-amino
or -imino-compound soluble in water or an alka
N:
line medium, as obtainable by the condensation
50 of diazo compounds with primary aliphatic or
0-011
2
-a,1ss,4sa
Example 2 l
A cotton tissue is printed with a printing color
containing in 1000 grams:
43.6 grams of the diazoimino compound from
diazotized 4-benzoylamino - 2.5-d1methoxy-1
aminobenzene and n-butylamino-acetic acid,
35 grams of the copper complex compound of
the monoazodyestuff from 4-chloro-2-diazo
10
phenol and resorcinol,
15'
'
tized 4-chloro-2-anisidine and piperidine-3-so
dium sulfonate, or 50.5 grams of the diazoimino
compound from diazotized 1-amino-4-benzoyl
amino-2.5-diethoxybenzene and methyl-gluca
mine, or 37.7 grams of the diazoamino com
pound from diazotized 1-amino-2.5-dimethoxy
4'-nitro-azobenzene and cyanamidsodium, there i
are likewise obtained after treatment with 10
500 grams, of a neutral starch tragacanth thick
ener, the remainder being water;
- A cotton tissue is printed with a printing color, 15
then the cotton is dried, steamed for ?ve min- ' containing in 1000 grams:
utes in steam containing acetic acid and/or for
mic acid, rinsed, soaped, again rinsed and dried. 34 grams of the copper complex compound of
the 'monoazodyestnif from 4-chloro-2-diazo
A full blackish brown is thus obtained.
The dyestufi.’ corresponds to the following for
20
.
steam containing vapours of acetic acid and/or
formic acid full dark brown prints.
Example 6
30 grams of aqueous caustic soda lye 38° Bé.,
50 grams of glycolmonoethylether,-
.
as described in Example 4, is substituted by 35.7
grams of the diazoimino compound from diazo
mula:
phenol and l-methyl - 2.6 - dihydroxybenzene
(cresorcinol) ,
'
bCH.
N=N
37.8 grams of the diazoimino compound from
diazotized l-amino-4-benroylamino-2 -meth
' oxy-5-methylbenzene and sarcosine sodium,
NH.CO.C0H|
50 grams of glycolmonoethylether,
b»
0-0u—0
>
30
.
_
_
Example 3
5.4 grams of the sodium- salt of the copper
complex of the monoazodyestuff prepared from
4-chloro-2-diazophenol and resorcinol are dis
‘ solved in 10 ccm. of aqueous soda lye 38° Bé.
and 10 ccm. of Turkey red oil, and diluted up
In this bath there
are treated 50 grams of cotton yarn for half
an hour at 30° C. The squeezed yarn is then in
troduced for half an hour into a developing bath
of 10-15° prepared in the usual manner from
40 2.89 grams of aminoazotoluol by diazotizing,
neutralizing the mineral acid with sodium ace
tate and filling up with water to 1 liter; 'then
the yarn is rinsed and soaped in a boiling bath.
A full reddish brown is thus obtained.
u'lihe dyestuff corresponds to the following for
45
35 to one liter with hot water.
m
a:
.
’
'
20 grams of aqueous caustic soda lye 38° 36.,
500 grams of a neutral starch tragacanth thick
ener, the remainder being water;
then the cotton is dried, treated for 5 minutes
with steam containing vapours of acetic and/or
formic acid and finished in the usual manner.
A full brown print is thus obtained somewhat
more yellowish than the analogous print with
the dyestuff from resorcinol.
The dyestu? corresponds to the following for
mula:
on,
c1
A
N=NQ~ooNacim
cast”
‘ O--Cu—0
1
n.
I
Example 7
A
.
With a printing paste containing in 1000'
grams:
32 grams of the copper complex compound of the
monoazo-dyestu? from anthranilic acid and
Grew
' I
on
m
m
-
Eeample 4
A cotton tissue is printed with a printing color,
containing in 1000 grams:
' ‘
82.6 grams of the copper complex compound of
the monoazodyestu? from 4-chloro-2-diazo
phenol and resorcinol,
anisidine (containing 52.2% base),
'
'50 grams of glycolmonoethylether,
30 grams of aqueous caustic soda lye 38° 34%.,
50 grams of' a. neutralchromate solution and
500 grams of a neutral starch tragacanth thick
ener, the remainder being water;
then the cotton is dried. treated for 5 minutes
with vsteam or steam containing, acetic acid
and/or formic acid vapours respectively, rinsed
and soaped. ’A' full dark brown is thus obtained.
.> The dyestuff is identical with the dyestuif de
scribed in Example 1.
Example 5
If
'
.
50 grams of glycolmonoethylether,
20 grams of aqueous caustic soda lye 38° 36.,
65
500 grams of neutral starch tragacanth thickener,
the remainder being water,
cotton tissue is printed. dried, treated for 5 min
.
35 grams of the nitrosamine from 4-chloro-2
70
resoi'cinol,
42.2 grams of the diazoimino compound from di
azotized 1 - amino-2.5-diethoxy-4-benzoylami
no-benzene and sarcosine sodium,
.
O-Cu-O
I
nitrosamine Iran‘ s-chloro-a-anisidinei
utes with steam or steam containing vapours of
acetic and/or formic acid and ?nished in the
usual manner. There is obtained a full dark
brown with good fastness properties.
The dyestu? corresponds to the following for-v
mula:
.
o-oini '
N=N
QHQ
I
NH- O O- COHI
70
In the following table there are given W
combinations prepared in accordance with the
15
invention.
2,185,488 '
Coupling component I
Diazotl nation component
0——Cu-—O
,
Shade
0cm '
\
N=N—<:>—OH
NH:
1
Roddish brown.
0iN(C:H5)g
0 cm
Dn
10
NH,
Yellowlsh brown.
0 CK:
Dn
NH;
Reddilh brown.
15
subdued brown.
20
CHI
0 CH:
Dn
Cq'EhC 0 NE
NH,
,
CH:
0—-Nl—-0
0 0,11
N=N-O—OH
clmc ONHQNEH
1
Dark blackish brown.
C111:
0 OH:
Dn
CQHICONH
NH!
D0.
C H]
O CH:
1 DD
mmconn
NH,
Full reddish brown.
El
01
40
m
0.11.0 ONHQNH;
Do.
_ ‘OH!
OCH:
1)“
45
NH,
Yellovish brown.
OaN(CaH|):
0 CH2
Dn
60
NH,
I
0-—M n-O
.
,
‘Y
/
Do.
0 0H,
,
N=N
0H
-c.mooNH
NH.
1
Rich subdued‘ brown.
0m
01
1)“
60
0.11.0 ONHQNH,
CH:
/
0-—-Co—-O
\
4
Q '=N—©-0H
.
Do.
65
0 0m
001.com;
NH,
1
Full dark brown.
cm
70
0 OH:
Dn
NH,
s O|N(O:H:)|
Reddlsh brown.
4-
'
2,186,488
Coupling component
_
‘Diuo?mtlon componentv
' Shade
.O-Oo-O
'
\
=N_C>-‘on
.
1y
'
mam blown.
I
DA
'
N'HI
D0
1
0-011-0
OCH;
MG”
I
‘
'
.
W]: m. M.
I
I
-
I,
NE,
NO!’
D“
I
.([>C!Hl
-
NH:
'
I
Do.
01H‘
01
D0
mmoonn
NH:
'mwmh brown.
OH:
°_.‘Qu--Q
001E!
\
.
N=N_<:>-on
a.
n
CIEICONH
v
m1:
‘
m
1)“
'
Do.
05H:
_
_
C1
O.H|OONH
NH;
Vlolo?sh brown.
,
OH:
0011;
m
‘
'
m1.
,
Reddish brown.
vDQ163111‘):
OCH;
1)“.
‘
n
'
'
_
NH:
'
D0._
OH;
00H:
m
'
Cn-
'
'
NH:
‘
0H;
N=N
E
‘
n“
Yellowish brown.
.
V
'
W21.
ma'mmwa
W
m0
7
NH‘
'
-
~
the. ?rst
coupling
oom
ponont indicated abova.
l
m
‘
‘
-
'
'
_
NH|
011N013‘):
3,135,433
Couplin: component
0—-Ou-
s
0
.
Diuotiution component
Shade
0011'
H‘
N=N
0H
s
NH'
‘
Shades similar 30 those
which are obtained with
on,
-
10
I
1»
on
ponent indicated above. 10
N=N
com
on
1
'
_
, @101,
1
0—Cu-0
20
the first coupling com
OCH.
<3“
O-Gn-
15
5
Vioiotisb brown.
15
_
2o
l
-
00,3;
/
OH—®—N=N
0.11.0 ONH
NH,
3'
Bluish black.
0,11‘
.
00H;
25
'
1)"
_
NH,
'
I
3o
a
,
OCH‘
'Dn
35
'
QNH,
‘
D0
Deep brown.
,7
m1,
,
:0
0cm
-
Do.
_ 85
0m
0—Cu-~O
4&0
25
Blackisb brown.
00in;
, '
.40
N=N
N=N
0mm
H.
OH
'
0.3.0 ONH
NH.
‘
Violetiab blackish brown.
01B;
00B;
45
v
Dn
45
NE;
subdued dark brown.
0E3
OOH:
50
'
m
O—-Cu—0
55
50
_ NH,
'
\
N=NOOH -
Dark brown.
00m
'
NB,
mum lrown.
55
OH:
00m
60
m
NH,
Do.
001B;
~
'Dn
.
65
CaH‘CONHQNH;
03H:
7o
60
We claim:
1. Water insoluble azodyestu?'s of the general
-—Me—0
wherein R stands for an aromatic radical, R’
75 stands for a radical of the benzene series capable
‘Blaekish brown I
_
.
65
.
oi.’ coupling twice, which is substituted in a posi
tion meta to O by a hydroxy group, R" stands 70
for the radical of a diazotized aromatic amine
generally used in the manufacture of ice colors, X _
stands for a member selected from the group con
sisting of an oxygen atom and the group COO, Me
stands for a metallic atom capable or yielding 75'
'
2,135,433
e
'1. Water insoluble azodyestuffs of the general
formula:
azodyestuff complex compounds, and wherein the
_ bridge X—Me—0 is attached to the nuclei in po
I
sitions ortho to the azo bridge, yielding when pro
duced on the ?ber in general brown shades of
‘alk'oxy
N:
' good fastness properties.
2. Water insoluble azodyestuifs of the general
formula:
.
'
-
10
10
‘ wherein X stands for a member selected from
the group consisting of hydrogen, halogen, the
wherein R stands for an aromatic radical, R.’
stands for a radical of the benzene series capable
of coupling twice, which is substituted in a posi
tion meta to O by a hydroxy group, R" stands for
the radical of a diazotized aromatic amine gen-.
erally used in the manufacture of ice colors, X
stands for a member selected from the group
consisting of an oxygen atom and the group COO,
nitro group and an alkyl group, Y stands for a
member selected from the group consisting of
alkoxy and alkyl, yielding when produced on the 15
fiber in general brown shades of good fastness
properties.
8. The water insoluble azodyestu? of the for
mula:
'
OCH:
yielding when produced on the ?ber in general
20 brown shades of good fastness properties.
3. Water ‘insoluble azodyestuifs of the general
formula:
20
.
~
0!
-
=N
OH
OH:
25
wherein R and R" stand for benzene radicals,
30 and wherein the bridge O—Cu--O is attached to
the nuclei in positions ortho to the azo bridge,
yielding when produced on the ?ber in general
\wfjrxqwn shades of good fastness properties.
ifw‘a'ter‘insoluble azodyestuifs of the generalv
formula:
-
.
x
yielding when produced on the ?ber a full black
ish brown.
9. Fibers dyed with a dyestuff as claimed. in 1
claim 1.
'
_
claim 3.
'
‘
12. Fibers dyed with a' dyestufi' as claimed in 85
claim 4.
7’ N=N—R"
30
10. Fibers dyed with a dyestu? as claimed in
claim 2.
11. Fibers dyed with a dyestuif as claimed in
'
13. Fibers dyed with a dyestuff as claimed in
claim 5.
-
14. Fibers dyed with a dyestu? as claimed in
claim 6.
wherein x stands for a member selected from the
group consisting of hydrogen, halogen, the nitro
group and an alkyl group, R” stands for a radical
of the benzene series, yielding when produced on
45 the ?ber in general brown shades of’ good fastness
properties.
,
.
15. Fibers dyed with a dyestu? as claimed in
claim '1.
16. Fibers dyed with a dyestuif as claimed in
claim 8.
'
1'1. Printing preparations comprising a_dye-'
stuff of the following formula:
.
5. Water insoluble azodyestuffs of the general
formula:
x—M6,-'O
alkoxy
wherein R. stands for an aromatic radical, R’ 50
stands for a radical of_the benzene series capable
of coupling twice, which is substituted in a posi
tion meta to 0 by a hydroxy group, X stands for
a member selected from the group consisting of
an oxygen atom and the group 000, Me stands 55
for a metallic atom capable of yielding azodye
wherein X stands for a member selected from
the group consisting of hydrogen, halogen, the
nitro group and an alkyl group, Y stands for a
60 member selected from the group consisting of
stuff complex compounds, and wherein the bridge
X—Me-—0 is attached to the nuclei in positions
ortho to the azo bridge, and a compound selected
60
from the group consisting of nitrosamines, diazo- .
when produced on the ?ber in general brown
amino- anddiazo-imino compounds derived from
aromatic amines generally used invthe manufac
shades of good fastness properties. 4
ture of ice colors.
hydrogen, halogen, alkoxy and alktyl, yielding
6. The water insoluble azodyestu? of the for
muia:
_
.
18. Printing preparations comprising a dye
stuif of the following formula:
70
wherein R means a radical of the benzene series,
and wherein the bridge O-Cu—0 is attached to
the benzene nuclei in. positions ortho to the azo
bridge, and a compound selected from the group
yieldingwhenproducedonthe?berafulldark‘ consisting of nitrosamines, diqo-aminc- and di-‘
2,135,433
azo-imino compounds derived from aromatic
amines generally used in the manufacture of ice
colors.
20. Printing preparations comprising a com- '
pound of the general formula:
_
x
-
I
19. Printing preparations comprising a com
pound of the general formula:
Gram/OOH
0—Ou——0
.
0-0u—-Q
-
wherein X stands for a member selected from the
, group consisting of hydrogen, halogen, the nitro
group and an alkyl group, and a compound se
15
'
'
wherein X stands for a member selected from the
lected from the group consisting of nitrosamines,
diazo-amino- and diazo-imino compounds de
rived from an amine of the following general
formula:
group consisting of hydrogen, halogen, the nitro 10
group and an alkyl group, and a compound se
lected from the group consisting of nitrosamines,
diazo-amino- and diazo-imino compounds de
rived from'an amine of the following general
formula:
15
HaN
alkoxy
_
20
HzN
.
.
y
.
Y
wherein Y stands for a member selected from the
25 group consisting of hydrogen, halogen, alkoxy
and alkyl.
-
wherein Y stands for a member selected from the
group consisting of alkoiw and alkyl.
DETLEF DELFS.
HELMUT KLEINER.
THEODOR KOLLMANN.
25
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