close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3053687

код для вставки
3,053,678
v United States Patent *0
Patented Sept. 11, 1962
1
2
SPUNDYED REGENERATED CELLULOSE
PRODUCTS
3,053,678
nuclei may be combined with ‘each other in any way, viz.
they may be condensed or directly or indirectly linked
with each other.
Konrad Mix, Frankfurt am Main, Fechenheim, Germany,
assignor to Cassella Farbwerke Mainkur Aktiengesell
tion may bear additional substituents of the group con—
The nitroaryl-hydrazones used according to my inven
schaft, Frankfurt am Main, Fechenheim, Germany, a
sisting ‘of alkyl, cycloalkyl, oxyalkyl, aryl, aralkyl, car
No Drawing. Filed March 17, 1961, Ser. No. 96,381
Claims priority, application Germany Mar. 23, 1960
4 Claims. (Cl. 106-165)
bonyl, alkoxy, aryloxy, acyl, nitro, h-alogeno, sulfonyl,
company of German
amino and 212-0 radicals.
Thus, products are obtained which, depending on the
constitution of the employed nitroaryl-hydrazone, are dyed
in clear yellow, orange, red to brown shades, the dyeings
This invention relates to the manufacture of regenerated
cellulose products spundyed with nitroaryl-hydrazone pig
ments.
of which distinguish themselves by excellent fastness prop
erties to light, ironing, washing, boiling, weather etc.
.
Among the current methods for the dyeing of rege
This result was surprising. In particular, it could not
nerated cellulose there is the spin dyeing with ?nely dis 15 be foreseen that the nitroaryl-hydrazones used according
persed pigment dyes which is of utmost importance.
to my invention would be stable in the strongly alkaline
In producing spundyed regenerated cellulose products,
viscose solution or remain unchanged in their color shade,
such as viscose rayon, ?bers and ?lms, the coloring matter,
particularly since it is known that one characteristic fea
such as pigment material, is dispersed in the spinning solu
ture of the simple nitrophenyl-hydrazones, which is de
tion which solution is then extruded through suitable spin
cisive for their analytical determination is that consider
nerets or other shape forming devices into coagulating and
able al-teration of shade occurs in the presence of alkali
subsequent processing baths before the spun or extruded
active agents.
products are ?nally dried. A colored product is thus pro
The ‘nitroaryl-hydrazones which are suitable for the
duced.
process of the present invention may be prepared in the
Such a process is frequently preferred to that process 25 known methods, such as being described in Houben-Weyl
wherein the products are dyed after the extrusion, coagu
lation and other processing steps. With spindyeing, col
“Methoden der organischen Chemie,” Fourth edition, vol
ume VII/=1, page 465, by reacting nitroaryl-hydrazines
ored or dyed products are initially provided which may be
with appropriate carbonyl compounds, preferably in an
further treated without the necessity of any subsequent
acid pH-range.
dyeing.
30
Especially suited are the hydrazones of the following
In the spin dyeing processes hitherto known there have
nitraoaryl-hydrazines:
.
.
been used as pigment dyes chie?y water-insoluble azo dyes,
. 2,4-dinitro-phenyl-hydrazine
such as ?-hydroxy-naphthoic-acid-arylides or high-quality
2,4-dinitrophenylene-1,S-dihydrazine
vat dyes.
Now, I have found that most satisfactory spundyed 35 2-nitro-4 (N) -methylsulfamido-phenylhydrazine
2-nitro-4 (N) -dimethylsulfamido-phenylhydrazine
products of regenerated cellulose may be easily obtained
2,4-dinitro-S-chloro-phenylhydrazine.
from the well-known viscose spinning solutions by incor
porating into the viscose spinning solutions mono- or di
The following tables enumerate a series of such hydra
nitroaryl-hydrazones in a ?nely dispersed form which con
zones together With the color shades obtained thereby in
tain in the molecule at least 3 phenyl nuclei. The phenyl 40 the SPH]. dyeing of viscose.
TABLE I
Formulae
N 02
Mono-2,4-dinitrophenylhydrazoues ot the following carbonyl
Color
compounds
X:
—NO3
I?L-NH-X
1, Benzonhennna
0\
.-_
‘
Yellow.
,WN__NH_X.
C
2. 4,4'-dibromobenzonhennne
.,
/ \
“
B
Do‘
Br
N-NH-X
I
3. 4-methoxy-benzophenone-
'
C
'
I
.
O CH;
-
Y~
.
Golden ye1low..
.
3,053,678
TABLE I—Contin1‘1ed
Formulae
N02
MOno-2,4-dinitropheny1hydmzones or the following carbonyl
Color
compounds
X—
NO:
N-NH—-X
ll
14. 2-acety1-dibenzofuran_.
/°\ 0H:
—
- yellow. ‘
Golden
.\o
15. l-naphthyl-methylketone ........................................ -_
Do.
1\[T—NH-—X
C
.
\CHs
16, Z-naphthyl-methylketone.
17. l-naphthyl-phenylketone ............................... __' _______ _.
Do.
\
Do.
18, 2-naphthy1-phenylketone ........................................ ._
Do.
19. 4-ace*°*ninn-benzoph¢=mm-
Orange,
20. 4-(4’-acetam1nophenyl)-acetophenone ......... -L .................. -- HaC/
Red.
N—NH--X
. ||
21. 4-(?-chloropropionylamino)-benzophenone...; .................... --
Orange.
\N/C O-GHz-OHr-Cl
.
H1
HaC-—C=N—NH—X
22, 4-[4'-(B-chloropropionylamino)-pheny1]-acetophen0ne ............. -.
1
'
Red.
3,053,678
TABLE I—C0ntinued
Formulae
N 0:
Mono-2,4-dinitrophenylhydrazones o! the following carbonyl
Color
compounds
X=
NO:
l?I-NH-X
23. Coupling product of dlazotlzed 4-aminobenzophenone with acetoacetani e.
V
V’ |
C—CH':
Yellowish brown.
%
—N=N-—O\
N-NH-X
I!
/C
24. 4‘(4’-dlmethylaminophenylazo)-benzophenone ................... ..
OH
Orange.
a
/
CH3
7
l
_
N-NH-X.
al
25. 1,4-dibenzoy1mnhrhallrw
/ \
Yellow.
\C/
H
..
,
v
..
.
l
.
0
0
(I :
26. Anthraqulnone-2~a1dehy?e
CH=N-—NH.X
Do_
(3/
II
0
-
‘a
/C\
we
' ' "
CH=N—NH.X
27. 1-mnlno-anthraqulnone-2-aldehyde ............................... -.
Red.
0
.H
0
TABLE II
TABLE II-—Continued
Formulae
Bls-2,4~din1tro-
phenylhydrazones
the following
50
carbonyl compounds
Formulae
Bls-ZA-dinitro
NO ;
I
phenylhydrazones
of the following
color
X_
N 09
color
carbonyl compounds
No:
X=—
l
55
N-—~NH——X
28. 4,4’-dibenzoy1djphenyl.
II
N-NH.X
/C
Yellow.
El}
II
I]
I?I-NH-X
70
Do.
‘u’
D0.
1%
N—NH.X
65
/C\
N-NH-X
0
30. 1,4-dibenzoy1
60
naphthalene.
\
N-NH-X
29. 1,5-dlbenzoy1
naphthalene.
N 03
75
8,053,678
TAP'LE III
Further nltro-phenylhydlazones
Formulae
3iilsllfiiegzzgghenone-(2-nitro-4-N—methy1snlfamido-phenyl-
v
NHV
H;C.NH.O4S—
32. BSHZODhBIlOllB-(‘Z -nitro - 4 - N,N-dlmethy1su1famidophenylhydrazone).
--N0a>
NH—N=C
33. Benzophenone - (2,4 - dinitro - 5 _-ch1orop'heny1hydrazone).
_ v
I
Color
Golden yellow.
A
// V
D
0'
Yellow
.
34. Condensation product of 1 mol 4,6-d1n1trophenylenel
1,3-dihydmzlne with 2 mols of benzophenone.
Greenish yellow.
35. Condensation product of 1 mol 4,6-'dinitro~pheny1ene
1,3-dihydrazine with 2 mole of benzaldehyde.
Golden yellow.
36. Condensation product of 1 mol 4,6-dinitro-phenylene
1,3-dihydrazine with 2 mole of anisaldehyde.
Red.
37. Condensation product 0! 1 mol 4,6-din1tro-pheny1ene
1,3-dihydrazine with 1 mol benzophenone and 1
Yellow. r
mol acetone.
‘
38. Condensation product of 1 mol 4,6'dlnitro-pheny1ene
Golden yellow. ‘
1,3-d1hydrazine with 1 mol benzophenone and 1
mol 4-methyl-4-hydroxypentanone-(2).
I
39. Condensation productoi 1 mol 4,64iinltro-phenylene
1,3~di,hydrazine with 1 mol benzophenone and 1
mol acetophenone.
‘
'
3,053,678
TABLE Ills-Continued
Further nitro-phenylhydrazones
Formulae
O1N—
40. Condensation product of 1 mol 4,64itnitro-phenylene
1.3-dlhydrazlne with 1 mol benzophenone and 1
mol propion-aldehyde.
\
C=N——NH
OzN
41. Condensation product of 1 mol 4,6-dinitro-phenylene
1,3—dlhydrazine with 1 mol benzophenone and 1
mol croton-aldehyde.
C=N—NH
OzN
42. Condensation product ofl mol4,6'dinitro-phenylene1,3-dihydrazine with 1 mol benzophenone and 1
Color
N0,
—-NH—N=CH—CHr-CH1
Do.
N01
——NH—N=CH-—-CH=CH—C H:
Do.
"N02
CHz-CH,
mol cyclo-hexanone.
C-—--N-—N H
—NH—N=C
/CH1
Yellow.
GHQ-CH2
43. Condensation product of 1 mo14,6-dinitro-phenylene1 3~dihydrazlne with 1 mol é-phenylacetophenone
OzN-
CH;
and 1 mol acetone.
\I
C=N-—NH
44. Condensation product of 2 mols benzophenone-(2,4dinltro-5-chlorophenylhydrazoue) with 1 mol 4,4’-
f
diamino-diphenyl.
OzN
\
C)
NO;
—NH——N=O
CH;
Golden yellow.
/
N02
,
Brown.
.
/C=N——NH
.
—NH
.
f
45. Condensation product of 2 mols 2,4-dinitro-5-(di-
OQN~
—N0;
phenylmethylene - hydrazine) - phenylhydrszine
Yellow.
with 1 mol glyoxal.
C=N—NH
NH—N=CH—
LO
46. Condensation product of 2 mols 2,4-dinitro-5-(dipliglrlnlrl - meéliylegni - hydrazino) - phenylhydrazine
w
mm
a e
c y
r
.
OaN-
N0,
Do.
.
G=N-—NH
icy
—NH—N=C—
2
To prepare the pigment dye paste 100 parts of one
Nitroaryl-hydrazones for the spin dyeing of viscose
are preferably prepared in form of an aqueous paste 50 of the before-mentioned nitroaryl-hydrazones are ground
together with 25 parts sodium dinaphthyl-methane-disul
which is obtained by grinding ?nely the pigment up to
tomato and about 300 parts of water, until a particle size
a medium granular size of about 1p. in the presence of
of about 1/.L is obtained.
water. Common dispersing and grinding auxiliaries can
Then the dyestuif content is adjusted to a content of
be added to the aqueous dispersion.
The introduction of the dye paste into the viscose may 55 20%‘ of the total mixture by means of water.
What ‘I claim is:
be made at any stage of its preparation.
1. A process of manufacturing spundyed regenerated
The following example will further illustrate how my
cellulose products from viscose spinning solutions com
invention may be carried out in practice, but the inven
prising the steps of incorporating into the viscose spin
tion is not restricted to this example. The parts given
are by weight and the percentages are percentage-by 60 ning solution nitroaryl-hydrazones selected from the group
consisting of vrnono- and dini-troaryl-hydrazones in a
weight. ,
Example
?nely dispersed form, said hydrazones containing in the
molecule at least 3 phenyl nuclei, and coagulating the
resultant spinning solution in an acid bath.
1000 parts viscose spinning solution prepared from
shredded cellulose, sodium hydroxide, carbon disul?de 65 2. A process of manufacturing spundyed regenerated
cellulose products {from viscose spinning solutions com
and water, corresponding to 85 parts regenerated cellu
prising the steps of incorporating into the viscose spin
lose, are admixed at a temperature of 15~25° C. with
ning solution nitroaryl-hydrazones selected from the
4.25 parts pigment dye paste which has been prepared
group consisting of mono- and dinitroaryl-hydrazones
according to the method described hereinafter, and the
in form of a ?nely dispersed dye paste, said hydrazones
mixture is stirred for half an hour. The mass is then
70 containing in the molecule at least 3 phenyl nuclei, and
spun or extruded in the usual manner or a spinning ma
coagulating the resultant spinning solution in an acid
chine. The coagulation of the viscose is e?ected in a sul
bath.
furic acid precipitation bath, then the material thus spun
3. A process of manufacturing spundyed regenerated
is aftertreated in the usual manner with water and solu
tions of diluted alkali, diluted acid and, if desired, with 75 cellulose products from viscose spinning solutions com
prising the steps of incorporating into the viscose spin
a solution of sodium hypochlorite.
3,053,678
13
ning solution nitroaryldhydrazones selected from the
group consisting of mono- and dinitnoaryl-hydrazones
in ‘a ?nely dispersed form, said hydrazones containing
in ‘the molecule at least 3 phenyl nuclei and hearing at
least ‘one of the substituents of the group consisting of
alkyl, cyclo‘alkyl, oxyalkyl, \aIyl, aralkyl, carbonyl, alkoxy,
aryloxy, lacy], nitro, halogeno, sulfonyl, amino and azo
radicals, and coagulating the resultant spinning solution
14
?nely dispersed nitroarylwhydrazones selected from the
group consisting of mono- and dini-troaryl-hydrazones,
said hydIazo-nes containing in the molecules at least 3
phenyl nuclei.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,911,314
2,944,050
4. Spundyed regenerated cellulose products containing 10 2,948,721
in an acid bath.
Armento et a1 __________ __ Nov. 3, 1959
Haubrick et -al. ________ __ July 5, 1960
Frey ________________ __ Aug. 9, 1960
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent N00 3,053,678
September 11,, 1962
Konrad Mix
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected belowa
Column 10! under item 36!, for the terminal carbon "C?"
on the right~hand nucleus read ~-= H M”; column 12, item 43,
the formula should appear as shown below instead of as in the
patent:
O2N
N02
CH
-
CINWNH
NH~N=C
/CH3
\CH3
Signed and sealed this 12th day oi March 19630
(SEAL)
Attest:
ESTON G, JOHNSON
Attesting Officer
DAVID Le LADD
Commissioner of Patents
Документ
Категория
Без категории
Просмотров
0
Размер файла
407 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа