IMPROVEMENTS IN MAKING ANILINE BLACK, AND IN APPLYING IT TO TEXTILE FABRICS AND YARNS
Year: 1868

page_text: LETTERS PATENT to James Higgin, of the City of Manchester, in the
County of Lancaster, Manufacturing Chemist, for the Invention of
"IMPROVEMENTS IN MAKING ANILINE BLACK, AND IN APPLYING IT TO
TEXTILE FABRICS AND YARNS."
Sealed the 22nd January 1869, and dated the 27th July 1868.
PROVISIONAL SPECIFICATION left by the said James Higgin at the
Office of the Commissioners of Patents, with his Petition, on the
27th July 1868.
I, JAMES HIGGIN, of the City of Manchester, in the County of
Lancaster, Manufacturing Chemist, do hereby declare the nature of
the said Invention for "IMPROVEMENTS IN MAKING ANILINE BLACK, AND IN
APPLYING IT TO TEXTILE FABRICS AND YARNS," to be as follows:-
My improvement consists in a new method of producing aniline black
upon textile fabrics and yarns, and more particularly those made of
cotton or linen. I use commercial aniline, which frequently contains an
admixture of toluidine; and the first part of my Invention consists in
making a solution of aniline by mixing it with a solution of a metallic

page_text: salt, such as the chlorides of iron, of tin, or of chromium. In some cases
the metallic base of the salt employed is precipitated and chloride of
aniline remains in solution, and in some cases the metallic base is only
partially precipitated, whilst in others no precipitation takes place and a
compound solution is the result. I can use along with the above-
described aniline solutions the other materials usually employed in
making aniline black, such as chlorate of potash and sulphide or other
copper salt in use for this purpose. Sulphates of the above metals can
be used instead of chlorides, but in this case as sulphate of aniline is
produced some alkaline chloride must be added to the colour.
By the second part of my Invention I use the salt of copper termed
disulphocyanide either in paste or powder. This salt of copper can be
used either to substitute the sulphide of copper usually employed, the
other materials being as at present used; or I make a new black with
one or more of the aniline solutions above described, the disulphocyanide
of copper and chlorate of potash. The treatment after printing in these
blacks may be that usually employed.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said James Higgin in the Great Seal Patent Office on
the 27th January 1869.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JAMES
HIGGIN, of the City of Manchester, in the County of Lancaster, Manu-
facturing Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Twenty-seventh day of July, in the year
of our Lord One thousand eight hundred and sixty-eight, in the thirty-
second year of Her reign, did, for Herself, Her heirs and successors, give
and grant unto me, the said James Higgin, Her special license that I,
the said James Higgin, my executors, administrators, and assigns, or
such others as I, the said James Higgin, 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 for "IMPROVEMENTS IN MAKING ANILINE BLACK,

page_text: the condition
AND IN APPLYING IT TO TEXTILE FABRICS AND YARNS," upon
(amongst others) that I, the said James Higgin, 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 James Higgin, do hereby declare
the nature of my 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) :-
My improvements in producing aniline black upon textile fabrics
consist, firstly, in a new method of making chloride of aniline, which
salt has been found the best for the production of aniline black, being
either used as such in the preparation of the color or formed during the
process of ageing the printed goods by double decomposition. Instead
of combining the aniline with an acid as at present when making aniline
black printing color, I mix it with a solution of a metallic chloride the
base of which is not injurious to the proper oxidation of the aniline. By
this means the aniline combines with the chlorine in definite proportions,
and chloride of aniline free from excess of acid is formed. According
to the metallic chloride used the metallic base is in some cases either
wholly or partially precipitated, and in other cases no precipitation takes
place, a liquid being obtained containing aniline, chlorine, and the metal.
I have found the sesquichlorides of iron and chromium most suitable
for this purpose, and although other chlorides may be used with various
degrees of success I shall only here describe the use of these salts.
When operating with sesquichloride of iron and aniline the proportions
I use are one hundred parts by measure of aniline of commerce, and
according to the saturating power of the aniline, from two hundred and
fifty parts to two hundred and eighty parts by measure of a solution in
water of sesquichloride of iron containing iron equal to twelve grains
of peroxide of iron in one hundred grains measure. When operating
with sesquichloride of chromium I use the following proportions:-One
hundred parts by measure of aniline of commerce, and from four hundred
to four hundred and fifty parts by measure of a solution of sesquichloride
of chromium in water, marking fifty degrees on Twaddell's hydrometer.

page_text: These mixtures may be used in place of the chloride of aniline of com-
merce in the aniline black made with sulphide of copper, using such a
quantity as will contain as much aniline as in the quantity of chloride
of aniline employed; but I prefer to use a compound of copper not
hitherto used in making aniline black, and this forms the second
portion of my Invention. The copper compound I employ is the di-
sulphocyanide, which possesses the advantage of insolubility in dilute
acids, and consequently is not dissolved by the chloride of aniline. It
has further the property of not becoming oxidized in the presence of
chlorate of potash until the color is printed and dried.
A soluble copper
salt in the color when printing is thus avoided. I make the disulpho-
cyanide as follows: I dissolve crystallized sulphate of copper and
crystallized sulphate of iron in water in the proportions of two parts of
the former and three of the latter, and add solution of sulphocyanide of
potassium or other alkaline sulphocyanide as long as a white precipitate
falls. After allowing this to settle I pour off the clear liquid and add
boiling water acidified with muriatic or sulphuric acid, and after well
stirring I allow it to settle and pour off the clear liquor. This process I
repeat until the precipitate has become perfectly white, when I pour
it
on a filter and drain until one gallon of the paste weighs sixteen pounds.
With this paste and either of the aniline preparations named above I
compound aniline black printing colors as follows:-
Number One.-Five and three-quarter pints of water, one and a quarter
pounds starch; boil and add eight ounces chlorate of potash in powder,
cool, and when nearly cold add thirty-three ounces measure of per-
chloride of iron solution (containing in one hundred grains measure iron
equal to twelve grains of peroxide of iron). When quite cold I add
gradually twelve ounces measure of aniline of commerce, and when this is
well mixed I add one and three-quarter ounces of disulphocyanide paste;
mix well and strain through a cloth. This color is then ready for
printing with. If the aniline is of average saturating power there will
be no perchloride of iron in excess.
Number Two. Five pints of water, one pound and a quarter of starch;
beat up the starch with a little of the water, and add one and three-
quarter ounces of disulphocyanide paste, add the rest of the water and
boil. Add when cooling eight ounces chlorate of potash, and when
nearly cold the following solution:-Twelve ounces of aniline of com-
merce, fifty-four ounces by measure of solution of sesquichloride of

page_text: chromium at fifty degrees of Twaddell's hydrometer; heat at one
hundred degrees Fahrenheit until all the aniline has dissolved, mix
well and strain, and it is then ready for printing with. I can also
make a good printing black with the disulphocyanide paste and the
ordinary chloride of aniline of commerce, in which case I proceed
as follows:-
Number Three.-One gallon of water, one and a quarter pounds of
starch; beat up with a little of the water, and add one and three-quarter
ounces of disulphocyanide paste. When this is beaten up add the rest
of the water and boil; when cooling add eight ounces of chlorate of
potash, and when nearly cold sixteen ounces of chloride of aniline of
commerce in crystals or cake; strain through a cloth and the color is
ready for printing.
Having described the method of carrying out my Invention, I do not
confine myself to the exact details herein set down, as they may be
slightly varied without departing from the spirit of my Invention.
I claim as novel in the production of aniline black upon textile fabrics,-
First. The formation of chloride of aniline by the reaction of aniline
upon those metallic chlorides the base of which is not injurious to the
proper oxidation of the aniline, and the use of chloride of aniline so
formed in making a printing color for producing aniline black.
Secondly. The use of the disulphocyanide of copper as an assistant
oxydizer in printing color for producing aniline black.
In witness whereof, I, the said James Higgin, have hereunto set
my hand and seal, this Twenty-sixth day of January, in the
year of our Lord One thousand eight hundred and sixty-nine.
Signed, sealed, and delivered by the
within-named James Higgin, in
the presence of
G. SEPTIMUS HUGHES,
Patent Agent,
JAMES HIGGIN. (L.S.)
Manchester.