Application of Nonsulphonated Azo-coloring Matters Insoluble in Water as Body-colors and in Substitution for Mineral Colors for Printing on Textile Fabrics.
Year: 1892

page_text: Date of Application, 21st Nov., 1892
Complete Specification Left, 21st Aug., 1893-Accepted, 14th Oct., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE vormals MEISTER LUCIUS
AND BRUNING, of Hoechst a Main, in the German Empire, Chemical
Manufacturers.]
Application of Nonsulphonated Azo-coloring Matters Insoluble in
Water as Body-colors and in Substitution for Mineral Colors
for Printing on Textile Fabrics.
I, OLIVER IMRAY of No. 28 Southampton Buildings in the County of London,
Chartered Patent Agent do hereby declare the nature of this invention to be as
follows:-
The development of insoluble azo-coloring matters, fast to light and washing, on
cotton stuffs by previously impregnating the stuffs with alkaline solutions of
phenols and subsequently treating them with the neutralised solution of a diazotised
base, has been taken up to a large extent.
In the Specification to Letters Patent No. 2818 of 1891 it is stated that the
same colors can also be fixed on indigo-dyed stuffs, by treating them first, for
example, with beta-naphthol sodium and afterwards printing them with a thickened
diazo-solution, to which some red prussiate of potash has been added; the stuffs
are then passed through an alkaline bath. The shade obtained in this way, for
example, the red from para nitraniline and beta-naphthol, are of extraordinary
beauty and great fastness, but this process unfortunately has certain inconveniences.
For example, by reason of the very difficult solubility of the ferri-cyanides it is not
possible to incorporate with the printing color a quantity of mordant sufficient to
permit of corroding dark indigo-shades and the indigo-blue stuff prepared with
beta-naphthol cannot be got white with the usual corroding agents, so that it is
impossible to produce with this process the so much liked combination "blue, red
and white."
It is known that similar inconveniences do not exist when vermilion is mordanted
upon indigo in such manner, that it is fixed by means of albumen under simul-
taneous addition of neutral chromates to the printing color, passing the stuff
through an acid bath at the temperature of coagulation of the albumen, as it is
well known that the indigo is oxidised to soluble isatin at this temperature, and by
this method there is obtained at the same time a good white.
The employment of vermilion has however other inconveniences, caused by its
high price and its high specific gravity. By reason of its weight, the mineral color
sinks into the printing color and deposits in the engraved lines of the printing
rollers, thereby causing unequal printing. A gallon of printing ink made from
pure vermilion costs about 13/- whereas the ordinary printing ink stands in at
from 1/- to 2/- or thereabouts.
In consequence of the above it has always been desired to obtain substitutes for
vermilion. For a long time there has been employed as such a substitute the
baryta lake of a certain sulphonised azo-coloring matter that was fast to chromic
acid but had the disadvantage of not being fast either to light, to washing or
to soap.
A further process for producing a fast red on indigo consists in printing on
oxidising alumina mordants, such as chlorate or bromate of alumina, steaming and,
after fixing, dyeing with alizarine. This process however is a complicated and
expensive one and moreover the red obtained has not the desired scarlet tint of
vermilion.
My foreign correspondents have discovered a process giving satisfactory results
in every respect, in utilising in place of the mineral acids or their substitutes

page_text: usually employed, the insoluble azo-coloring matters, which were heretofore only
developed on the fibre, as body-colors in the form of powders or pastes.
On white stuffs they are fixed just like the ordinary albumen colors, such as
ultramarine &c., and on indigo blue stuffs according to the process mentioned
above, such as it is used for example for vermilion.
In this process the albumen and also the oxidising agent may be replaced by any
other suitable body and moreover when white grounds are used, the coloring
matters may be dissolved in alcohol and the printing color which must of course
not contain albumen be admixed with mordants, Turkey red oil &c.
The result obtained is an excellent one in particular in printing indigo blue
stuffs. The shades obtained are extraordinarily brilliant orange reds, reds and also
claret reds; they are fast to water, washing and light and are much lower in price
than vermilion; they do not suffer from the disadvantage of precipitating from the
printing color and adhering to the engraved surfaces and moreover they are by far
finer than the shades from vermilion.
EXAMPLE.
100 parts by weight of dry lake from para-nitraniline and beta-naphthol
" gum-water
400
water
"
"
"
".
80
"
"
"
140
"
"
"
70
"
"
"
,, neutral chromate of soda
دو
albumen-water (1:1)
are well ground up and printed on the fabric.
After being dried, the fabric is taken for 20 seconds through a bath of 60° C.
containing per gallon about 7-0 ozs. of sulphuric acid of 66° Bé. and 70 ozs. of
oxalic acid; the fabric is then well washed and dried.
Dated this 21st day of November 1892.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Application of Nonsulphonated Azo-coloring Matters Insoluble in
Water as Body-colors and in Substitution for Mineral Colors
for Printing on Textile Fabrics.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, in the County of London,
Chartered Patent Agent, do hereby declare the nature of this invention and in
what manner the same is to be performed to be particularly described and
ascertained in and by the following statement :-
The development of insoluble azo coloring matters, fast to light and washing,
on cotton stuffs by previously impregnating the stuffs with alkaline solutions of
phenols and subsequently treating them with the neutralized solution of a diazotised
base, has been taken up to a large extent.
In the Specification to Letters Patent No. 2818 of 1891 it is stated that the
same colors can also be fixed on indigo-dyed stuffs, by treating them first, for
example, with beta-naphthol sodium and afterwards printing them with a thickened
diazo solution, to which some red prussiate of potash has been added; the stuffs
are then passed through an alkaline bath. The shade obtained in this way, for
example, the red from para-nitraniline and beta-naphthol, are of extraordinary
beauty and great fastness, but this process unfortunately has certain inconveniences.
For example, by reason of the very difficult solubility of the ferri-cyanides it is not
possible to incorporate with the printing color a quantity of mordant sufficient to
permit of corroding dark indigo shades and the indigo blue stuff prepared with
beta-naphthol cannot be got white with the usual corroding agents, so that it is
impossible to produce with this process the so much liked combination "blue red
and white."

page_text: It is known that similar inconveniences do not exist when vermilion is mordanted
upon indigo in such manner, that it is fixed by means of albumen under simul-
taneous addition of neutral chromates to the printing color, passing the stuff
through an acid bath at the temperature of coagulation of the albumen, as it is
well known that the indigo is oxidised to soluble isatin at this temperature, and by
this method there is obtained at the same time a good white.
The employment of vermilion has however other inconveniences, caused by its
high price and its high specific gravity. By reason of its weight, the mineral color
sinks into the printing color and deposits in the engraved lines of the printing
rollers, thereby causing unequal printing. A gallon of printing ink made from
pure vermilion costs about 13/- whereas the ordinary printing ink stands in at
from 1 to 2- or thereabouts.
In consequence of the above it has always been desired to obtain substitutes for
vermilion. For a long time there has been employed as such a substitute, the
baryta lake of a certain sulphonised azo coloring matter that was fast to chromic
acid but had the disadvantage of not being fast either to light, to washing or
to soap.
A further process for producing a fast red on indigo consists in printing on
oxidising alumina mordants, such as chlorate or bromate of alumina, steaming and,
after fixing, dyeing with alizarine. This process however is a complicated and
expensive one and moreover the red obtained has not the desired scarlet tint of
vermilion.
My foreign correspondents have discovered a process giving satisfactory results
in every respect, in utilising in place of the mineral acids or their substitutes
usually employed the insoluble azo coloring matters, which were heretofore only
developed on the fibre, as body colors, in the form of powders or pastes.
On white stuffs they are fixed just like the ordinary albumen colors, such as
ultramarine &c., and on indigo blue stuffs according to the process mentioned above,
such as it is used for example for vermilion.
In this process the albumen and also the oxidizing agent may be replaced by any
other suitable body and moreover when white grounds are used, the coloring
matters may be dissolved in alcohol and the printing color which must of course
not contain albumen be admixed with mordants, Turkey red oil &c.
The result obtained is an excellent one in particular in printing indigo blue
stuffs. The shades obtained are extraordinarily brilliant orange reds, reds and also
claret reds, they are fast to water, washing and light and are much lower in price
than vermilion; they do not suffer from the disadvantage of precipitating from the
printing color and adhering to the engraved surfaces and moreover they are by
far finer than the shades from vermilion.

page_text: azo colouring matters insoluble in water applied as body colours in lieu of mineral
colours.
Dated this 21st dow of August 1802
ABEL & IMRAY,
Agents for the Applicant.