THE MANUFACTURE OF MORDANTS AND COLOURING MATTERS FROM GLUCOSIDES, TANNIN AND BITTER PRINCIPLES
Year: 1884

page_text: PROVISIONAL SPECIFICATION,
I, WILLIAM LLOYD WISE, of N° 46 Lincoln's Inn Fields in the County of
Middlesex Consulting Engineer and Patent Agent do hereby declare the nature
of said invention for "THE MANUFACTURE OF MORDANTS AND COLOURING MATTERS
FROM GLUCOSIDES, TANNIN AND BITTER PRINCIPLES" (a communication from Carl
Heinrich Knoop, of Dresden in the Kingdom of Saxony, German Empire) to be as
follows:-
This invention has for its object the production of Mordants and colouring
matters by treating Glucosides (Gly-Koside) Tannin and Bitter principles with
oxidising re-agents and metallic salts (or substances forming metallic salts). These
products have the property of precipitating themselves from weak solutions
without any further interfering action on to vegetable fibre, they can therefore
be employed as fast dyes or as mordants for dyes.
They are prepared in the following manner:-
A
The Glucoside (Glykoside) Tannin or Bitter principle (such as Quercitrin,
Mimo-tannic acid Chestnut-tannic acid, Braziline etc) are first produced in a
sufficiently pure state by known methods from their raw materials or extracts
(such as Quercitron, Catechu, chestnut extract, Brazilian wood extract).
solution of a suitable oxidising re-agent is prepared, the re-agent employed
varying according to the required tint and quality of dye. The re-agents may
consist of Tetrachloride of tin, chlorate of potash, chromate of potash, per-
manganate of potash, nitrate of mercury, chloride of mercury or such acids as
arsenic acid, nitrous acid &c or compatible mixtures of these, as well as with
neutral and acid salts. By varying these mixtures various tints and shades of
colour besides several Mordants can be produced.
The same colour or mordant may also be produced in various ways, by either
using larger quantities of the oxidising re-agent or by mixing smaller quantities of
several oxidisers. By a partial oxidation the product partakes of the character
of a mordant, by a higher oxidation that of a dŷe.

page_text: The two solutions are carefully mixed whilst being kept constantly agitated.
Variation in temperature has but slight influence. Any precipitates are to be
separated and re-dissolved in acids, acid salts, or under certain circumstances
alkalies. The solution is finally neutralized in the usual manner.
The solution so produced can be sold either in this condition or condensed to a 5
paste or dried.
COMPLETE SPECIFICATION.
"
I, WILLIAM LLOYD WISE, of No 46 Lincoln's Inn Fields, in the County of 1
Middlesex, Consulting Engineer and Patent Agent, do hereby declare the nature
of said invention for "THE MANUFACTURE OF MORDANTS AND COLOURING MATTERS
FROM GLUCOSIDES, TANNIN, AND BITTER PRINCIPLES (a communication to me
from abroad by Carl Heinrich Knoop, of Dresden in the Kingdom of Saxony,
German Empire) and in what manner the same is to be performed to be
particularly described and ascertained in and by the following statement :-
This invention relates to the preparation of derivatives from glucosides, tannins
and bitter principles, in the form of colouring matters, and to the utilisation of
such derivatives either as fast colouring matters or simultaneously as colouring
matters and mordants, the object of this invention being to considerably shorten
and simplify the method of dyeing as heretofore employed.
The three intimately connected groups of tannins, glucosides, and bitter principles
have not in the present state of science, been yet definitely determined; These
substances have this in common, that they form homologous compounds with the
chemical agents employed in the manufacture hereinafter described. The higher
the degree of oxidation of the above mentioned derivatives is, the more suitable
they are as colouring matters which can be employed without mordants for dyeing
animal and vegetable fibres, while when these substances have only a low degree of
oxidation, they can be suitably and simultaneously used as colouring matters and
mordants.
It is obvious that, with the immense number of glucosides, tannins, and bitter
principles present in the animal and vegetable kingdoms, and capable of being,
according to the hereinafter described process, converted into colouring matters and
mordants there may, according to the oxidizing, reducing or acid agents employed,
and to the different proportions in weight of the substances used, and also according
to the various temperatures employed in the process, be formed dyes of numerous
shades of colour and various properties.
All these preparations contain a crude material in common, which whether
nitrogenous or not is extracted from different plants or animal products and
belongs to the glucosides tannins or bitter principles. A common feature of the
said preparations is that they are produced by the action of chemicals which either
decompose, with formation of sugar, their crude material (or separate its elements)
and form salts with one part of the products of decomposition or serve as weak or

page_text: strong oxidizing means and more or less oxidize (with abundant formation of
sugar) the said crude material whereby its original nature is entirely or to a great
extent altered, this action taking place mostly with a complex formation of salts.
The properties of these compounds are of the greatest importance in tinctorial
industry.
The said compounds are soluble in water (thus differing from lac and printed
dyes) and are not only precipitated from their solutions by alkaline liquors, but
they separate, whenever spun or woven fabrics composed of animal or vegetable
fibres (especially vegetable) are introduced in the diluted solutions (dye-bath) of
such compounds without the use of mordants being required, and deposit upon
such fabrics (colouring the cellulose) from which they cannot afterwards be removed
either by cold or boiling water.
I will now proceed to describe by way of example, a process of preparation
according to which can be produced the derivatives of glucoside, bitter principle
and tannin in the form of suitable' products for dyeing purposes, these products
forming a fast dye without the employment of mordants or acting simultaneously
as a dye and as a mordant. This example will also shew how many deviations
from the process can be resorted to in order to obtain various shades of colour
without departing from the nature of the said invention.
When it is desired to prepare a direct fast colouring dye of a reddish violet color,
I proceed as follows:-
20 kilos of extract of Brazilian wood are dissolved in boiling water to which is
added a little nitric or hydrochloric acid in order to precipitate the resin; the
braziline which is in solution and rises to the top of the liquor is removed. Then
5 kilogrammes of permanganate of potash are dissolved in water, this solution being
added to that of the braziline under constant and slow agitation.
The resulting precipitate is filtered off and lixiviated; it is then treated with
acids (nitric, hydrochloric, sulphuric or oxalic acids) until dissolved, then it is boiled
if necessary.
After cooling, the liquor is cautiously neutralized with acetate or carbonate of
ammonia. The reddish colouring matter thus obtained would have essentially
different properties and a different appearance if the liquid had not been filtered
from the precipitate, obtained by means of permanganate of potash, and if the
unfiltered mass had been treated as above and then concentrated in a vacuum or in
the open air.
The colouring matter has the consistency of a paste and is then ready for the
market.
The above mentioned difference in the properties of the colouring matters
exhibits itself in their yield, their brightness, their shade, the energy and
regularity of their dyeing power, and their being alterable or unalterable at a
dry heat.
It is not a matter of indifference whether the colouring matter is prepared with
5 kilos of permanganate of potash, with less or more of that substance or partly
with chromate of potash or altogether with the latter or with chlorate of potash
and hausmannite or pyrolusite (manganese ores) or with chrome alum or chrome
acetate and nitrous acid or with one or several of the above or similar substances,
although the chief properties (its chemical action on fibres) of the resulting colouring
matter will in all cases almost be the same.
Generally, the colours are brighter, but not so fast, when they are slightly or not
at all oxidized (or even reduced) and the operations are then limited to the formation
of salts with chromium tin, manganese and the like.
In this case, the colouring matter partakes also of the nature of a mordant in so
far as when it is mixed with aniline colours it fixes the latter upon vegetable
cellulose without requiring the usual mordants. By the introduction or interchange
of other chemical substances such as sulphur, mercury, arsenic, and the like further
bye products may be produced,

page_text: In a similar manner to that above described yellow and greenish colours may be
obtained from frangulin, maclurin, exantic acid, quercitrin, while orange colours will
be produced from curcumin, munjistin, and blueish and grey colours from haema-
toxylin. Further red and violet colours may be obtained from rubiretic acid,
sautalin, haematein, carthamin, and brown colours from catechin, castanin and
the like.
All these colouring matters have the property (not hitherto known) of fixing
themselves directly upon animal or vegetable fibres so that there is no need to
employ several baths in order for instance to fix catechin or quercitrin upon the
fibres.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what
I claim is :-
The treatment of tannin and homologous substances including glucosides and
bitter principles according to the above described processes and the preparation of
derivatives therefrom which, when highly oxidized, will act as colouring matters
for dyeing vegetable and animal fibres without the use of mordants and when they
have a low degree of oxidation or when reduced will act simultaneously as a
colouring matter and as a mordant substantially as described.
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