AN IMPROVED COLORING MATTER, CHIEFLY APPLICABLE FOR DYEING AND PRINTING PURPOSES
Year: 1867

page_text: LETTERS PATENT to Alexander Melville Clark, of 53, Chancery Lane,
in the County of Middlesex, for the Invention of "AN IMPROVED COLORING
MATTER, CHIEFLY APPLICABLE FOR DYEING AND PRINTING PURPOSES," A
communication from abroad by Jean Theodore Coupier, Chemist,, of
29, Boulevart St. Martin, Paris.
Scaled the 16th June 1868, and dated the 24th December 1867.
PROVISIONAL SPECIFICATION left by the said Alexander Melville Clark
at the Office of the Commissioners of Patents, with his Petition, on the
24th December 1867.
I, ALEXANDER MELVILLE CLARK, of 53, Chancery Lane, in the County of
Middlesex, 'do hereby declare the nature of the said Invention for "AN
IMPROVED COLORING MATTER, CHIEFLY APPLICABLE FOR DYEING AND PRINTING
PURPOSES," to be as follows:-
;.
This Invention relates to the preparation of a black coloring matter by the
reaction on a salt of aniline, preferably hydrochlorate of aniline, either of
direct oxidizing agents, such as nitrous products and oxyacids, or indirect such
as chlorine or bromine. The proportions which I consider most suitable for
the production of the improved coloring matter, although I do not bind myself
to those given, are 175 parts of nitrobenzine to 175 parts of aniline, .200
parts of common hydrochloric acid, and 16 parts of iron filings or turnings.
To this may be added two parts of copper for making a perfect black. The
operation is effected in a glazed iron retort or other distilling apparatus, and

page_text: occupies from 6 to 8 hours, the reaction taking place at from 300 to 400
degrees Fahrenheit, according to the nature of the reagent employed. The
operation is complete on the matter thickening sufficiently to be drawn out in
threads, breaking on exposure to the air, the mass presenting a Florentine
bronze aspect. The product is soluble in acids, alcohol, and also in methyl.
The raw matter if dissolved in a strong acid (sulphuric acid, for example)
will serve, after adding water, to form a dye bath for dyeing a blue or violet
black according to the length of the treatment in the dye bath; the black
being deepened by saturating the excess of acid contained in the bath by
means of an alkali or hyposulphite of soda. By aniline I mean the alkaloid
or alkaloids derived from benzine, distilling at from 170 to 180 degrees, and
by nitro-benzine I mean the nitrous product or products derived from the
benzine. By employing less pure products black may also be obtained, but
of a reddish or violet hue.
The Invention thus consists in the preparation of tinctorial products of a
black tint or approaching thereto by means of the above reactions, such pro-
ducts being more especially applicable for dyeing and printing purposes, it
being understood that these reactions are given as examples only of the
principle of the Invention.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Alexander Melville Clark in the Great Seal Patent Office
on the 18th June 1868.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, ALEXANDER
MELVILLE CLARK, of 53, Chancery Lane, in the County of Middlesex, send
greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fourth day of December, in the year of our
Lord One thousand eight hundred and sixty-seven, in the thirty-first year of
Her reign, did, for Herself, Her heirs, and successors, give and grant unto
me, the said Alexander Melville Clark, Her special licence that I, the said
Alexander Melville Clark, my executors, administrators, and assigns, or such
other as I, the said Alexander Melville Clark, my executors, administrators,
and assigns, should at any time agree with, and no others, from time to time
and at all times thereafter during the term therein expressed, should and
lawfully might make, use, exercise, and vend, within the United Kingdom of
Great Britain and Ireland, the Channel Islands, and Isle of Man, an Invention

page_text: for "AN IMPROVED COLORING MATTER, CHIEFLY APPLICABLE FOR DYEING AND
PRINTING PURPOSES," a communication to me from abroad by Jean Theodore
Coupier, Chemist, of 29, Boulevart St. Martin, Paris, upon the condition
(amongst others) that I, the said Alexander Melville Clark, my executors or
administrators, by an instrument in writing under my, or their, or one of their
hands and seals, should particularly describe and ascertain the nature of the
said Invention, and in what manner the same was to be performed, and cause
the same to be filed in the Great Seal Patent Office within six calendar
months next and immediately after the date of the said Letters Patent.
NOW KNOW YE, that I, the said Alexander Melville Clark, do hereby
declare the nature of the said Invention, and in what manner the same is
to be performed, to be particularly described and ascertained in and by the
following statement (that is to say):-
This Invention relates to the preparation of a black coloring matter by the
reaction on a salt of aniline, for example, (preferably hydrochlorate of
aniline), either of direct oxidizing agents, such as nitrous products and
oxyacids, or indirect oxydizing agents, such as chlorine or bromine. The
proportions which I consider most suitable for the production of the improved
coloring matter, although I do not bind myself to those given, are 175 parts
of aniline obtained from benzine, distilling at from 176 to 180 degrees
Fahrenheit, 175 parts of nitro-benzine obtained from benzine, also distilling
at from 176 to 180 degrees Fahrenheit, 200 parts of common hydrochloric
acid, and 16 parts of iron filings or turnings. To this may be added two
parts of copper for making a perfect black. This mixture is heated in an
enamelled cast-iron boiler provided with a distillatory apparatus until the
thick matter assumes the desired tint, either a blue black or violet black.
This is readily ascertained during the course of the operation by withdrawing
small quantities and dissolving them in alcohol or wood spirit. The operation
occupies from 6 to 8 hours, the reaction taking place at from 360 to 380
degrees Fahrenheit, according to the nature of the reagent employed. The
operation is complete on the matter thickening sufficiently to be drawn out
in threads, breaking on exposure to the air, the mass presenting a Florentine
bronze aspect. The product, as above mentioned with reference to the tests,
is soluble in alcohol, and also in methyl. When the operation is terminated
the product is cooled, ground, and dissolved in 5 or 6 parts in weight of sul-
phuric acid at 66 degrees Beaume's areometer. The dissolution is effected in
a heated bath at a boiling temperature, and when complete, which takes
place after heating from 24 to 30 hours, the matter dissolved is precipitated
by means of cold water in the proportion of about ten parts to one of the

page_text: sulphuric solution. The matter is then placed in filters, drained, and again
washed either with hot or cold water until the sulphuric acid is almost
entirely eliminated from the product. The paste thus obtained is slightly
soluble in water, and may be applied direct for dyeing wool and silk by adding
to the dye bath a small quantity of acid or mordant. The same paste is also
applicable for printing in grey or black. A blue or violet black may be pro-
duced from this matter according to the length of the treatment in the
distillatory vessel, the black being deepened if desired by saturating the
excess of acid contained in the bath by means of an alkali or hypo-sulphite
of soda.
The paste obtained in the manner above described may also after the final
washing be digested with two per cent. in weight of caustic soda for twenty-four
hours, care being taken to stir it every hour, in order to effect a mixture and
completely neutralize any sulphuric acid it may still contain. In this manner
the product is rendered more soluble in water, the solution having a red or violet
tint according to the amount of the soda employed. A few drops of strong
acid in the dye bath will immediately restore the tint, and this bath may be
used for dyeing with or without a mordant. By aniline I mean the alkaloid
or alkaloids derived from benzine distilling at from 170 to 180 degrees
Fahrenheit, and by nitro-benzine I mean the nitrous product or products
derived from the benzine. By employing less pure products black may also
be obtained of a reddish or violet hue.
Having described the nature of this Invention, and the manner of per-
forming the same, I declare that what I claim as the Invention to be protected
by the herein-before in part recited Letters Patent is,-
1st. The preparation of tinctorial products of a black color or approaching
thereto by the reaction of a salt of aniline, and an oxidizing agent in presence
of iron and copper, substantially in the manner herein-before described.
2ndly. I claim the application of these products for dyeing and printing
purposes, all as herein-before described.
In witness whereof, I, the said Alexander Melville Clark, have hereunto
set my hand and seal, this Eighteenth day of June, in the year our
Lord One thousand eight hundred and sixty-eight.
A. M. CLARK. (L.S.)