Method of Producing the Tannin-antimony- and the Chromium- compounds of the Quinoneimide Dyestuffs from their Components- on the Fibre prepared with a Phenol, and on the Fibre not so prepared, in Printing.
Year: 1898

page_text: Date of Application, 11th Mar., 1898
Complete Specification Left, 12th Dec., 1898-Accepted, 28th Jan., 1899
PROVISIONAL SPECIFICATION.
Method of Producing the Tannin-antimony- and the Chromium-
compounds of the Quinoneimide Dyestuffs from their Components-
on the Fibre prepared with a Phenol, and on the Fibre not so
prepared, in Printing.
¸Ï, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention (as communicated to me from abroad by The Farbwerke
vormals Meister Lucius & Brüning, of Hoechst a/Main, in the Empire of Germany,
Chemical Manufacturers,) to be as follows:-
It has been impossible hitherto to produce directly on the naphtholated fibre fine
violet, blue and green insoluble azo-colours, fast to washing and acid.
It was necessary to combine the basic colours with the azo-colours, the cost of
producing the former including the resisting agents, however, being a great deal
higher than that of the latter. This disproportion is felt particularly in countries
having a high duty on dyestuffs, but a low duty on raw or intermediate products
necessary for their production.
My foreign correspondents have found a method by which this evil can be
obviated and which at the same time enables the printing industry, depending as
it does so much on cheap production, to prepare the usual shades on common,
unprepared material in as cheap a manner as possible. My correspondents have
endeavoured, therefore, to produce on the fibre dyestuffs which can be prepared
comparatively easily, and at a temperature which is not higher than that employed
for steaming the printed goods, and are not destroyed by the necessary thickening
or fixing-substances. When combining these dyes with the insoluble azo-colours,
it is important that the time required to develop them by steaming is not longer
than can be endured by the azo-colours without injury...
The formation of the quinoneimide dyestuffs in question is not quite as smooth
and simple as that of the azo-colours, since by-products are formed. These, how-
ever, do not take part in the formation of the dyestuffs and do not give rise to the
production of secondary products influencing the shade, as they are easily soluble
and can be removed by ordinary washing.
The tannin added to the printing colour and used for fixing the basic dyestuffs
forms dyestuffs with some of the related components, but these require far more
time for their production than is required for the reaction of the two chief com-
ponents, and therefore the tannin present is rapidly used up by the quickly formed
dyestuff giving its tannate; thus no secondary reaction takes place.
Colours produced on the fibre by this method are as, a rule finer than the shades
obtained from the purest colours on the market and this is probably due also to the
fact that the tannate produced during the formation of the dye has no time to act
upon the by-products. As is known, the dyestuff itself is formed in an acid solu-
tion and in preparing the bodies acetic acid is used. This acid can also be used
in the present case, but requires quick work, and, as it is very volatile during the
steaming and varying results are often obtained, it is best to assist the reaction by
adding non-volatile organic acids or such inorganic acids as do not attack the fibre,

page_text: ABEL & IMRAY,
Agents for the Applicant.

page_text: Method of Producing the Tannin-antimony- and the Chromium-
compounds of the Quinoneimide Dyestuffs from their Components
on the Fibre prepared with a Phenol, and on the Fibre not so.
prepared, in Printing.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the nature
of this invention (as communicated to me from abroad by The Farbwerke vormals
Meister Lucius & Brüning, of Hoechst a/ Main, in the Empire of Germany, Chemical
Manufacturers,) and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-.
It has been impossible hitherto to produce directly on the naptholated fibre-
fine violet, blue and green insoluble azo-colours, fast to washing and acid.
It was necessary to combine the basic colours with the azo-colours, the cost
of producing the former including the resisting agents, however, being a great,
deal higher than that of the latter. This disproportion is felt particularly in
countries having a high duty on dyestuffs, but a low duty on raw or intermediate
products necessary for their production.
My foreign correspondents have found a method by which this evil can be
obviated and which at the same time enables the printing industry, depending
as it does so much on cheap production, to prepare the usual shades. on common
unprepared material in as cheap a manner as possible. My correspondents have
endeavoured, therefore, to produce on the fibre dyestuffs which can be prepared
comparatively easily, and at a temperature which is not higher than that employed
for steaming the printed goods, and are not destroyed by the necessary thickening
or fixing-substances. When combining these dyes with the insoluble azo-colours, it
is important that the time required to develop them by steaming is not longer than
can be endured by the azo-colours without injury.
The formation of the quinoneimide dyestuffs in question is not quite as smooth
and simple as that of the azo-colours, since by-products are formed. These, however,
do not take part in the formation of the dyestuffs and do not give rise to the
production of secondary products influencing the shade, as they are easily soluble
and can be removed by ordinary washing..
The tannin added to the printing colour and used for fixing the basic dyestuffs
forms dyestuffs with some of the related components, but these require far more
time for their production than is required for the reaction of the two chief components,
and therefore the tannin present is rapidly used up by the quickly formed dyestuff,
giving its tannate; thus no secondary reaction takes place.
Colours produced on the fibre by this method are as a. rule finer than the shades
obtained from the purest colours on the market and this is probably due also to the
fact that the tannate produced during the formation of the dye has no time to act
upon the by-products. As is known, the dyestuff itself is formed in an acid solution
and in-preparing the bodies acetic acid is used. This acid can also be used in the
present case, but requires quick work, and, as it is very volatile during the steaming
and varying results are often obtained, it is best to assist the reaction by adding
non-volatile organic acids or such inorganic acids as do not attack the fibre, for
instance boric acid and other solvents as used in calico-printing.
Of the quinoneimide dyestuffs, my correspondents produce on the fibre chiefly
the oxazines and the oxazones as well as the azines-and the azine-dyestuffs alkylated
at the azine-nitrogen (azonium,dyes). They are formed by, letting nitroso-

page_text: compounds of secondary or tertiary aromatic bases or alkylated amidophenols act
on amines, diamines, phenols or oxycarboxylic acids in proportion of 1 molecule to
1 molecule, or by taking instead of nitroso-bodies their reduction products and
oxidising them together with the other components. The latter method, however,
has up till now given few good results for my correspondents' purposes.
The printing colours are prepared by dissolving cold or only mixing the two
bodies, which are to react in organic acids, in the given proportion, then thickening
them with acid-starch thickening and adding tannin or basic chromium acetate
according to the nature of the dye to be formed. Instead of using the isolated
nitroso compound it will also do to prepare it directly sufficiently cold as a con-
centrated solution and to employ the substances in this state for the printing-
colour. In the cold no dyestuff is formed and the printing colour can be kept a
If good
long time if put in a cold room or placed in ice-water in summer.
prints are to be obtained no dyestuff must be formed in the printing colour. The
printing colour is printed in the ordinary way, dried and passed immediately,
without being left to lie about, once or twice through the Mather Platt, then
washed and soaped.
Compared with the printing of ordinary basic dyes this short steaming bas its
great advantages. Besides, very even and smooth prints are obtained, and a
corrosion of the fibre does not take place as is often the case when employing the
ordinary basic dyes on account of the hydrochloric acid they contain-and the long
steaming they require. The colours produced by my correspondents' new method
can be reserved by the well known tannin-tartar emetic resist or by the under-print
oxidation or reduction resists. They can be discharged white by employing
oxidising agents which are printed immediately after drying the printed goods, and
coloured discharges can be obtained by adding to the discharge-colour direct dyeing
colours which withstand the oxidising action, or pigment colours with albumin.
Of the nitroso-compounds my correspondents employ chiefly :-
Nitrosodimethylaniline,
Nitrosodiethylaniline,

page_text: compounds of quinone imide dyestuffs from their components, this method consisting
first in dissolving in acids or mixing with acids the salts of nitroso-compounds of
secondary or tertiary aromatic bases either alone or mixed with amines, phenols,
oxy-carboxylic acids, alkylated amidophenols or dye wood extracts, then in thickening
this solution or mixture in the usual manner; adding according to the nature of the
dye to be formed, tannin or a chromium salt, for instance chromium acetate, then
in printing or padding with the printing or padding colour, thus obtained, in case
it contains only the nitroso-compound, upon webs, warps or yarns prepared with a
phenol such a B-naphthol, or in case it contains mixtures of nitroso-compounds with
amines, phenols &c. upon unprepared webs, warps or yarns, then in drying and
steaming, and finally in passing the tannin colours through an antimony bath
or directly washing and soaping the chromium colours, substantially as described.
Dated this 10th day of December 1898.
ABEL & IMRAY,
Agents for the Applicant.