IMPROVEMENTS IN OBTAINING COLOURING MATTERS FOR DYEING AND PRINTING."
Year: 1864

page_text: LETTERS PATENT to John Dale, of Manchester, in the County of Lancaster,
Manufacturing Chemist, Heinrich Caro, of the same Place, Chemist, and
Carl Alexander Martius, of Warrington, in the said County, Chemist,
for the Invention of "IMPROVEMENTS IN OBTAINING COLOURING MATTERS FOR
DYEING AND PRINTING."
PROVISIONAL SPECIFICATION left by the said John Dale, Heinrich
Caro, and Carl Alexander Martius at the Office of the Commissioners of
Patents, with their Petition, on the 9th November 1864.
We, JOHN DALE, of Manchester, in the County of Lancaster, Manufacturing
Chemist, HEINRICH CARO, of the same Place, Chemist, and CARL ALEXANDER
MARTIUS, of Warrington, in the said County, Chemist, do hereby declare the
nature of the said Invention for "IMPROVEMENTS IN OBTAINING COLOURING
MATTERS FOR DYEING AND PRINTING," to be as follows:-
Our Invention consists, firstly, in the production of a yellow colouring
matter by the action of nitrous acid or its salts upon nitrate of napthylamine,
or upon mixtures of other salts of napthylamine with nitric acid. This yellow
colouring matter (which we call chrysonapthylic acid) possesses acid pro-
perties and is capable of dyeing animal substances without the aid of a
mordant, while vegetable substances may also be dyed with it after having
been "animalized" by any of the well-known methods.

page_text: A method we adopt for carrying out our Invention is as follows:-We take
a cold aqueous solution of nitrate of napthylamine and add to it one equivalent
of nitric acid. This mixture is then diluted with water until a solution of
nitrite of sodium added to a portion of it ceases to produce a precipitate. This
acid and dilute solution of nitrate of napthylamine is afterwards mixed with a
solution of one equivalent of nitrite of sodium and allowed to stand for several
lays, or it is heated to hasten the reaction. In either case the yellow
colouring matter separates on the surface of the mixture, and when no further
formation of the substance takes place it may be obtained in a solid condition
by filtering, washing, and drying.
For dyeing and printing purposes we either employ the yellow acid prepared
as above described or we use salts thereof with ammonia, sodium, or other
metals. Another yellow colouring matter of a more orange tint we produce
by substituting toluidine for napthylamine, the process of manufacture being
in other respects similar, to, that above described.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said John Dale, Heinrich Caro, and Carl Alexander Martius in
the Great Seal Patent Office on the 9th May 1865.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, JoпN
DALE, of Manchester, in the County of Lancaster, Manufacturing Chemist,
HEINRICH CARO, of the same Place, Chemist, and CARL ALEXANDER MARTIUS,
of Warrington, in the said County, Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Ninth day of November, in the year of our Lord
One thousand eight hundred and sixty-four, in the twenty-eighth year of
Her reign, did, for Herself, Her heirs and successors, give and grant unto
us, the said John Dale, Heinrich Caro, and Carl Alexander Martius, Her
special licence that we, the said John Dale, Heinrich Caro, and Carl Alex-
ander. Martius, our executors, administrators, and assigns, or such others as
we, the said John Dale, Heinrich Caro, and Carl Alexander Martius, our
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 for "IMPROVEMENTS IN OBTAINING COLOURING MATTERS
FOR DYEING AND PRINTING," upon the condition (amongst others) that we, the

page_text: said John Dale, Heinrich Caro, and Carl Alexander Martius, by an instrument
in writing under our hands and seals, or under the hand and seal of one of us,
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 Heinrich Caro, 'do hereby declare the
nature of our said Invention, and in what manner the same was to be performed,
to be particularly described and ascertained in and by the following statement,
that is to say:-
Our Invention consists, firstly, in the production of a yellow colouring
matter by the action of nitrous acid or its salts upon nitrate of napthylamine,
or upon mixtures of other salts of napthylamine with nitric acid. This yellow
colouring matter (which we call chrysonapthylic acid) possesses acid pro-
perties and is capable of dyeing animal substances without the aid of a
mordaunt, while vegetable substances may also be dyed with it after having
been "animalized" by any of the well-known methods.
A method we adopt for carrying out our Invention is as follows:--We take
a cold aqueous solution of nitrate of napthylamine, the strength of which is
not important, and add to it one equivalent of nitric acid. This mixture is
then diluted with water until a solution of nitrite of sodium added to a portion
of it ceases to produce.a precipitate. This acid and dilute solution
te
of napthylamine is afterwards mixed with a solution of one equivalent of
nitrite of sodium, or such other quantity of nitrite of sodium that an excess of
alkali added to a portion of the liquid will produce a red precipitate which
does not turn purple on the addition of muriatic acid. The whole is then
slowly heated to about 140° F., when a reaction takes place accompanied by
the evolution of gas.
Another method of carrying our Invention into effect consists in taking a
cold aqueous solution of chloride of napthylamine and adding to it one equi-
valent of muriatic acid and so much water that nitrite of sodium added to a
test portion ceases to produce a precipitate. We then add to this instance a
cold solution of one equivalent of nitrite of sodium, or such other quantity of
nitrite of sodium as will produce the effect mentioned in the description of our
first process. We then add two equivalents of nitric acid, and the whole
is heated as before mentioned. In either case a yellow colouring matter
separates on the surface of the mixture, and when no further formation of the
substance takes place it may be obtained in a solid condition by filtering,
washing, and drying.

page_text: For dyeing and printing purposes we either employ the yellow acid prepared
as above mentioned, or we use salts, thereof with ammonia, sodium, or other
metals. Another yellow colouring matter of. a more orange tint we produce
by substituting toluidine for napthylamine, the processes of manufacture being
in other respects the same as those above described.
Having thus described the nature of our Invention, and the manner, of
carrying the same into effect, I desire it to be understood that we do not limit
ourselves to the precise methods above described or to the quantities men-
tioned, but we claim as secured to us under the above in part recited Letters
Patent,―
Firstly, the production of a colouring matter by the action of nitrous acid
or its salts upon nitrate of napthylamine, or upon other salts of napthylamine
mixed with nitric acid.
Secondly, the production of a colouring matter by substituting toluidine for
the napthylamine mentioned in our first claim.
In witness whereof, I, the said Heinrich Caro, have hereunto set my hand
and seal, this Eighth day of May, in the year of our Lord One
thousand eight hundred and sixty-five.
IAתזוז
ADC