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Патент USA US2024975

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Patented!’ Dec'. 17,1935
2,024,915 *
I UNITED} STAT‘Esp
PATENT OFFICE
VATAPPLICATION
DYE CODIPOSITIONS
THEREOF
Herbert A. Lubs and John Elton Cole, Wilming
ton, Del., assig'nors to E. I. du Pont de Nemours
& Company, Wilmington, DeL, a corporation of
Delaware
No Drawing. Continuation of application Serial
No. 504,274, December 23, 1930. This applica
,tion December 19, 1933, Serial No. 703,156.
‘23 Claims. (Cl. 8-6)
( This invention relates to the art ofv applying
vat dyes to textiles, and more particularlylto
the art of textile printing. It also" relates to new
vat dye compositions.
_
This application is a continuation ofour co
pending application, Serial No, 504,274 ?led De
cember 23, 1930. It‘ also contains subject matter
disclosed in our co-pending application Serial
No. 703,155.1i1ed December 19, 1933.~
10
Except for indigo, vat dyes (which are unlike
all other types" of dyes both in properties and
mode of application to the ?ber) were not known
prior to the beginning of the present century.
“By the term vat dye is meant a colouring mat
ter insoluble in water, but which can be converted '
on reduction ‘into a so-called Ileuco compound,
which is soluble in alkalis, and in such a solution,
termed a vat, the actual dyeing process is ef
fected; on removing the material from the bath
"20 and exposing to the air oxidation‘ takes place, the
dye being precipitated on the ?bre in insoluble
form; . . .”
From page 423 of “A Textbook of Dye Chem
istry” by Georgievics and Grandmougin (1920).
In the application of vat dyes to textile ?bers,
a distinction is to be made between dyeing (that
is, coloring of the entire fabric) and printing, in‘
which only a portion of the fabric is colored.
The mode of applying the dye in each case is
30
different.
'
The process of dyeing comprises suspending
the insoluble vat dye in an alkaline solution and
thereafter adding a reducing agent to change
tive, penetrate the ?ber and, upon removal from
the solution followed by oxidationyare regen
erated, resulting in a dyeing taking place as in
the general process ?rst described. ' As will be
obvious‘, some of the dye‘is lost from the ?ber by
reason of going into solution in the vat. If this
process is continued long enough, su?lcient dye ‘
would be removed from the ?ber to render the
reducing solution a dye vat of ordinary concen
tration. Inasmuch as a reduction to the hydro 10
derivative is necessary‘both in dyeing from a
solution and by the padding method, the so1u->
tion-dyeing process is the one most widely used
where space and equipment permit.
s
While various reducing agents may be used 15
in the dyeing (as differentiated from printing)
of vat dyes, the one most commonly utilized is
a hydrosiil?te.
“For some years past solid 'hydrosulphite‘of
soda, containing amounts of Nazsaoi varying 20'
from 60 to 95 per cent., has been in the -market
in the form of a dry,‘almost white, powder“ It
is largely used in the dyeing“ of indigo and other
vat dyes, but, owing to the rapidity with which
its solutions oxidize in contact with the air, it 25’
is not suitable for textile printing.”
From page 250 of the “Principles and Practice _
of Textile Printing” by Knecht 8: Fothergill
(1924) . As indicated in the above quotatio , the
ordinary reducing agent utilized in the dyeing 01.30‘
vat dyes cannot be used practically in the print
ing of vat dyes on textile. This is a serious dis
advantage because vat dye printing is, for other
the vat dye to its hydro derivative (the reducing ‘ reasons, much more complicated than vat dyeing. I
This particular difficulty has been partially over- 35
come by the discovery and commercial produc
tion ofthe compound sodium formaldehyde sul
foxylate which only exerts its reducing in?uence
at elevated temperatures. By use of this and
soon as a su?icient amount of ' the leuco
body solution has been ‘absorbed. Exposing the equivalent compounds the vat dye can be im
soaked fabric to an oxidizing in?uence, usually printed on a fabric in the desired design and
the oxygen oft/the atmosphere, regenerates the thereafter reduced and ?xed to the ?ber.
At the present time, the most extensive textile
vat dye on the ?ber producing a dyed material.
There is an alternative process known _' as printing is done with cylinder or roll printing ma
chines. The fundamental principles in this proc- 45 y '
“padding” which is used to some extent at pres
ess are simple and. comprise passing the cloth
ent. According to this process the ?ber is im
mersed in a suspension of a‘ vat dye until a to be printed under some tension and pressure . "1 '
over an intaglio metal roll, the engraving of which
sumcient quantity of the dye has adhered me‘
is ?lled with a printing paste. After leaving the
chanically to the ?ber (this adherence is analo
printing machine, the printed cloth is quickly ‘0
gous to wet sand clinging to stick used for stir
ring a sand and water mixture). Thereafter the passed into a drier. This dries the printing paste
?ber, with the dye particles mechanically held on the cloth in its proper place and prevents the
dye from spreading to other portions of the fabric thereon, is immersed in an alkaline solution con
taining a reducing agent whereby the dye pare‘ with consequent ruination of the design (in dyeing
agent may also be added before or simultaneously
with the dye). The ?ber is then steeped in the
solution of the. hydro derivative (referred to
above as leuco compound) and is removed as
:1,$1" ticles are reduced to the soluble
deriva
with vat dyes, spreading of the colorsolution over?“ '
2
the entire cloth is earnestly sought for, but in the
printing of vat dyes, the slightest spreading of
the color destroys the value of the printed cloth
to such an ‘extent that the same is ‘not salable).
The printing paste applied to the cloth from
theroller is a material thickened to such an ex
tent that it does not run readily. It varies with
different fabrics and manufacturers, but usually
consists of a ‘mixture of unreduced vat dye, a
10
strong reducing agent such as sodium formalde
hyde sulfoxylate, an alkali and a thickening
agent. The thickening agent is usually a gum
(for instance, British gum) , starch, or both. The
printing paste is usually prepared .by mixing a
15 dye paste or pastes with the other ingredients
enumerated, said other ingredients being in the
form of a gummy mixture hereinafter called
'“printing gum”. The dye pastes are essentially
?nely divided suspensions of dye with or without
20 a dispersing, agent.
These dye pastes (herein
after referred to as “dye pastes”, “dyestu? pastes”
or “color pastes”) usually have the dye sus
pended in water.
.
In order to complete the printing, the cloth,
25 after leaving the drier, is passed into an ager
(usually a steam ager) for a period of a few min
utes, during which time the vat color undergoes
reduction ‘(the sodium formaldehyde sulfoxylate
in the printing paste producing its reducing action
30
r
2,024,975
because of the elevated temperature in the ager)
and passes to the ‘?ber. The fabric is then sub
jected to oxidizing conditions which may include
passing it into a steeping bath, usually of water
or water containing an oxidizing agent.
Any ex
erty enables them themselves to exert a reducing
action upon the vat-dyestuif used; this enhance- ‘
ment of the reducing power of the vats is also
favourable for the setting and working of the
vats, because on the one hand the dyestuff is re
duced more quickly and on the other hand the
oxidation of the vats is better checked. . . .”I
This patent indicates that substances such as
anthraquinone act as assistants in reducing the
dye and in checking oxidation, thereby effecting 10
a better utilization of the dye, but it does not
indicate that better dyeings are obtained. Simi
larly, Remlein, U. S. Patent No. 1,750,942, dis
closes a padding process (de?ned above) in which ,
anthraquinone is used, although its use is not I i.)
claimed nor is its function given.
The following tests indicate that anthra
quinone does not in fact give stronger dyeings:
A cotton skein was introduced into a vat whose
volume in cubic centimeters was approximately 2 0
twenty times the weight of the skein in grams.
The vat was maintained at a temperature of
about 160° F. and contained 5% of a color paste
comprising approximately 12% 6:6’-diethoxy
thioindigo, about 4% caustic soda and about 1:
7.5% sodium hydrosul?te (all percentages based
on the weight of the skein).
The reduction >
took place at about 180° F. The skein was then
oxidized and soaped in the well known manner.
A similar dyeing, except that the vat contained a
one gram of anthraquinone per liter of solution,
was judged to be only about 33% as strong as the
dyeing made from the vat in which no anthra
quinone was present.
’
' . cess color is washed off in a soap solution with
On account of the greater complexities, it is 3
which the textile‘ material is treated‘ following much more dif?cult to obtainv suitable assistants
the steeping.
'
for printing than for dyeing. However, a num~
j Vat dyes at the time of printing are not in true ber of such assistants have been proposed. One
solution. For this reason,_ the effecting of com
such compound is tri-ethanolamine (U. S. Patent
40 plete reduction of the dye and the transfer of the ’
No. 1,790,950) and with it markedly improved re- 4
color to the fabric‘ in the brief time which the sults have been produced. Another compound
goods are steamed is a process accompanied by which has been proposed for this use is
‘ great difficulties, as previously stated.
In‘ order
to make sure that satisfactory resultsare ob
45" tained, it is important’ that the dye paste be of
special ?neness, but even then a great deal of '
color is lost because of its failure to dye the cotton.
This excess color is washed oif during the soap
ing which follows the steaming.
In both dyeing and printing it has been pro
posed to assist the process by the addition of
various substances, for convenience called “as
sistants”. The purpose for‘which such assistants
are added and the functions which. they perform
- may vary widely. _ Thus, in dyeing, some assist
ants are added to speed up reduction of the dye,
others to retard oxidation of the vat. ’ It does not
follow, however, that more brilliant and brighter
6
dyeings are obtained.
0v in 8.
Y
-
The same is true of print-,.
.
. 0 illustrate this distinction, attention is called
to British Patent No. 3241 of 1911, in which it is
stated that: “. . . the preparation and the work
ing of vats of indigoid dyestuifs (that is to say
dyestuffs, except indigo, which, like indigo,
‘contain the chromophorous group —CO—-C=
C—CO-—) can be greatly facilitated by adding
anthraquinone or a derivative thereof, such, for
example, as (alpha-): or .(beta) -oxyanthraquin
- one, a dioxyanthraquinone or a sulphonic acid
1 of one of these, to the stock-vats and to the dye
vats. The action of the anthraquinone-and its
derivatives in the vat is due to the ease with
which they are reduced and to their power of
Y 75 acting as hydrogen carriers. This latter prop
U
beta:beta'—dihydroxy-diethyl ether (British Pat
ent No. 368,910). Further examples might be
given without adding anything to the discussion 4;
of the prior art.
_
Practical experience has shown those skilled in
the art the utter futility of attempting to predict
what substances will or will not be good assistants
in dyeing and/or printing; or that assistants in -
dyeing produce stronger and brighter printings;
or that assistants in printing produce stronger
and brighter dyeings. It is well recognized by
those skilled in the art, and is therefore worthy
of note, that assistants in dyeing and printing
other types of dyes cannot be expected to be
assistants in dyeing and printing vat dyes because
the mechanisms of the reactions involved are
different.
'
'
It is an object of this invention to produce new (I;
and improved “dye compositions of the indigoid
type. A further object is to provide new and
improved dye compositions of the indigoid type
which are suitable for use in printing pastes and
when printed on the textile ?ber yield .prints of (.
unusual strength and brilliancy. A more spe
ci?c object is to provide new and improved thio
indigoid dye compositions. Other objects are to
produce improved printing pastes, improved
printing gums, improved dye pas‘es and to pro- 7;
vide new and improved results in textile printing.
Still further objects will appear hereinafter.
These objects are accomplished by the-produc
tlon of dye compositions comprising an indigoid
dye, or mixture of indigoid dyes, containing as an 7
2,024,975
the silver salt was omitted, was prepared and
prints made from the two pastes under similar
conditions. The prints obtained from the print
ing paste containing silver salt were v10 to 25%
stronger than those obtained fromrthe other 5
assistant an alkali metal or ammonium salt of
anthraquinone-Z-sulfonic acid, or a mixture of
said salts, and by the application of such com
positions to textile ?bers and fabrics. The new
printing assistants may be used alone or in con
junction with other assistants. They may be in
corporated into the dye paste, printing/gum, or
printing paste either as such or in the form of the
free sulfonic acid. It will be recognized that the
10 free sulfonic acid may be converted to the alkali
metal salt by reaction with alkalis such as are
present in the printing gum or printing paste.
printing paste.
<.
and made into a printing‘ gum having the follow'
1
__
67.5,
Potassium carbonate...v _____ __‘ __________ __
8
SulfoxiteC _______________ ___T _________ __
4
.
.
Percent
'
following composition:
.
5
15.5
,
'
p Percent 25
i.
Printing gum __________ __., __________ __'_'__ 79.5
Sulfoxite C (sodium formaldehyde-sulfoxy
‘
15
A dye paste-containing 12% of ~6:6'-dimethoxy- 20
thioindigo and the sodium salt of .anthraquinone
2-sulfonic acid were incorporated into the print
ing gum to produce a printing paste having the
Thickener _____________________________ __ 57.5
Potassium carbona‘te ___________________ __ 16.0
Dye paste ______ __'_____ "a _______________ __ 20
__
11.
Glycerine; ______________ ....d.__‘ __________ __
5
'
____ __
Water ______ __'_ ______________ __,________ __
From this thickener a printing gum consisting of :
Water- ,
Percent
_
Glycerine ___________________ _, _____ __-____
A thickener was prepared containing 10%
late)
'
Thickener
wheat starch, 30% British gum and 60% water.
r
‘
ing composition:
Ezrdmple I
‘
.
A'thickener consisting‘ of 10% wheatstarch,
is not limited, by the following examples.
20.
'_
30% British gum and 60% water was prepared 10
The invention will be further understoo’dfbut
15
,
Example III
Strong alkalis also tend to replace weak alkalis
such as ammonia.
3 ,
___
'
Anthraquinone-2-sodium
sulfonate______ __
.5
10.5
Example IV
30 was prepared.
This printing gum was made into
a printing paste by incorporating therein a dye
\_
I’
30
A thickener containing 10% wheat starch, 60% "
paste of 4:4’-dimethy1-6:6'-dichloro-thioindigo. water and 30% British gum was prepared and
and anthraquinone-2-sodium sulfona‘e._ The made into a. printing paste having the following
35
percentage composition:
percentage. composition of the printing paste was
as follows:
'
.
-
-
'.
'
Thickener____. __________________________ __ 67.5
Percent
Potassium carbonate _________ __‘ _________ __
Sulfoxite C_'_ ________ __‘.. _________________ __
Printing-gum __‘ ________________________ __ 79.9
Dye paste (12.5% dye) __________________ __ 20
40 'AnthraQuinone-Z-sodium sulfonate ______ __
Water __
-
v
‘-
.
_
-
1
_
Percent
Dye paste
-
Sil
er
I
“"1 2o
t _____ __' ______________________ __
~
P°ta53ium_carb°mte ___________________ __ 16_
, was printed on cotton, dried, aged and developed
sulfoxite c ____________________________ __v 11
Glycerin?
_____
5
_ in the usual way. The prints obtained were more ,,
- ‘than 10% stronger than those .obtainedTrom a "d
The thickener consisted of:
,
I
I
'
10.5
>
.
J
.v
‘0.5
Thickener___-_ _________________________ __. 57.5
Water ____________________ "Q ____ _; _____ ._
60
15.5 4°
Prmtmg gum --------------------------- -- 79-5 59
Percent
.-
_
mixture. the printing paste, / which was com
A printing gum was prepared comprising:
‘
'
paste by stirring the same with a 20%. dye paste
of 5:5’:7:7’-tetra-brom-indigo (C; I. No. 1184,
brominationinnitrobenzene) and anthraquinone- 45
2-sodium su1fonate.- After producing a uniform
posed of:.
J
I
___
This printing gum was made into a‘ printing
Example II
v
8_
4
Glycerine ______________________________ __ \ 5
0.1
This product was printed on textile material
which was then aged and developed in the usual‘
and well known way. .'The prints obtained were
from 10 to 25% stronger than those obtained
from a similar composition which differed only in
the omission of the anthraq'uinone-Z-sodium sul
fonate'.
I '
Percent 35
-
.
‘
paste printed under similar conditions which was
similar in every respect except that the anthra
- quinone-Z-sodium sulfonate had been omitted.
Percent
Example V .
Wheat-starch"; _______________________ __ 10
60
Britishgum ________ -, __________________ __‘_ 30
WBWL.
__ _ _ _ _
_ _ _ _:_
6O
1 A thickener was prepared including 10% wheat
starch, 30% British gum and 60% water. From
This printing gum was made into a printing paste
by mixing it with a 6_:6'-diethoxy-thioindigo
(C. I. No. 1218) dye paste containing 11.5% solids.
To this mixture there was added silver salt (the
Thickener--.‘ ______ -7 ______ .._' ____ -Q _____ __ 57.5
sodium salt of anthraquinone-Z-sulfonic acid) .
Potassium carbonate}, ___________________ __ 16
this thickener a printing gum consisting of:
‘
Percent
The percentage composition‘ ot_ the resulting , Sodium formaldehydelsulfoxylate ____ __,____ >11
printing paste was as follows:
Glycerine; ________ _'7__' _________________ __
5
~
Percent
Printing gum __________ __' _____ -; __________ _. '79
Dye paste---
Silver salt
75
'
I’
-_~
1
...~
a
'
i
20
1
Water ____
'
70
__ ‘10.5
was prepared. This printing gum was made into
a printing paste by incorporating therein a dye . paste of 5:5’z'lzT-tetra-brohr-indigo containing
Another paste, similar in all respects except that‘ 20%‘ solids (C. 1.. No. 1184), anthraquinone—2- 75'
2,024,975
‘
~
'
sodiumwulfonate. The percentage composition
wheat starch, 30% British gum and 60% water.
of the printing paste was asfollows:
From this thickener a printing gum consisting of:
vPercent
79.9
Printing gum-
.
Percent
Thickener
Dye paste ‘(20% dye) ___________________ .... 20
I
-
57.5
'
Potassium carbonate ____________________ __ 16
Anthraquinone-2~sodium sulfonate________- 0.1
5
Sodium formaldehyde-sulfoxylate (Ronga
This product was printed on textile material
which was then aged and developed in the usual
way. The prints obtained were from 10 to 25%
lite)
11 i
'Glycerine
_
5
_ Water _________________________________ ___.
10.5
10 stronger than those obtained from a similar com
was prepared. This printi‘hg gum was made into 10
position whichidi?ered only in the omission of v a printing paste by incorporating therein, anthra
the anthraquinone-2-sodium sulfonate.
Example v1
15
quinorie-Z-sodium sulfonate and a dye paste of
the dye resulting from condensing 5:7-dibrom
'
isatin chloride with 3-hydroxy-4-methyl-6
chloro-thionaphthene. The percentage compo 15v
[A thickener was prepared consisting of 10%
wheat starch, 30% British gum and the remainder
water.
sition of the printing paste was as follows:
Percent
This thickener was incorporated in a
printing gum having the following composition:
20
Printing gum
‘
.
Percent
Thickenen-
Anthraquinone-Z-sodium sulfonate _______ __
“V 56.5
Potassium carbon ate
1
\
Commercial glucose ______________ __“ ______ __ 15
Glycerine _____ __'_ ______________________ __
Water-
_____ __
'
____ __
5
12.5
anthraquinone-Z-sodium sulfonate.
This printing gum was mixed with a 16% (solids)
Example IX
The printing paste having the following com- 30
dye paste of bis-beta-naphthio-naphthene indigo
30 and the sodium salt of anthraquinone-beta
sulfonic acid to produce a printing paste. Thi
printing paste, being composed of:
position:
>
»
Per cent
5:5 '-dichloro-7 :7 '-dimethyl-thioindigo
(20 %
‘
dye paste) (C. I. No. 1209) ______________ __ 20
20
AnthraquinoneJ-sodium sulfonate _______ ..
i
_
,
Percent
Printing gum ___________________________ ___ 79
35 Dye paste
20
0.1
This product was vprinted on textile material
which was then aged and developed in the usual
way. The prints obtained were from 10 to 25%
stronger than those obtained from a similar com- 25
position which differed only in the omission of the
10
Sodium hydroxide ______________________ __
25
79.9
Dye paste (10% dye) ___________________ __ 20
"Thickener"-
1 >
was printed on- cotton textile material in the well
known way.- Comparison of these prints with
prints obtained under similar conditions from a
_____
55 35 i
Glycerine _______________ __; ______________ __'
Sodium hydrosul?te ______ _b ______________ __
5
5
Sodium hydroxide (36% strength); _______ ___
5
Sulfoxite C __________________________ __-____ -5
40 similar printing paste which omitted the anthra
quinone-2-sodium sulfonate showed them to be
about 15% stronger.
Water_______________________ ___V_____ ______ ___
3 4O
Anthraquinone-betaisodium sulfonate _____ __
1
was prepared. In the preparation of this com
position all of the ingredients except the last three
mentioned (namely, the sulfoxite C, water and
silver salt, were brought together, ‘uniformly 45
Example VII
A thickener was prepared consisting of 10%
wheat starch, 30% British gum and the remainder _ mixed and heated until reduction was complete,
water. This'thickener was incorporated in a whereupon the remaining ingredients were added
and the product stirred to uniformity.
printing gum having the following composition:
50
thickener in this case consisted of:
Percent
56.5
Thickener
80% of a thickener consisting of :_
10%; ______________________ __wheat starch
Potassium carbonate ____________________ __ 10
Sodium hydroxide _____ ___ _______________ -_‘ 1
Commercial glucose _____________________ _.. 15,
55
Glycerine
v
Water __
30% ____________ __~_ _________ __British gum
60%
'
5
-
dye paste of 6:6’-di?uoro-thioindig6 and sodium
salt of anthraquinone-beta-st?fonic acid to pro
duce a printing paste. This printing paste, being
w‘
“
V.
‘
-
Percent‘
Printing gum ___________________________ __ 79.1
65
Dye paste____
'
20
Anthraquinone-Z-sodium sulfonate"; ____ __
0.9
was. printed on cotton textile material in the well
known way. Comparison with prints obtained‘F
under similar condition from a similar printing
70 paste which omitted the anthraquinone-Z-sodium
sulfonate showed that the (silver salt) paste gave
prints about 15% stronger.
Example VIII
75
,
_
_water
5% __________ __, _____________________ __water
15% ____________________ __potassium carbonate 55
This product was printed on textile material
which was then aged and developed in the usual
way. The prints obtained were stronger than
those obtained from a similar composition which _60
differed only in the omission of the anthraquiné
12.5
This printing gum was mixed with a 16% solids
composed of :
The
q
'
one-2-sodium sulfonate.
.
_
'
Example X
A printing paste was made from the following
ingredients:
'
'
6:6'-dichloro-thioindigo
solids)___..
'
dye
__
___
'
paste
(55
Per cent
(10%
_ 20
Thickener ________________________________ __ 55
Glycerine _______________________________ __' 5 70
NazSzOr __________________________________ _..
5
NaOH (36% strength) ____________ -._ ______ __ x 5
Sodium formaldehyde-sulfoxylate (Rongalite)
6
Water ______________________________ __'____ > 3 v
A thickener was prepared containing 10%
_Anthraquinone-Z-sodium sulfonate__=_' ____ __
1 75
_
2,024,975
5 .
- The method of preparation was as follows:. The
composition adding 5% water and 15% potassium
dye _ paste, thickener, glycerine, NazSaO. ' and
NaOI-I wereuniformly mixed and heated until re
carbonate. When the product was printed on‘ a
textile material, aged and developed, the prints
' duction'was complete.“ The Rongalite, water and
were found to be 10 to 25% stronger than those
made without. any anthraquinone-2-sodium 5111- 5'
anthraquinone-2-sodium sulfonate were there:
after added. The product _was stirred to uni
'fonate.
-
)
80% of a composition comprising:
.
A thickener was ' prepared containing 10%
'
.wheat starch, 30% British gum and the re
mainder water. This thickener was incorporated 1°
10% ______________________ "wheat starch
10 \
30%
,
British gum
60%
' in a printing gum having the following composi
tion:
Per cent
__water
I 5%
___water
. 15%
K2003‘
Thickener
Y
Potassium carbonate
"15 The product was printed on‘ textile material.
This was aged and developed in the usual way.
The prints were 10 to,25% stronger than those
_ made with a similar composition from which the
' anthraquinone-2-sodium sulfon'ate had beerromit
ted.
~
I
'
-
v
Example XI
_
-
Water
‘
Gly'cerine
\
/
~
'
___
(7.5
>
5
. This fprinting gumwas mixed with a 12.5% color-g2o
.
paste of -4:fi'-dimethyl-6:6'-dichloro-thioindigo ‘_
‘and sodium salt of anthraquinone-beta-sulfonic
The following ingredients were incorporate
into a printing paste: .
56.5
\ 10 15
‘Sodium hydroxide
‘
1
Preserver’s syrup___-___.,_ _______________ ___.. 20
.
I
v
I’ ' Example XIII
formity. \ The thickener used was: I
'
acid to produce a printing paste.
This printing
, .
Per' cent . paste, being composed of:
5:5’-di?uoro-thioindigo dye paste (10%so1ids) . V20
Thickener
Glycerine
,
~' ,
‘
NazSiO:
'
‘
_
L
55
'
.
Printing gum
-
'- .
a
Per cent
J
Dye paste
.2
25
'
'79
‘
- 20
Anthraquinone-2-sodium sulfonate _______ __
NaQH (36% strength) __________ __g__'_ ____ __
'1
was printed on cotton textile material in the well 30
Sodium formaldehydel-sulfoxylate (Rongalite) 6 known way.
~
Water
‘'
Comparison with prints obtained
under similar conditions’ from a similar'printing
paste which omitted the silver salt showed about
20% greater strength in the print from the print
a
_ Anthraquinonee2-sodium sulfonate____.-._____
The dye, thickener, glycerine, Nazszdi andNaOH
were brought together and uniformly mixed. ing paste of this invention.
Heat was applied until reduction wasfycomplete.
Ezample‘XIV
,Then' the Rongalite, water and anthraquinone-2- ’
,
9
35
' A thickener was prepared containing 10%
sodium sulfonate were added. The product was
stirred to uniformity.
~
wheat starch, 30%_ British gum and-the re
.
The thickener used was prepared as follows: 1‘ mainder water. This thickener was-incorporated 40
, In a composition consisting of 10% wheat starch, in a printing gum having-the following composi
40
30% British ,gum and 60% water, ‘there were
tion:
'
I
"
Per cent
stirred K300: 'and water until" the resultant ma
terial was as follows:
as u
'
' Thickener
56.5
Potassium carbonate__g_-_ _________ __'_____ __ 10 ' 45
-_Per cent
~
'
. J
.
Composition‘ ’~
Water
'
~
'
'
'
v
>
KaCOa
'
~
'
” Sodium hydroxide _______ __' _______ -__ ____ _-
80
-
‘
-
'
‘
'1
,
I Commercial glucose _____ _1 __________ _r_____ 15
5
Glycerine
15
‘
Water
The printing paste obtained was printed on
5
"
-
12.5
This printing gum was mixed‘ with a 20% solids 60
50 a textile material and aged and developed as usual.
These prints were from 10 to 25% stronger than ‘dye paste of 5:5'-dibrom-7:'l'-dimethyl-thioin- .
_digo and anthraquinone-betaesulfonic acid ,to
a corresponding paste without the silver salt.
produce a printing paste. This printing paste,
“T ‘
Example XII
being composed of:
m
,.
~
‘
>‘
-
Printing gum
I
Glycerinev
-
65
_
/
~
>
g
'__
_
i
75 ‘British gum’and 60%‘water and to 80% or such
-
‘ Example‘ XV
‘ 3
was. stirred to uniformity. The thickener used
was made by mixing 10% wheat starch, 30%
> '79‘
20
were about 15% weaker.
Sodium 'formaldehyde-sulfoxylates-nr _____ -1 6
‘
'
1
omitted the anthraquinone-2-sodium sultonate' '
NazSzQa
. i
',
'
v
f
' NaOH-_"(36% strength) ...a _______________ __ I 5
Water
I
'
known way. The prints-obtained under similar 60‘
conditions from a similar printing paste which‘
‘5
- Anthraquinone-2-sodiu1n sulfonate_‘___.._'____ 1
The method used in preparation was this: The
dye paste, thickener, glycerine, N82S2O4 and
70 NaOH were uniformly mixed and heated to com
plete reduction. The sulfoxylate,‘ water and an
thraquinone sulfonate were added. This product
'
was printed on cotton textile material in the'weil
55.
y"
'
Anthraquinone-2-sulfonic acid__- _____ __'____..
1189) (20% solid dye paste) ____________ .._ 20 Thickener
'
>
Dye paste
Percent
4:4'-dichloro-5;5'-dibromo-indigo (C. I. No.
60
'
cent 56 J
Agprinting paste of the following composition
was prepared:-
’
.
-
_
The printing paste having <the following com
position:
.
.-
'
-
.
.
Per cent
4;4'-dimethyl-thioindigo (10% dye) _______ __ 20
Thickener
'
-
»
55 70
Glycerine
5'
Sodium hydrosul?te ______ n. ______________ __
‘5
Sodium hydroxide (36% strength) _v__..______ 5
Commercial glucose_-_-__‘ __________________ __
9
Silver salt
1 76
-
-'
G
2,024,975 ‘
and the product stirred to uniformity. The
was prepared. In the preparation of this compo
' sition all of the ingredients except the commer
thickenerlin this case consisted of:
cial glucose, water and silver salt were added,
Water
complete, whereupon the remaining ingredients
Wheat starch
listed were added and the product stirred to uni
formity. The thickener in this case consisted of :
Potassium carbonate ____________________ __-
15
British gum
24
,
>Water
'
Per cent
uniformly mixed and heated until reduction was
8 5
_‘
which was then aged and developed inthe usual.
way. The prints obtained were from 10 to 25% m
8
stronger than those obtained from a similar '
composition which differed only in the omission .
of the silver salt.
'
Potassium carbonate___'_ _________________ __ 15
'
British gum ________________________ ___'.____ 24
This product ;was printed on textile material
151 which was then aged and developed in the usual
Example xvm
way. The prints obtained were from 10 to 25%
stronger than those obtained from a similar com
position whi'ch'di?ered only in the omission of
-
.
.
-
‘Example XVI
Per cent 20
6:6'-diethoxy-thioindigo (C. I. No. 1218)
(11.5% solids dye paste) ______________ -The printing paste having the following com- '
position:
Thickener
25 ‘e
Glycerine
Dye paste of the thionindigo dye prepared
by well known methods. from 2-thio
glycol naphthalene (14% solids) ______ _K___ 20
II'hickener ‘
55
Glycerine
»
5
Sodium hydroxides (36% strength) ________ .._
Commercial‘gluco ______________ __\___-___.._
5
9
Anthraquinone-beta-sodium sulfonate _____ __
1
55
,
5 25
Sodium hydroxide (36% strength) _i..____-_..
5
Commercial glucose _____ __' ______________ .._
9
Silver salt
1
'~
complete, whereupon the remaining ingredients
mercial glucose, water and anthraquinone-beta
Per cent
sodium sulfonate were added, uniformly mixed
Water
' and heated until reduction was complete, where
the product stirred to uniformity. The thickener
'53
_
British gum
the anthraquinone-2-sodium. sulfonate.
Example XVII
_
Per cent
droxy - 4 - methyl-?-chloro-thionaphthene
Thickene'r
20
'
55
'
5
,. Sodium hydrosul?te _______ -_'_ ______ _-v..___
5
70.
Sodium hydroxide. (36% strength) _______ __
5
Commercial glucose____;___, ____________ __
9
Anthraquinone-2-sodium sulfonate _______ __ 1 1
was prepared.
c
>
I
" ’
the silver salt.
’
\
.
Example XIX
60
The, printing paste having the following com
position:
'
~
'
,
Per cent
4:-i'-dichlor-5:5'-dibrom-indigo.(20% solids
,5
dye paste)
20
Dye paste of the dye resulting from condens
ing 5:7-dibrom-isatin chloride with 3-hy
Glycerine
24
.
The printing paste having the following com
position:
65
British gum_
position which differed only in the omission of
___.. 24
(10% solids‘)
-
15 40
stronger than those obtained from a similar. com- 45
This product was printed on textile material ,
which was then aged and developed in the usual
50 way. The prints obtained were from 10 to 25%
stronger than those obtained from a similar com
position which di?ered only in the omission of
60/
8v
Potassium carbonate ___________________ ...:..
way. ‘The prints obtained were from 10 to 25%
8
Potassium carbonate____.. ________________ __ 15
-
53
This product was printed on textile material
which was then aged and developed in the usual
Per cent
‘
45 Wheat starch
i
-
;
I
.
"as
1
Wheat starch
40 upon the remaining ingredients were added and
Water‘
5
'
were added and the product stirred to uniformity.
The thickener in this case consisted of:
35
35 was prepared. In the preparation ’of this ‘com
position all of the ingredients except ‘the com
in this case consisted of:
.
20
was prepared. In the preparation of this com
position all of the ingredients except the com- 80
mercial glucose, water and silver salt were added,
uniformly mixed and heated until reduction was
5 .
Sodium hydrosul?te _..___- _______________ __
,
Sodium hydrosumte
Per cent
30
)1‘
The printing paste having the following com
position: a
the silver salt.
20
53
This product was printed on textile material '
Per cent
_ 53
Wheat starch ____________________ __> ______ __
'
Thickener
'
Glycerine
55
_
5
-
Sodium hydrosul?te ____ -_._-_'_' ____ _.>._..;_'__ ' 5
Sodium hydroxide (35% strength) _____ -_.._l_
5 60
Commercial glucoseuii. ____________ .._'_____
Anthraquinone-beta-sodiuni sulfonate____ ..-
9
1
' was prepared.
‘
In the preparation ‘of this com- ‘
position all of the ingredients except the glucose,
vwater and anthraquinone-beta-sodium sulfonate 66 V
were added, uniformly mixed and heated until
reduction was complete, whereupon the remain- _
ing ingredients were added and. the product
stirred to uniformity. The thickener in this case
consisted of:
In the preparation of this-com- '
“
‘
.
‘l0
Per cent '
position ‘all of'the ingredients except the glucose,
water and silver salt were added, uniformly
mixed and heated until reduction was complete,
Water
53‘
Wheat starch
‘
Potassium carbonate
8
15
whereupon thelremaining ingredients were added
British gum ____________ __' ________ ..-........_..
24 76
-
3r
'
7
2,024,975
Example XXII
This product was printed on textile material
which was then aged and developedin the usual
way. The prints obtained were from 10 to 25%
stronger than those obtained from a similar com
position which differed only in) the omission of
Thickener
the anthraquinone-beta-sodium' sulfonate.
K2003 _______________ _Q ________________ .. 10
A printing gum was made from:
.
'
_. Per cent
___
56.5
NaOH
___-
tose) _________ __‘___ _______________ __‘___
Glycerine_
A printing gum was prepared from:
'
,
Thickener ___. ________________________ _,__
57.5’
E0031.
16
15
___
Sultoxite C-.. -
11
iGlycerine ___
.
Water
5
10
I e The thickenercontained 10% wheat starch, 30%
British gum and 60% water. A printing paste
was .made from the printing gum by adding 6:6’
diethoxy-thioindigo (C'. I. No. 1218) dye paste
containing 11.5% solids. To this ‘mixture was
added milled silver salt (sodium. salt of anthra;
quinone-Z-suli'onic acid). The resulting print
-
-
Per cent
gum_ ____________ _1 ______ ________ 79.9
Dye paste
_ 20
Milled silver salt ________ ____'__________ _..__
0.1
Two other pastes were prepared, similar vin all
respects except that in one the ‘silver salt was
not milled and in the other the silver salt was
omitted. Prints were‘ made from the’ three pastes
under similar conditions. The prints made from
the two printing pastes containing the silver salt
were 10 to 25% stronger than those made from
the paste from which silver salt was omitted.
But it is also worthy of notice that those prints
made from the paste containing the milled silver
salt were noticeablystronger than those printed
with the paste containing silver salt which had
not been milled.
.
Per cent
KaCOa __________ __'________ _'__. _________ __
8
Sulfoxite C :3. ____________ __, ___________ __
4
. Glycerine___;
'
'
\
5
____ __
wasJused to make a printing paste by mixing uni
60 Iormly with a dye paste containing 12.5% of 4:4’
Jdimethyl-6:6'-dichloro-thioindigo and, a small
amount of milled silver salt. The following pro
portions were present in the ?nished composi
tion:
.
~
)Dye paste.
Per cent
__
79.9
1
'
20
Milled silver salt--. ____________________ __
0.1
70 Prints made from this printing paste were 10 to
25% stronger than those made from a‘ similar
paste in which silver salt was absent, and vnotice
ably stronger than those made from a similar
paste which contained silversalt which had not
75
'
Per cent 20
Printing gum
'79
' Dye paste
____
20
Milled anthraquinone-beta-sodium sulionate- 1
.Prints were made from this paste. These prints
paste which lacked the presence of the milled
assistant. The prints from the paste with the
milled silver salt assistant were 10 to 25% strong
er than the others. They were also noticeably
‘ stronger than prints made from 'a similar paste
in which the silver salt assistant used was not
milled.
Example XXIII
A printing gum was prepared containing:
1
I
'
‘ 35
Per cent
Thickener _____________________________ __ » 56.5
Potassium carbonate _______________ _l______ 10
Sodium hydroxide ________________ ...' ____ ___
1
40
Commercial‘ glucose ____________________ __ 15
Glycerine-
__
water
5
___-
12.5
undergone themilling process.
This printing .vgum was made into a
'quinone-Z-sulfonic acid.. The composition of the 50
printing paste was:
,
Per cent
Printing gum__
79
Color paste (12.5% dye solids) ____________ __ 20
Anthraquinone-2-sulfonic acid. ________ _'.._-_ 1 55
15.5
The thickener contained 10% wheat'starch, 30%
British gum and 60% water. This pririting gum
Printing gum _
lowing proportions:
printing paste with a 5:5'-dichloro-6:_6’-di
methyl-thioindigo dye paste containing anthra:
Thickener ______________________________ ___ 67.5
65
The thickener contained 10% wheat starch, 30%
British gum and 60% water._ A printing paste
was made from this gum by mixing uniformly 1
with a 16% solids dye paste of bis-beta-naph
thio-naphthene indigo, and the milled sodium salt
of anthraquinone-beta-sulfonic acid in the fol
water.
A printing gum was made from:
Water__‘__
7.5
The composition of the thickener herein utilized
was 10% wheat starch, 30% British gum and 60%
Example XXI
60
-
10
were compared with prints made from a similar
.ing paste had the following composition:
Printing
20
5
E20 ___________________________________ __
.
'
_ p
Per cent
.
_
1
Preserver’s syrup (mainly glucose and truc
Example XX
10
5
‘
'
This paste gave prints several percent stronger
than a similar paste not containing anthraquin
one-2-suli'onic acid when printed, dried, aged and‘
developed in the usual way.
00
Example XXIV I
A thickener whose composition was 10% wheat
starch, 30% British gum and 60% water, was in
corporated into a printing gum whose composi
tion was:
v
.
'
1
>
Per cent
Thickener _____________________ _________ ___
57.5
Sodium formaldehyde-sulfoxylate _______ __ 11
Glycerine ___________________ __~-_ ________ __
5
'
7o
LThis printing gum was made into a printing paste
by mixing the same ‘with appropriate quantities
of a 20% dye paste 0! 5:5'-_dichloro-7:'l'-dibrom- 7§~
8
2,024,975
indigo and a water suspension of anthraquinone
the speci?c embodiments thereof except as de
2-sodium sulfonate which had been milled in
?ned in the following claiins.
water. The composition of the resulting print'-'
We claim:
1. A dye composition comprising a vat printing
and a substance selected from the group consist $1
ing paste was as follows:
Per cent
20
Anthraquinone-2-sodium sulfonate ______ __
-
and alkali metal salts of anthraqulnone-Z-sul
‘0.1
ionic acid.
It is to be understood that the invention is not
10 limited to the speci?c dyes listed in the above
examples.
Other indigoid dyes are well known - ing and a substance selected from the group con
publications as:
sisting of anthraquinone-Z-sulfonic acid; the am
monium salt of anthraquinone-2-sulfonic acid
and alkali metal salts of anthraquinone-2-sul-y
-
.1. Technologie Der Textilefasern- Kiinstliche
ionic acid.
15 Organische Fabsto?e H. E. Fierz-David, 1926.
2. Color Index (1924) , Supplement (‘1928), So
ciety of Dyers and Colourists.
Friedlaender.
’
sisting oi'anthraquinpne-Z-sulfonic acid, the am
monium salt of anthraquinone12-sulfonic acid
'
and alkali metal’ salts of anthraquinone-2-sul- L
4. Farbstoiftabellen Gustav Schultz (1931).
fonic acid.
5. Enzyklopadie der Kiipenfabstoffe Truttwin
(1920).
Speci?c mention may be made of such other *
digo,
indigo,‘ . in-
thioindigo 2- (5:7-dibrom-indol) -2'-an
'
methyl-bis-thionaphthene indigo,-bis-alphanaph- '
prepared by the condensation of reactive 2-isatin
' derivatives with naphthocarbazole bodies-(e. g.,
ortho-tolu-5 -hydroxy-alpha-naphthocarbazole) ,
35
indolacenaphthene indigos, thionaphthene-indol
indigos, and the like. The speci?c dyes of U. S.
Patents Nos. 1,558,252 and 1,792,648 also merit.
particular mention.
Theamount of the assistant is ordinarily va
40 ried directly with the amount of solid dye andv
the paste used, based on a 12.5% solids dye‘paste.
In printing, ‘the preferred amounts are about} 1
to about 5%. Greater or smaller amounts than
this may be used when desired. For example, the
use of 0.5 to 10% of the assistant'in printing gives
good results. Less than 0.5% maybe used if de
sired, although the result is‘not as'noticeable as i
that produced by using an amount falling within
the preferred range. ‘Generally, more than 10%
ing and the sodium salt of anthraquin'one-Z-sul
1
'
5. A printing paste comprising an indigoid dye 2'51
1. and an alkali metal salt of anthraquinone-2-sul-
thalene indigo 4:4'-diet_hyl-thioindigo, 5:5'-di
indigo, dimethyl-indirubin, dibrom-indirubin, dyes
.
ionic acid.
thracene indigo, 2- (5 : 7 -dibrom-ind'ol) -2'-naph
30 thindol indigo, 4:516:7z4':5’:6':7’-octo~chloro
.
4. A dye paste comprising a thioindigoid prlnt- ‘
compounds as 2:3:2’ :3’-di-anthraquinone indigo,
bromo-2~beta-naphthindol-2~indol
15.
- 3. A dye paste comprising a thioindigoid print
ing and a substance selected from the group con
3. Fortschritte der Teerfarben—Fabrikation 'P.
25
.
2. A dye paste comprising an indigoid print- 10
to those skilled in the art and are disclosed in such
20
.
ing of anthraquinone-Z-sulfonic acid, the am
monium salt of’ anthraquinone-Z-sulfonic acid
Printing gum _______ _1 __________________ __ 79.9
Coloripaste ______________ __' ____________ __
’
fonic acid.
'
J
6. A printing paste comprising a thioindigold
dye and an alkali metal salt .of anthraquinone-2
sulfonic acid.
‘
30
'7. A printing paste comprising 4:4'-dimethyl
6:6'-dichloro-thioindigo> and an alkali metal salt
of anthraquinone-Z-sulfonic acid.
8. A printing paste comprising ?z?i-diethoxy
thioindigo and an alkali metal salt of anthra
quinone-2-sulf0nic acid.
‘
'
9. An indigoid printing'gum comprising an al
kali metal salt of anthraquinone-2-sulfonic acid.
10. A thionindigoid printing gum comprising
an alkali metal salt of anthraquinone-2-sulionic 40
‘acid.
-
11. The ‘process of printing indigoid dyes which
comprises applying to the ?ber a printing paste‘
comprising the indigoid dye, an alkali metal salt
of anthraqulnone-Z-sulfonic acid, printing gum, 45
alkali and a reducing agent suitable for printing,
and thereafter drying, aging and developing the
print.
'
v
12. In the process of printing indigoid‘v dyes on
50 may be used without detriment to'the printing _ textiles, the step'which comprises incorporating 50
a substance from the group consisting of anthra
process.
quinone-Z-sulfonic acid and an alkali metal salt‘
It will be recognized that the type of reduc
_ ing agent is to be chosen according to the method
to be used in applying the dye to the ?ber.
55 Sodium formaldehyde-sulfoxylate is a material
well adapted for printing vat dyes, inasmuch as it
is not oxidized at ordinary temperatures and ex
ercises its reducing action at elevated tempera
tures.
'
This invention is of great technical and corn-7'
mercial importance since it has been-found that
the presence of assistants of the type described
in indigoid printing pastes, and especially in the
printing of thioindigoid dyes, makes possible the
production of prints of superior strength and
brightness to those obtained fromia similar print
ing paste from which the assistant has been omit
ted. The prints are also much stronger and
brighter than printing‘ pastes in which the as
70 sistant is a substance such as anthraquinone.v
As many apparently widely di?erent embodi
ments of this invention may be made without de
parting from the spirit and scope thereof, it is to
N be understood that we do not limit ourselves to
thereof into the printing paste.
' ’
13. In the process of printing thionindigoid
dyes on textiles, the step which comprises'incor- 55'.
porating a substance from the group consisting of
anthraquinone-2-sulfonic
acid
and
an _ alkali
metal salt thereof into the printing paste.
.14. In the printing of textilematerial, the step
of printing on the textile material with a printing 60
paste comprising an indigoid dye and an alkali
metal salt of ‘anthraquinone-Z-sulfonic acid.
15. In the printing of textile material, the step
of printing on the textile material with a printing
paste comprising an indigoid dye and-milled so- 65 /
dium anthraquinone-2-sulfonate.
16. The. process of printing thioindigoid dyes
which comprises applying to the ?ber a printing '
paste comprising the thioindigoid dye, an alkali
metal salt of anthraquinone-2-sulfonlc acid, 70v
printing gum, alkali and a reducing agent suit?
able for printing, and‘ thereafter drying, aging
and developing the print.
~
17. The process of printing thioindigoid dyes
which comprises applying to the ?ber a printing ‘75"
9
2,024,975
paste comprising a thioindigoid dye, an alkali
metal salt of anthraquinone-Z-sultnnic acid,
printing gum, potash and sodium formaldehyde
sisting of anthraquinone-2-sulfonic acid and al
kali metal salts thereof.
>
_, ,-
'
the indigoid type which comprises applying to the
21. The process of preparing printed textile
materials which comprises printing on a textile
material with a printing paste containing a water- 5
insoluble thioindigoid color, a. printing gum and
from about 0.1 to about 1.0% of an alkali metal
. goods a composition containing the indigoid dye,
a reducing agent suitable for printing, an alkali
22. The process of preparing printed materials ‘
sulfoxylate, and thereafter drying, aging and de
veloping the print.
i
'
18. The method of printing with vat dyes of
metal salt of anthraquinone-2-sulfonic acid and
10 an alkali ._ metal carbonate, aging the same in
steam, and re-oxidizing in a developer.
.
‘19. A vat dye-printing paste comprising a wa
ter-spluble polyhydric alcohol and a substance
from the group consisting of anthraquinone-2--v
15 sulfonic acid, the ammonium salt of. anthraquin
one-2-sulfonic acid and alkali metal salts of an
thraquinone-2_-.sulfonic acid.
.
20. A printing, paste comprising a thioindigoid
dye, glycerin and a substance from the group con
salt of anthraquinone-2-sul1onic acid.
'
which comprises printing on a textile ‘material low
with '4:4'-dimethyl-6:'6'-dichloro thioindigo in
the presence of an alkali metal salt of anthra- ’
, quinone-Z-sultonic acid.
-
23. The process of preparingprinted materials
which comprises printing on a textile material 15
with 6:6'-diethoxy thioindigo in the presence of
an alkali metal salt of anthraquinone-2-sulfonic
acid.
HERBERT A. LUBS.
JOHN ELTON COLE. 20
Certi?cate of Correction
Patent No. 2,024,975
December 17, 1935
HERBERT A. LUBS ET AL.
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered patent requiring correction as follows: Page 4, second column, line
39, for “Sulfoxite C___5” read Sulfowite C'___6; page 5, ?rst column, line 2, for
“M2520” read Na2S2O4; page 8, second column, lines 4, 10, 16, and 22, claims
1, 2, 3, and 4, respectively, for “dye” read printing; and lines 4, 10—11, 16—17,
and 22—23, claims 1, 2, 3, and 4, respectively, for “printing” read dye; same page and
column, line 39, claim 10, for “thionindigoid” read thioindigoid; and that the said
Letters Patent should be read With these corrections therein that the same may
conform to the record of the case in the Patent Of?ce.
Signed and sealed this 11th day of February, A. D. 1936.
[sEAL]
LESLIE FRAZER,
Acting Commissioner of Patents.
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