The Manufacture and Production of New Mordant Dyeing Colouring Matters.
Year: 1895

page_text: Date of Application, 21st Sept., 1895
Complete Specification Left, 19th June, 1896-Accepted, 25th July, 1896
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Mordant Dyeing Colouring
Matters.
1 BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me by the Badische Anilin & Soda Fabrik of Ludwigshafen-on-
Rhine in the Empire of Germany) to be as follows
This invention consists in the manufacture and production of new mordant dyeing
colouring-matters by the suitable oxidation of aromatic hydroxy-carboxylic acids.
The said oxidation may be effected in sulphuric acid solution by the use of a
chemical oxidizing agent, such for example as a persulphate, or it may be effected
by treating the sulphuric acid solution of the hydroxy-carboxylic acid by means of
electricity and at the positive pole of the cell.
The colouring-matters obtained dye chrome-mordanted wool, giving fine strong
yellow shades possessing great fastness against the action of light and of milling.
The following examples will serve to further illustrate the nature of the invention
but it is not limited to the methods, or conditions, described in these examples as
the said methods or conditions, can be varied in many respects; thus, for instance,
the concentration of the sulphuric acid may vary within very wide limits, a higher
temperature may be applied, or a larger quantity of oxidation agent be used and
when an electric current is used, its quantity and tension can be varied. The parts
given in the examples are by weight.
EXAMPLE 1.
OXIDATION OF SYMMETRICAL META-DI-HYDROXY-BENZOIC ACID WITH AMMONIUM
PERSULPHATE.
Dissolve about ten parts of symmetrical meta-di-hydroxy-benzoic acid in about
two hundred parts of cold concentrated sulphuric acid (containing about ninety-five
per cent. H₂SO) and add slowly at the ordinary temperature about fifteen parts of
ammonium persulphate. A rise of temperature above about fifty degrees Centigrade
must be avoided. After mixing is effected continue to stir for say about twelve
hours. The melt assumes a brown-yellow colour. Pour the whole into about one
thousand parts of cold water, and collect on a filter the colouring-matter, which
separates out; wash and preserve for use in the form of paste.
EXAMPLE 2.
OXIDATION OF SYMMETRICAL META-DIHYDROXY-BENZOIO ACID BY MEANS OF
ELECTRICITY.
Suspend about ten parts of symmetrical meta-dihydroxy-benzoic acid in about
forty parts of sulphuric acid (containing about sixty-three per cent. H₂SO).
Place this mixture in an electrolytic cell at the positive pole thereof the negative
pole being surrounded by sulphuric acid, separated from the mixture by a suitable
diaphragm. Keep the mixture cool say at a temperature between ten and twenty
degrees Centigrade; stir thoroughly and pass the electric current through the cell.
[Price 8d.]

page_text: Good results for instance can be obtained by using a current of about eight volts
and twenty ampères per square decimeter of anode surface. Continue the treatment
till no meta-dihydroxy-benzoic acid remains unchanged.
Pour into cold water,
filter and wash.
The product resulting according to both examples is identical, it dyes wool,
mordanted with chrome, or with alumina, fine strong and fast yellow shades. A
fine yellow can also be obtained on cotton with the aid of an alumina mordant.
The colouring matter forms a yellow, to greenish-yellow paste, or in the dry state,
a greenish-yellow powder. It is soluble in, and can be crystallized from, glacial
acetic acid, or from alcohol. It is hardly soluble in water even on boiling.
This invention can be applied to a large number of aromatic hydroxy-carboxylic
acids such as, for instance, salicylic acid, meta-hydroxy-benzoic acid, symmetrical
meta-di-hydroxybenzoic-ethyl-ester, gallic acid, gallic ethyl-ester, tanniu and the
The products obtained possess similar properties to those hereinbefore
like.
described.
Dated this 21st day of Sentember 1805
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Mordant Dyeing Colouring
Matters.
I, BENJAMIN WILLCOX, of 47 Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Badische Anilin and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany) and in what manner the same
is to be performed to be particularly described and ascertained in and by the following
statement :-
This invention consists in the manufacture and production of new mordant dyeing
colouring matters by the suitable oxidation of aromatic hydroxy-carboxylic acids.
The said oxidation may be effected in sulphuric acid solution by the use of a
chemical oxidizing agent, such for example as a persulphate, or it may be effected
by treating the sulphuric acid solution of the hydroxy carboxylic acid by means of
electricity and at the positive pole of the cell.
The colouring matters obtained dye chrome mordanted wool giving fine strong
yellow shades possessing great fastness against the action of light and of milling.
The following examples will serve to illustrate further the nature of the invention
and the manner in which it can be carried into practical effect, but the invention
is not limited to the methods, or conditions, described in these examples as the
said methods or conditions can be varied in many respects; thus for instance in
all cases the concentration of the sulphuric acid may vary within very wide limits,
a bigher temperature may be applied, or a larger quantity of oxidizing agent may
be used and, when an electric current is used, its quantity and tension can be
varied. The parts given in the examples are by weight.
EXAMPLE 1.
OXIDATION OF SYMMETRICAL META-DI-HYDROXY-BENZOIC ACID WITH AMMONIUM
PERSULPHATE.
Dissolve about ten parts of symmetrical meta-di-hydroxy benzoic acid in about
two hundred parts of cold concentrated sulphuric acid (containing about ninety-five
per cent. H₂SO) and add slowly at the ordinary temperature about fifteen parts

page_text: f ammonium persulphate. A rise of temper
Centigrade must be avoided. After mixing is effected continue to stir for say about
Pour the whole into
welve hours. The melt assumes a brown yellow colour.
about one thousand parts of cold water and collect on a filter the colouring matter,
which separates out; wash and preserve for use in the form of paste.
EXAMPLE 2.
OXIDATION OF SYMMETRICAL META-DI-HYDROXY-BENZOIC ACID BY MEANS OF
ELECTRICITY.
Suspend about ten parts of symmetrical meta-di-hydroxy-benzoic acid in about
forty parts of sulphuric acid (containing about sixty-three per cent. H₂SO). Place
this mixture in an electrolytic cell at the positive pole thereof, the negative pole
being surrounded by sulphuric acid, separated from the mixture by a suitable
diaphragm. Keep the mixture cool say at a temperature, between ten and twenty
degrees Centigrade, stir thoroughly and pass the electric current through the cell.
Good results, for instance, can be obtained by using a current of about twenty
ampères per square decimeter of anode surface and about eight volts tension.
Continue the treatment till no meta-di-hydroxy-benzoic-acid, or practically none,
remains unchanged. Pour into cold water, filter and wash.
The product resulting according to both examples is identical; it dyes wool,
mordanted with chrome, or with alumina, fine, strong, and fast, yellow shades.
A fine yellow can also be obtained on cotton with the aid of an alumina mordant.
The colouring-matter forms a yellow to greenish-yellow paste, or, in the dry state,
a greenish-yellow powder. It is soluble in, and can be crystallized from, glacial
acetic acid, or from alcohol. It is hardly soluble in water even on boiling.
This invention can be applied to a large number of aromatic hydroxy-carboxylic
acids such as for instance, salicylic acid, meta- and para-hydroxy-benzoic acid,
cresotic acid, symmetrical meta-dihydroxybenzoic-ethyl-ester, symmetrical meta-
dihydroxy-benzoic-anilide, gallic acid, gallic-ethyl-ester, gallaminic acid, gallanilide,
tannin, protocatechuic acid, beta resorcylic acid, and the like. The products obtained
possess similar properties to those hereinbefore described.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of new mordant-dyeing colouring-matters by subjecting an
aromatic hydroxy-carboxylic acid hereinbefore set forth in sulphuric acid solution
to the action of a chemical oxidizing agent such as a persulphate substantially as
herein before described.
2. The manufacture of new mordant-dyeing colouring-matters by subjecting an
aromatic-hydroxy-carboxylic acid hereinbefore set forth, in sulphuric acid solution
to the action of an electric current at the positive pole of the cell substantially as
hereinbefore described.
3. The manufacture of new mordant dyeing colouring-matters in the manners
described in the foregoing examples.
4. As new articles of manufacture the new mordant-dyeing colouring-matters
5 such as can be obtained substantially as herein before described.
Dated this 8th day of June 1896.
JOHNSONS & WILLCOA,
47 Lincoln's Inn Fields, London, W.C., Agents.