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Патент USA US2132846

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2,132,846
Patented Oct. 11, 1938
UNITED _ STAT-ES PATENT
2,132,845
OFFICE
WATER-INSOLUBLE 'MONOAZO DVYE
Miles Augustinus Dahlen, Wilmington, Del., and
Martin Edwin Friedrich, Carneys Point, N. J.,
assignors to E. I. duyPont de Nemours & Com
pany, Wilmington,_Del., a corporation of Del
aware
No Drawing. Application December 1'7, 1935,
Serial. No.‘ 54,851.
2 Claims.’ (012504-204;
This invention relates to new compositions of
matter and to dyeing. More particularly the in
vention relates to new compositions of matter
including azo dyes, and to processes of employing
5
them, particularly in printing processes. The
invention will be described with reference to
particular examples which are illustrative but
not limitative thereof.
7
The azo dyes are a well-de?ned group con
'10 taining the chromophor -—N=N—. The chromo
gen of azo dyestuffs comprises two aryl radicals
with the chromophor between them. The mono
azo dyes are generally prepared by joining two
components of which the ?rst, an amine, is called
the azo component, and the second, usually a
phenol, an amine, or an active methylene com-.
pound, is’ called the coupling component. In
coupling the components, the azo component is
diazotized, and is reacted with the second com
20 ponent, usually in solution.
The azo dyes of the prior art are applied by
one of several processes that have been devised
to take advantage of the nature of particular
dyes: (a) The dyestuff is dissolved or ‘dispersed
2.5 in a suitable liquid medium and the material
to be dyed is dipped therein. Satisfactory re
sults are obtained by this method only if the
completed dyestuff is substantive to the material
which is to be dyed. (b) A substantive coupling
component, or a substantive azo component, is
.30 directly
affixed to the material, and the diazo
tiz'ed component or the coupling component,-re
spectively, is coupled thereto, completing the
dye on the material.
(0) An azo component is
.35 diazotized and coupled to a compound with which
apparent and in part more fully hereinafter set
forth.
-
The objects of the invention are accomplished,
generally speaking, by stabilizing a diazotized
primary arylamine against reaction with a cou- ~5
pling component in alkaline or neutral medium
and by mixing it with a. compound having the
formula:
"
CH3 X
"
OH (JOHN
‘10
(311$
1.15
in which X is one of, the group consistingv of
hydrogen, halogen, ‘and alkyl. Other objects of
the invention are attained by preparing the said
mixtures as dry powders, as paste, or in solution, 120
and by incorporating them in printing pastes '
and other dyeing compositions. The objects of
the invention are accomplished, in onev speci?c
modi?cation, by, impregnating .a fabric or a
?brousginaterial with abasic or neutral paste .25
containing a mixture of thestabilized azo com- ‘
ponent and the coupling component and expos
ing the impregnated material, preferably at ele
vated temperature, to the action of a preferably
mild acid. Still other objects of the invention _30
are accomplished by the processes of applying ‘
the new compositions of matter more fully here
inafter set forth. Another object of the inven
tion is accomplished by dyeing a material with a
dye having the formula:
on, X
“35
it forms a new compound stable in alkaline or
neutral medium, and is mixed with the coupling
component and with the other ingredients of a
vbasic or neutral printing paste,>or solution. The
40 material to be dyed is impregnated with the
paste, or with the solution, by printing or in any
other satisfactory manner and the dye is formed
on the material by reaction with an acid, where
by it is freed and enabled to react with the
45 coupling component. This invention relates to
(Y)...
011 COHN
CH,
,- GM
'40
inv which Y is one of a group consisting of hydro
gen and an n-auxochrome, m is an integer less
than 6 andX is ‘one of the group consisting of 45
new compositions of matter to be applied by
the third of these methods, and to processes of
hydrogen, halogen, and alkyl. Another object of
the invention is accomplished by carrying out
applying them.
the processes of the invention by methods which
are economically and technically satisfactory.
In our copending application ?led of even date 50
herewith there is set forth a'class of new com
pounds which we have discovered to be useful as
coupling components for azo dyes.
In the practice of the invention the azo com
It is an object of the invention to make, use,
5,0 and vend new dyestu?s: to make them by proc
esseslwhich are economically and technically
satisfactory and to apply them to dye-susceptible
‘materials by methods and in compositions best
suited to the attaining “of ‘optimum results.
Other objects of the invention will be in part
ponent is stabilized against reaction in alkaline 55
2
2,132,846
or neutral medium with a coupling component
either by forming the nitrosamine or a diazo
imino compound thereof. The stabilized azo
component will then be mixed in the form of dry
with and subjected to the action of weak acids.
Any of the usual stabilizing agents may be used
in the preparation of water-soluble diazoimino
compounds. The following are exemplary, but
not limitative, of the class:
Sarcosin
powder, a paste, or a solution with the alkaline
or neutral mass containing the coupling com
ponent. The details of the processes of practic
ing the invention will differ somewhat accord
ing to the state of the ingredients but the general
10 method is to impregnate the‘ colorable material
with the so-formed mixture, and to act upon it
with enough acid to regenerate the azo com
ponent and permit it to act upon the coupling
component.
l-methyl-amino-ethane-2-sulfonic—acid
Proline
Nipecotinic-acid
Benzylene-imine-para-sulfonic-acid
2‘-ethyl-amino-4-sulfo-benzoic-acid
Examples of other derivatives of diazotized aryl
_
amines which are inactive toward coupling com
In the form of the invention which involves
the dyeing of a cloth by the so-called process of
printing, the azo component, diazotized and
stabilized as hereinabove described, is mixed in a
ponents under alkaline conditions, but which re
vert to the diazo form when reacted upon by
acids, are for instance the so-called diazo-sul
fonates, compounds which have the type formula
basic paste with the coupling component, the
Aryl—N=N-—SO3Na.
20 paste is applied to an etched or “printing” roller'
The following examples, in which parts are 20
by Weight, are designed to illustrate but not to
limit the various features of the invention:
which impregnates the fabric by contact, the
fabric is placed in a closed container, and is
subjected for a few seconds, at elevated tem
perature and usually in the presence of water
25 vapor, to the action. of the fumes of an acid
which-neutralizesthe basicity of the paste, breaks
up the-‘stabilized complex, and frees the azo com
ponent for reaction with the coupling component.
The azo components may advantageously in
30 clude as substituents in thearyl nucleus from
one to ?ve of the group alkyl, alkoxy, halogen,
EXAMPLE I
A solution of the 2:3-hydroxy-naphthoyl de 25
rivative of 2:4:5-trimethyl-aniline was prepared
as follows: 8 parts of the 2:4:5-trimethyl-anilide
of 2:3-hydroXy-naphthoic-acid were pasted up
with 10 parts of ethyl alcohol, 10 parts of caustic
sodaof; 35° Bé. were admixed, and after the 30
arylamide had dissolved completely, sufficient
Water was added to bring the total volume up to
aryloxy, aralkyl, aralkoxy, aryl, hydroaryloxy,
and trifluoro-alkyl, which are called n-auxo
1600- parts.
chromes, but generally speaking satisfactory re
sults are obtained by the use ofazo components
Illustrative of the general utility as azo com
ponents of the primary arylamines are the fol
lowing:
Ortho-chloro-aniline
razo solution was made slightly alkaline with 45
I-methoxy-Z-naphthylamine
4-chloro-2-amino-diphenyleether
Meta-amino-benzo-trifluoride
sodium-bicarbonate.
rinsed, ,andldried, giving a bright blue dyeing,
having good fastness to light and excellent fast
4 :4! -diamino-diphenylamine
ness to chlorine.
0cm '
_N=N'_
50
——0 ONE
ooze
,
OH
' CH3
~on
‘
Other methods of coloring dye-susceptible ma
terials with the new dyes include the following:
65 Textile ?bers are impregnated with our new cou
pling components and are developed in diazoe
salt solutions prepared from the ‘diazotized aryl
amines ‘hereinabove described; textile fibers may
be voverprinted with the paste containing the
70 diazo-salt' of‘ an arylamine, producing the color
according to the pattern of the printing roller;
the‘ new arylamides may be mixed with the di
azotates (nitrosamines) derived from the diazo
tized arylamines useful as azo components, dye
susceptible materialsmay befimpregnated theref
55
N: j
([3113
5 75
It is represented by the for
mula:
Y
~55
60
'
The dyed cloth was rinsed, soaped at the boil,
Ortho-amino-azo-toluene
3-amino-carbazole.
7
40 parts of cotton piece goods, well-boiled and
dried,.were impregnated with the solution of the
naphthoyl derivative, the impregnated cloth was
wrung, out and, without drying, developed in the
tetrazo solution. Just before coupling, the tet
4-chloro-2-amino-phenetol‘
Ortho-anisidine
4-chl0ro—2 : E-dimethyl-aniline
4-benzoyl-amino-2:5-dimethoxy-aniline
5-nitro-2—amino-anisole
50
,
water.
2 : S-dichloro-aniline
45
,
12 parts of ortho-dianisidine were dissolved in
a mixture of 22 parts of sulfuric-acid of 66° Bé. 35
strength and 60 parts of hot water, the solution
was poured onto an excess of ice, and the
tetrazotization carried out with a solution of 7
parts of sodium nitrite dissolved in 15 parts of
having from one to three of these substituents.
40
10
1-naphthylamine-2 : 4 : 8-trisulfonic-acid
CH3
(‘3H3
,
——CONH—QCH3
CH3
60
EXAMPLE II
The cloth was impregnated as in Example I
and was developed in a solution prepared as
follows:
'
14.1 parts of 4-chloro-2-amino-toluene were
dissolved in 25.0 parts of hydrochloric-acid
(37%) and 40 parts of water, the solution was ’ 70
cooled to 0—5° C., by means of external cooling,
and a solution of 7 parts of sodium-nitrite dis
solved in 20 par-ts of'water was‘ added. The tem
perature was held at 0-5“ C. by the addition of
about 50~parts of ice until diazotization was com
75
3
12,132,8416
Exempt.‘ v
plete, :the solution of the tdiazo salt was ?ltered,
and ‘its mineral acidity was neutralized by the
addition .of sodiumeacetaW- ~
The dyed cloth was rinsed, soaped at ‘the boil,
Q."
A printing paste was prepared, according to the
following formula:
rinsed, and dried, giving a bright red £01011, hav
ing good fastness properties. The .dye is repre-- 1
sented by the formula:
I
V 3.2 parts of the 2:3-hydroxyenaphthoy1deriva- 1*.
tive of 2:4:5:6-tetramethyl-ani1ine
'2.7 parts of "the dried anti-diazotate obtained
from 2: 5-dichloro-aniline
3.0 parts of caustic soda ('§l0°_Bé.)
10
65.0 parts of starch tragacanth thickener
26.1 parts of water
=10
Cotton piece goods were printed with the print 615
ing paste, and developed in the usual manner in
1|
£15
—0 ONE‘
. on;
an acid ager. vThere ‘was obtained ‘an orange
printing from a dye of the probableformula: ‘
ea ,
51120
11520
EXAMPLE ~
A printing paste ,wasprepared according .to the
formula :
'
1.8 parts of ‘the '2:3-ihyd;r0xy-naph-thoyl deriva
tive of 2 : 4 : 5-trimethyl-aniline
2.2 parts of a diazoimino compound prepared
from diazotized 4-,c1r11oro-2-amino-aniso1e
and piperidine-alpha-carboxylic acid
‘5.30
3.0 parts of caustic soda (40° Be.)
65.0 parts of starch tragaeanth thickener
use
28.0 parts of water
‘EXAMPLE
-
Cottonlpiece- goods were printed with a printing
paste of the formula ,given in Example III, except
100.0
Clattongpiece goods ‘were printed ~~with thenplrint
ing paste, then developed by subjecting toyvthe
action of :live steam containing the vapors of
acetic-acid.
lgthis'lmahnergthepa'ttern was de
veloped as a red dyeing, having very good fast
40 ness properties. The new color has the following
formula:
that the :6t-:brom_o.-'214:,5-trimethyhanilide of 2:3- I
hydroxyenaphthoic-racid was used‘as the coupling
component. ion {treatment with live steam con—
taining the rvapors .‘of acetic-acid, the pattern was
developed in red. The new color is represented by
40
the formula:
OOH:
OCH:
NL:
45
45
N=N
01
OH
OH
on‘
CONHQCH;
50
CH:
-
C ONH-
CH2
50
CH:
EXAMPLE V11
Cotton goods were impregnated with the penta
EXAMPLE IV
55
Cotton goods were impregnated with the
2:4:526 - tetramethyl - anilide of 2:3 - hydroxy
naphthoic-acid, by the method described‘in Ex
ample I. The “padded” goods were developed in
60
a diazo solution prepared as in Example‘ II.
‘The dyed cloth was rinsed, soaped at the boil,
rinsed, and dried.
A bright red dyeing was ob
tained. The dye has the probable formula:
65
methyl-anilide of 2:3-hydroxy-naphthoic-aci~d by
the method described in Example I. The
“padded” goods were developed in a diazo solu
tion prepared as in Example II. The dyed cloth
was rinsed, soaped at the boil, rinsed, and dried.
A bright red dyeing was obtained, the dye having
the probable formula:
0H:
HQ
CH:
55
65
01
OH
01
70
OH
C ONH
OH:
H: CH;
75
70
CH:
CONH
CH: CH:
OH:
OH: CH3
The following examples describe a variety of 75
4-
5
2,132,846
other colors WhlCh have been successfully pro-
As many apparently widely d1£terent~emb0d1~
duced by the use of other combinations of cou-
ments of this invention may be made without
pling components and d1azot1zed arylammes.
departing from the spirit-and‘ ‘scope thereof,'1t
Exléggple
1'
Diazo component
p-nitro-o-anisidine _____________________ __
_
_
2:4:5-trimetl1yl-aniline ___________ -_
p-chlor-o-nitro-aniline _____ _'_ __________ __
do ___________ _.
2:5—dichlor-aniline_
4:4’-diamino~3:3’-dimethoxy—diphenyl___-
o
0..-.
I Shade ‘7
Red.
Scarlet to orange.
e blue.
.
5-n1tro-2-an11no-anisole- _ __
___ __do__._
Bordeaux.
p~amino-dipl1e11yl-ether
p-nitro-o~anisidine_-
__.__do _______________________ _.
2-4z5-trimethyl
' '
_
2:5-dichlor-aniline _____ __
XX_-
4-benzoyl-amino-2:5-diethoxy-aniline____ _____do__._
do_
_
XXI-
-amino-4’-ethoxy-diphenyl-amine __________ __do___.
____ __
Gray blue.
XXII
5-nitro—2-amino-anisole_ ____________________ "do_--.
____ __
Bluish red.
XXIIlI: p-amino-diphenyl-ether ____________________ __do ___________________________ ._
Orange red.
Greeuish blue.
is to be understood that we do not limit ourselves 20
OCHa
.
y
Among the other new arylamides of 2:3-hy-
'
_QH '
.
Arylamzde of 2.3 hydroxy naphthow aczd
__CONH
6-chloro-2 : 4 : S-trimethyl-anilide
6-?uoro-2 : 4 : 5-trimethy1-anilide
01
0H,
30
|
.
CH3
H3
3-chloro-214:5-trimethyl-anilide
6-ethyl-224:5-trimethyl-anilide
3-ethyl-2z4:?-trimethyl-anilide
25
_
30 mentioned:
3-bromo-2:4z5-trimethyl-anilide
.
.
N=N
droxy-naphthoic-acid, suitable for the preparation of the new colors, the following may be
35
,
to the speci?c embodiments thereof except as
de?ned in the appended claims.
We claim:
1. A dyestuff represented by the formula:
?ber.
.
15
Reddish blue.
25 color pigments when produced apart from the
.
10
Orange.
___do_
The invention is applicable to the dyeing of
9
Scarlet.
XVIII___
cotton, regenerated cellulose, cellulose esters and
ethers and, with somewhat less satisfactory results, to the dyeing of wool, silk, and leather.
The new products are also valuable as insoluble
.
Scarlet.
Pink to scarlet.
_d
___
i
Scarlet.
__
Reddish blue.
Blue.
15 XIX_.__. 4:4’-diamino-3:3’-dimethoxy-diphenyl__
_
__
4-benzoyl-amino-2:5;diethoxy-aniline- ___
_do___.
4-annno-4’-eth0xy-d1phenyl-amine .......... __do___.
p-chlor-o-nitro-anilin
20
.
Coupung colri‘gggrggnog 12.3‘hydroxy' I
2. A ?brous material dyed with the color of 35
claim 1. '
'
>
MILES AUGUSTINUS DAHLEN.
MARTIN EDWIN FRIEDRICH.
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