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Патент USA US2406004

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Patented Aug. 20, 1946
2,406,004
~ UNITED STATES PATENT" OFFICE 1}
MONOAZO COMPOUNDS
‘Joseph B. Dickey and James G. McNally,'Roch- .
ester, N. Y., assignors to Eastman Kodak Com
pany, Rochester, N. Y., a corporation of New
Jersey
No Drawing. Application May 20, 1942,
Serial No. 443,718
.6 Claims. (01. 260—205)
-
This invention relates to new azo dye com
.2
,
.
tate, cellulose formate, cellulose propionate‘ or
pounds and their application to the art of dyeing.
cellulose butyrate and the hydrolyzed as well: as
We have discovered that dyeings which can be
discharged to a clear white can be obtained by
dyeing a suitable textile material with a dye
the unhydrolyzed mixed organic acidesters of
having the formula:
cellulose such as cellulose acetate-propionate,
cellulose acetate-butyrate and the cellulose
ethers such'as methyl cellulose, ethyl cellulose
-
or benzyl cellulose. ‘ While our invention will ‘be
alkyl '
described more particularly ingconnection: with
the dyeing of cellulose‘ acetate, silk, it will- be
understood that it is applicable to the Idyeing ‘of
the other textile materials'which have been in
/
R—N=N—R1—N
\
_
.
v
R:
_
v
wherein R stands forv the residue of a benzene
“nucleus containing an NHz group inpara posi
“tion; to the azo bond shown and a
.
R4
group, wherein R3 stands for a member selected
- .from the group consisting of hydrogen and an
.alkyl group and R4 stands for a member selected
from the groupconsisting of an alkyl group .and
a benzene nucleus, in 'ortho or meta position to
sulting from the development operation have the
formula:
‘
a benzene nucleus and R2 stands for a member
selected from the group consisting of any alkyl
group and a benzene nucleus, diazotizing the
_
.
T
1 25
‘
.
.
alkyl
D~N=NV—_B—N=N—_R1—N/‘> '
"
dye on the ?ber and developing with a developer
r
'
dyeings can be obtained.‘ The use of components,
such as '2-hydroxy-3-carboxynaphthalene, yield
ing dischargeable navy'vblue to black shadesap
pears to‘ be of greatest importance-since these
.20 shades are in demand and dyes which» can. yield
. them are highly desirable. The disazov dyes re
the azo bond shown, R1 stands for the residue of
,
'
15 ?ber yellow, scarlet, violet, navy blue’ and black
/
.—SQ2N
component.
'
ponent used to develop the diazotized dye' on‘ the
Ra
'
dicated hereinbefore.
_ ' Dependingupon' the particular developer/com
-»
I
'
R2
wherein D stands for the residue of a developer
component, B stands for the residue of a benzene
I
So far as we are aware both the monoazo dye
nucleus containing a,
compounds and the disazor dye compounds re
sulting from the development operation consti
tutenew compounds. Accordingly, it isan ob
‘Y
»
.
~
I
~.
R3
‘~——SO2N/
ject of our invention to provide new azo dye
R4
compounds. Another object is to provide dye
group and wherein R1, R2,, Rsand R4 have the
ings on textile materials which are of good fast- ~ 35
meaning previously assigned to them.
ness to light and washing and which can’ be dis
charged to a clear white. A particular object is
to provide cellulose acetate textile materials dyed
navy blue or blackshades of good fastness to
light and washing and which are dischargeable
The dye compounds of our invention possess
properties which make them of unusual indus
trial importance. The free amino dye. com‘
pounds combine ,good speed of ‘dyeing with ‘good
exhaustion and for the most part can be applied
to'a, clear white.
_
,
‘
'
to the ?ber at. a temperature as low as 60". C.
~
The dyeing process of our invention appears
Further, generally speaking, these free amino
to, be particularly of, value in. connection with
dye compounds possess good solubility in water
the production of navy blue to black shades on
.anddo lnot gum'on heating with steam; When
cellulose acetate textile materials. However, the .45 vdiazotized on the ?ber and coupled with a’ de
dye compounds‘of our invention are applicable to
veloper component, such as 2-hydroxy-3-car
the coloration of organic derivatives of cellulose
boxynaphthalen'e, desirable shades of color are
in general as well as'to other textile’ materials
obtainedwhichare of good fastnessto ‘light and
such as nylon, wool and silk. Our invention
washing and which arereadily dischargeable to a
seems to be of greatest utility in connection with 50v clear white. _Ready_ dischargeability to a clear
the coloration of cellulose acetate and nylon
white is a very important property vfor a‘ dye to
textile materials.
possess.
Typica1 organic derivatives of cellulose include
?thehydrolyzed as well as the unhydrolyzed cel
lulose organic acid esters such ‘as cellulose ace
'
V
y
'.
>.
;
.
‘q
‘
The qualities above enumerated,- as previously
55
noted, makethe-dye compounds of'our- inven
tion vvery valuable commercially; Rapid dyeing
2,406,004
‘
4
3
at low temperatures coupled with good exhaus
the dye compound formed tends to coagulate as a
gummy mass unless it is well stirred to keep the
product broken up. 11.3 grams, which is 67.45%
of the theoretical yield of 4'-amino-2'-sulfone
tion are qualities of utmost importance in jig
dyeing operations which normally are conducted
at temperatures of 60-65° C. Thus dye com
pounds, which dye rapidly at temperatures of
methylamidobenzeneazo - 4 - dimethylaminoben
80-85° C. and which .are otherwisesatisfactory
.zeneis obtained in the form ofsmall?nely formed
but whichposses's poora?inity forthe?ber at
red-orange crystals. The dye compound formed
Gil-65° C. have little or no utility for present day
commercial jig dyeing operations. Accordingly,’
the discovery of dye compounds which .dye.
is recovered by ?ltration, washed with water and
'.' dried.
'
do not form gummy deposits.randlwhichxyield.
By substituting an equivalent gram molecular
weight of 4’-nitro-2’-sulfonemethylamidoben
zeneazoeei-diethylaminobenzene for the starting
wdye'compound'aof the example 4'-amino-2'-sul
dyeings of excellent fastnesslto light and'w'ashing
‘fonemethylamidobenzeneazo - 4 - diethylamino
and which are readily dischargeable to white
constitutes an important as well as unexpected
benzene is obtained. This dye ‘compound is like
wise obtained as red-orange crystals and has prop
‘ rapidly at low temperatures, which exhaust well,
which have excellent solubilityin water; which _
technological advance.
'
’ erties substantially the same as the dye compound
Concentrations, for example, from 1/a% to 3%,’
by weight of the dye tothe material undergoing
dyeing can be employed-in the initial dyeing op
eratic-n,iprettyuorangewellow dyeings being ob
of the example.
_
I
V
ExampZeZ
20
23 grams of ‘i’-nitro-'2’-sulfonethylamidoben
zeneazo '-4-di-c- hydroxyethylaminobenzene are
heated in 100 cc. of ethyl alcohol in a reaction
vessel to boiling. A solution 0158 grams of‘fused
tained. For the development operation follow
ling1thediazotization of ‘the free ‘amino dye com
.pounduon Jthe ?benan excess of. the developer
‘component is ordinarilyv employed. The in
tensity of shade-obtained varies depending on
theiamount‘of the free ‘amino ‘dye-absorbed by
:the ?ber: in the vinitiali'd'yeing‘operation. To
'iThus'it ‘is seen that the'intensity of the sgiade
60% sodium sul?de in 18 cc, of water is'then
added in small portions because the reduction re
action proceeds very vigorously. After all of the
sul?de solution has been added, the reaction mix
ture is boiled for 45-60 minutes and then poured
through a filter paper into two liters of cold water
which is vigorously stirred.‘ 13 grams, which is
65% of the theoretical amountiof £4’-'amino-2"
sulfonethylamidobenzeneazo-4-di <- ,8 -ilhydroxy
ethylaminobenzene is recovered by ?ltration as
increases" with an‘increase in the amount :of_' the
3:) well formed orange crystals. The dye compound
illustrate, when 12 -<hydroxyi3i-carboxynaphtha
llenetis the developer ‘component 'at lower con
centrations, the icolor "appears navy ‘blue ’ but as
the concentration increases the intensity of the
color‘ increases until :thecolor appears black.
‘free-‘aminordyeiappliedto the ‘?ber.
‘
7
obtained is washed with'water and dried.
-~ ‘Themonoazo"dyefcompoundsiof ‘our invention
Example 3
can ' be ‘prepared by‘v reducing the corresponding
‘nitro dye compounds to the 1free amino ‘form.
‘Thus > 4 ' - ' amino-2 'l-sulfonemethylainidobenzene
-az‘o-4-zdimethylaminobenzene ‘having the ,ior
'mul'az
"
'
-
Id
'
H.N_<I;;I rink
<3: 34CH:
I /H
.
‘
SOgN
'CHt'
"
f
can be prepared by reducing
.
.
'
aminobenzene are'placed in a reaction vessel to
getherwith 200cc; of ethylalcohol and the mix
ture resulting'is heated to boiling. 8 grams of
fused 60% sodium sul?devin 18‘cc.>of water is
1then added in small portions to prevent the reduc
tion-reaction from being too vigorous. vAfter all
of ‘the sul?de ~'solution has been added the re
action mixture is re?uxed for 45-60 minutes and
then'poured through a'?lter paper into 2 liters of
‘coldrwaterl which is being stirred'vigorously. 17.5
\
CH3
/
OrN
23.9 grams of 4'-nitro-2'-sulfonethylamidoben
zeneazo-Z-chloro - 4 - (ethyl, ?-hydroxyéthyD
grams, which is 82% of the theoretical amount of
'4'-a-mino - 2' -' sulfonethylamidobenzeneazo' - 2
_
I
v
7
. 80%
‘
CH:
chloro-'4-‘(ethyl, ‘p-hydroxyethyl) ‘aminobenzene
‘is obtained after ?ltration of the'reaction mixture
in the form of wel1iormed red-orange crystals.
‘The dye --compoundiobtained is washed with
.
CH3 '
‘The preparationof the monoazo nitro compounds
is'illustrated in our U- saPatent 2,261,175‘, issued
water and dried.
'November4,i194l, wherein a ‘considerable num
‘1, 2 and 3; the following monoazo dyes of our in
vention can be prepared. In naming the dye
berofsuch compounds isdisclosed.
'v
.. ' The following. examples illustrate ‘the ‘invention:
. .
.
‘Example 1
. ‘117.’? grams‘ of '4i-nitro-2'esulfonemethylamido
benzeneazo-iledimethylaminobenzene are ‘heated 65
in 100>ccrof ethyl ealcoholto boiling. A solution
of‘ 8 .gram-s'off60% sodium sul?de fusedwith 2
:gramsof sulfurin 20 cc. of'water is then added
in‘ small portions because the reduction reaction
Following the procedure described in Examples
compounds tabulated hereinafter,v the numbering
indicated in connection with the dye 4'-amino-2'
sulfonemethylamidobenzeneazo - 4 - dimethyl
aminobenzene has been followed.
,
1-.‘ 4'-'amino- 2' -sulfone-/3-hydroxyethylamido
lbenzeneazo#l-dimethylaminobenzene.
2. 4' - amino-2'-sulfone-p-methoxyethylamido
benzeneazo-4-dimethylaminobenzene.
.
3. 4’ - amino-2‘-sulfone-;8-methoxyethylamido
‘which take‘siplace is ‘very vigorous. After all of ' "0 benzeneazo-4-diethylaminobenzene.
\the‘sul?de reaction mixture has been added, the
4.- 4"- amino-2"-sulfone-p-methoxyethylamido
resulting reaction mixture is re?uxed for 45460
"minuteslafter-lwhich’ it is'p'oured through a ?lter
paper- into two liters of cold‘water'which is stirred
benzeneazo-‘i- (ethyl, ?-hydroxyethyl) -aminoben—
lvigorously. Vigorous :s'tirring is required‘ because
benzeneazo-4-di-p-hydroxyethylaminobenzene.
zene.
.'
,
V
.
'5. 4’ - amino-2'-sulfone¢;3—methoxyethylamido
‘
32,406,004
7
"1‘. .4’ efamino' :12‘ J-- sulfonem‘ethylamidoben -
-- ."Whil? .a'considerable number of compounds il
illustrating the monoazo dye‘compounds of our
invention have been vgiven, ‘it is to be clearly
understood that the compounds disclosed are il
lustrativeand not limitative of the invention.
Thus, .any of the nitrobenzene-sulfoneamide
compounds disclosed herein'can be diazotized and
coupled with any of the coupling components in
zeneazoeéledimethylaminobenzene.
-.
‘
2. 4’ - amino - 2' - sulfonethylamidobenzene -
azo-4-di-p-hydroxyethylaminobenzene.
'
3. 4' - amino - 2’ - sulfonethylamidobenzene —
azo - 2 - chloro-li- (ethyLe-hydroxyethyl) -amino
benzene.
-
'
a
4.4’ - amino - .2’ - sulfonemethylamidoben -
dicated herein to yield 'monoazo , dyes which
zeneazo-4-diethylaminobenzene.
can be converted in accordance with the Procedure
described in‘Examples 1, 2 and 3 to yield the
monoazo dye compounds of our invention.
:The monoazo dye compounds of the invention
'
>
5. 4’ - amino .- 2’ - ,sulfonephenylami'doben
zeneazo - 4 - (ethyLe - hydroxyethyl)
- amino
benzene.
'
6. 4' - amino - ,3' - sulfonethylamidobenzene -
azo-4-dimethylaminobenzene,
can bezapplied to the textile material such as an
7. 4'.- amino - 3' -_sulfonethylamidobenzene
organic derivative of cellulose textile material 15
by methods well known in the art. They may be
azo-4-di-p-hydroxyethylaminobenzene.
8. 4’ - amino - 3' -sulfonethy1amidobenzene
applied, for example, from an aqueous solution
azoei-(methylphenyl) -aminobenzene.
orsuspension of the dye or dyes. In this method
9. 4' - amino - 3' - sulfon‘ethylamidobenzene
the dye is ?nely ground and ordinarily inti
mately admixed'with a dispersing or solubilizing 20 azo-‘l-di-B-hydroxyethylaminonaphthalene.
agent such as soap, sodium sulforicinoleic acid
-
10. 4' - amino - 2' - sulfonethylamidobenzene
azo-4-di~p-hydroxyethylaminonaphthalene.
,orrsodium lignin-sulfonate and dispersed in water
to ‘form an aqueous dyebath. The material-to be
ll. 4’ - amino - 6’ - chloro - 2’ - sulfonemeth —
y1amidobenzeneazo-4-dimethylaminobenzene.
dyed is then added to the dyebath thus prepared
12. 4’ - amino - 2’ - sulfonedimethylamidoben
and dyeing is conducted at a temperature of 25
zeneazo-ll-di-?-methoxyethylaminobenzene.
50:85". C. until complete. In accordance with the
usual dyeing practice, the material to be dyed will
When the above compounds are diazotized and
‘ordinarily be added to the dyebath at a tempera
coupled with 2-hydroxy-3-carboxynaphthalene,
ture lower than that at which the main portion
navy blue to black dyeings are obtained; when
of the dyeing is to be effected, a, temperature ap 30 coupled with I-phenyI-B-methyl-S-pyrazolone,
proximating 45-55" C., _for example, following
which thetemperature of the dyebath is raised to
"that selectedfor carrying out the dyeing opera
yellow dyeings are_obtained’;_when_coupled with
tion. Usually one to two hours is su?icient for
the dyeing ‘operation. As this method of dyeing
and modi?cations‘ of it arewell known to those
‘skilled'in the artto which this invention is di
35
e-naphthol, scarlet dyeings are obtained; when
coupled with 1-diepehydroxyethylamino-2¢meth
oxy-S-methylbenzene, violet dyeings are obtained
and when 1e?rv-dihydroxypropyl-Z-methyltet
rahydroquinoline is the developer component
navy blue dyeings are ‘obtained.
1
The monoazo dye von the ?ber can be diazotized
rected, further discussion is believed unnecessary.
The monoazo dye compounds Of the invention
‘are principallyof importance in connection with 40 in accordance with‘ the procedure described here
inafter. Itwill be understood, however, that any
so-called developed dyeing operations. In this
other suitable method can be used.
method of dyeing the monoazo dye (or dyes) is
Diazotization of the monoazo dye on the ?ber
diazotizedom the ?ber and the diazonium com
pound resulting is coupled with a compound
,After the material has been rinsedafter dye
known as a developer compound. These‘ latter
ing, it is diazotized in a hath made up as fol
compounds are well known to those skilled in the
lows: For each 10 grams of cloth, one gram of
.art asa considerable‘number of them are dis
sodium nitrite is dissolved inra mixture contain
closed in the prior art. Representative developer
ing_2 grams of concentrated (35 %) hydrochloric
compounds arejgiven hereinafter but no attempt
‘acid and 300 v(Bo/‘of water. The diazotization
.has been made to givean exhaustive list. It will 50 treatment is‘ given for ,30-45-minutes at a tem
be apparent that compounds of the general char
perature of ‘about'20b C’. Upon ‘completion of the
.acter. as those indicated can also be employed.
diazotization reaction, the fabric is removed and
. ,Developer compoundsthat canbe employed in
vthoroughly rinsed'with water following which it
is ready for development.
clude 2-hydroxy - 3 - carboxynaphthalene, 1
_phenyl-S~methyl-5-pyrazolone, phenol, a cresol
such as p-cresol, v13-naphthol,,arylamides of 2-hy
,droxy-3-carboxynaphthalene such as the anilide,
the m-nitroanilide or’ the p-methoxyanilide
The development operation of the invention
will be illustrated in connection with 2ehydroxy
3-carboxynaphthalene. Generally speaking, the
developing operation will be carried out in a
moderately acid medium although in certain
derivatives, 1 - di - e- hydroxyethylamino - 2
pmethoxy-?~methylbenzene, N-di-B-hydroxyethyl
aminobenzene, N-‘(ethyL e-hydroxyethyl) -amino
60 cases it may be deemed more desirable to carry
benzene, N-13,11-dihydroxypropyltetrahydroquino
line, 1-b,'y-vdihydrogpropyl-2-methyltetrahydro
,quinolineand 1-B-hydroxyethyl-2? - dimethyl
‘tetrahydroquinoline.
I
The colors
-
obtainable when representative
monoazo dyes of our invention are applied to cel—
lulose acetate textile materials, diazotized on the
?ber and then developed with various represen
tative developer compounds are givenhereinafter. ‘
Twelve monoazo dyes are ?rst listed and the col
ors obtained when they are yd‘iazotized and de
out the development operation in a slightly al
kalinev medium.
‘
a
Following thediazotization treatment, the ma
terial is developed, preferably immediately?n a
bath made up as follows: ‘for every 10 grams of
‘cloth, 10 cc. of a 5% stock solution of Z-hydr'oxy
S-naphthoic acid and 1 cc. of glacial aceticlacid
are added to 300 cc. of Water.
The stock solu
»tion of. 2-hydroxy-3enaphthoic acid is made by
dissolving 10 grams of 2-hydroxy-3-naphthoic
acid inlOO .cc. of 5% .NaOH and then adding 100
cc. of water. " The cellulose acetate cloth from
veloped with the developer compounds indicated
the diazotization treatment is entered in the de
are given in the paragraph immediately follow- , v
veloping bath.ats~30°jC; and "the temperature is
gradually raised to 60° (Lover a 30 minute-ipei
ing.
2,406,004
10
riod at which temperature the bath is kept for
another 30 minutes. Following this treatment,
selected from the group consisting of hydrogen,
a lower alkyl group, a lower alkoxyalkyl group
and a lower hydroxyalkyl group, R4 and R5 each
stands for a member selected from the group con
The developing bath made up as described CI sisting of a lower alkyl group, a lower alkoxy
above has a pH of approximately 4.0. By increas
alkyl group, a lower hydroxyalkyl group and a
the cellulose acetate silk is removed, washed well
with water and dried.
ing the amount of acetic acid, the pH will be low
ered and the shade obtained on the fabric will
be greener. If the pH is raised by decreasing the
monocyclic group of the benzene series, X1 stands
for a member selected from the group consisting
Using the above procedure, navy blue to black
ber selected from the group consisting of hydro
of hydrogen, a lower alkyl group, an acetamino
amount of acid added a redder shade is obtained. 10 group and a chlorine atom, X2 stands for a mem
shades can be obtained depending upon the con
gen and a lower alkoxyl group, 2Q stands for a
centration of the monoazo dye on the ?ber. The
member selected from the group consisting of
colors obtained are readily discharged to sub
hydrogen, a lower alkyl group, a lower alkoxyl
stantially a pure white by the usual reduction 15 group, a chlorine atom and a bromine atom, and
discharges such as, for example, the monozinc
X4 stands for a member selected from the group
salt of the formaldehyde sulfoxylic acid (Ron
consisting of hydrogen and a lower alkyl group
galite).
and wherein at least one of X3 and X4 must be
While the development operation has been 11
lustrated in connection with the use of 2-hy
droxy-3-carboxynaphthalene, it will be under
hydrogen.
20
stood that it can be carried out in a similar man
ner using one of the other developer components
indicated herein. That is, the pH of the devel
oper bath can be about 4.0 although as previous 25
ly indicated the pH is not restricted to this value.
The shade obtained will vary somewhat depend
ing upon the pH of the developer bath. If de
sired, the dyeing can be topped by treating with
2. The azo compounds having the formula:
R5
I /Rz
SO2—N\H
wherein R2, R3 and R5 each stand for a lower
alkyl group.
3. The azo compounds having the formula:
a direct dye of another shade. Also the develop
ment operation can be effected using more than
one developer compound. To illustrate, the di
azotized ?ber can be developed with both 2-hy
droxy-3-carboxynaphthalene and
1-phenyl-3
methyl-5-pyrazolone at the same time.
Although the use of the dye compounds of our
H
invention has been described more particularly
in connection with cellulose acetate, it will be
wherein R2 and R5 each represents a lower hy
understood that they can be applied to the other
droxyalkyl group and R3 represents a lower alkyl
textile materials named herein by the methods
group.
described or by methods similar thereto. Fur
4. The azo compound having the formula:
ther, while the disazo dye compounds of our in
CH: 0 H2 0 H
vention have been shown as being prepared on
/
HgN
the ?ber, it will be understood that the diazo
N=N
—N\
tized monoazo dyes can be coupled with the de 45
CHgCHzOH
|
C2115
veloper components without being applied to the
S OzN
?ber and if this is done the disazo dyes are ob
tained per se. Normally the disazo dye is formed
H
on the ?ber.
Coupling components wherein the benzene or 50
naphthalene nucleus contains an amino group
which is substituted with a phosphorus grouping
can be prepared as described in our copending
5. The azo dye compound having the formula:
application Serial No. 225,198, ?led August 16,
1938.
55
We claim:
1. The azo compounds having the formula:
X4
|
X3
I
X1
I
6. The azo dye compound having the formula:
CgHs
R5
60
l
3
R'
X1
R:
H.N@_N=N@_N/
O f) H
\CgH5
SOaN
R4
wherein R2 and R3 each stands for a member
JOSEPH B. DICKEY.
JAMES G. MCNALLY.
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