IMPROVEMENTS IN DYEING AND PRINTING TEXTILE FABRICS AND YARNS
Year: 1866

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 DYEING AND PRINTING TEXTILE FABRICS AND YARNS."
PROVISIONAL SPECIFICATION left by the said James Higgin at the
. Office of the Commissioners of Patents, with his Petition, on the 27th
March 1866..
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 DYEING AND PRINTING TEXTILE FABRICS AND YARNS," to
be as follows:-
My improvements consist in a new method of producing black and other
shades from aniline by the use of chromates or chromites of metals along
with other agents. The chromate of copper I have found to be a useful
agent in producing shades from 'grey to black, and I-employ it as follows:-
I add a solution in water of neutral chromate of potash or soda to a solution
in water of a salt of copper, such as sulphate, whereby a precipitate of a
chromate of copper, insolube in water is thrown down; this I filter out, and
dissolve in dilute ammonia forming a green solution; with this I impregnate
the yarn or cloth by padding. or. otherwise, and squeeze out and dry, and as
the ammonia evaporates the chromate of copper remains fixed; or chromate
of copper may be produced on the goods by first padding in the solution of
salt of copper, and subsequently padding or rinsing in the solution of neutral
chromate of potash or soda, then washing and drying. The prepared goods

page_text: are next padded or steeped in a solution of a salt of commercial aniline, by
preference the hydrochlorate, squeezed out and dried, and hung up to age
for a day or two, then rinsed in water, to which may be added an alkali or
alkaline salt, such as hypochlorite of lime or soap. An admixture of chlorate
of potash with the salt of aniline where an intense black is required is ad-
vantageous; or I print a thickened salt of aniline, mixed or not with chlorate
of potash, upon the prepared goods, and after ageing to clear the white ground
I steep or rinse the goods in a solution of an alkali in water, generally using
ammonia, and then wash in water. The strength of the preparation of the
cloth and that of the aniline salt must be proportioned to the shade intended
to be produced.
When it is inconvenient from any cause to prepare goods with the chromate
of copper or other metal, I make such a mixture as will produce the same
result by the gradual reaction of its ingredients; for instance, I make a
chromate of copper by mixing sesquin-chloride of chromium with a salt of
copper, both in solution in water, and add an alkali, filtering the resulting
chromite of copper to a paste or pulp. I take some of this and mix with
it a solution of a salt of aniline, by preference hydrochlorate, and about as
much; chlorate of potash as of salt of aniline; I then pad the goods with this
or I thicken the mixture with gum or any convenient thickening, and print
on the cloth or material, drying and ageing as before until the niaximum
effect is produced, then rinse in water, to which may be added advan-
tageously an alkaline salt or alkali.
Although chromite or chromate of copper has alone been mentioned, other
chromates or chromites may be used to produce various modifications of
SPECIFICATION in pursuance of the conditions. of the Letters. Patent, fileil
by the said James Higgin in the Great Seal Patent Office on the
27th September 1866.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JAMES
'HIGGIN, of the City of Manchester, in the County of Lancaster, Manufac-
turing Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing-date the Twenty-seventh day of March, in the year of our Lord
One thousand eight hundred and sixty-six, in the twenty-ninth 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,

page_text: 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
DYEING AND PRINTING TEXTILE FABRICS AND YARNS," upon the condition
(amongst others) that I, the said James Higgin, my executors or adminis-
trators, 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 per-
formed, to be particularly described and ascertained in and by the following
statement (that is to say) :-
The use of chromic acid and its salts in oxidizing aniline is well known,
and various attempts have been made to make use of this action for the
production of aniline black upon fabrics. Soluble chromates act too rapidly
to be of value for this purpose either when mixed with the aniline salts and
applied to the cloth, or by padding the cloth in a soluble chromate, and after
drying printing on a solution of salt of aniline. I have described a mode of
using a chromate insoluble in water in my Provisional Specification for this
Patent, but as I have since found that the use of insoluble chromato has
been proposed in a Patent taken out previous to the date of this Patent I
make no claim thereto. The use of an insoluble chromate previously fixed
in the cloth is however inconvenient, and of only partial value, inasmuch.as
only few colors can be printed along with the black, and the removing of the
insoluble chromate from the unprinted part is always troublesome. By
printing however with a color so composed of aniline salt and other ingredients
that although there is no chromic acid or chromate present at the time of
printing, by subsequent "ageing' or hanging up for a day or two chromic
acid is developed gradually, all these objections I get rid of, inasmuch as the
chromic acid as fast as it is formed re-acts on the aniline, thereby forming
a dark green color, which on passing through an alkaline solutions becomes
jet black, and is found to be very firmly fixed in the fibre. This gradual
re-action due to chromic acid in a nascent state is what constitutes my
Invention, and the way in which I carry it into effect is as follows:-I make
"

page_text: a mixture of oxide of chromium with one or more oxides of metal, "which are
easily reducible to a lower state of oxidation and are capable of attracting
oxygen easily again. The metals I have found useful for this purpose are
arsenic, iron, and copper, I add this mixture of oxides to a color composed of
hydrochlorate of aniline and chlorate of potash suitably thickened, and print
on cotton fabrics, and after ageing raise in an alkaline solution.' I 'subjoin
the mode of making some of the oxide mixtures which I have found useful.
Paste A., or Arseniate of Chromium.-First, thirty pounds of arsenious acid,!
twenty one pounds and three-quarters of a pound of caustic soda solution at
70° Twaddell, eighty gallons of water; dissolved by boiling.. Secondly, thirty
pounds of bichromate of potash, eighteen pounds of sulphuric acid, specific.
gravity 1-85, eighty gallons of boiling water. Mix Numbers One and Two'
solutions whilst hot, and stir for half an hour; wash the precipitate with hot
water and filter it to a stiff paste.
Paste B., or Arseniate of Chromium.-Thirty pounds of bichromate of potash,
ninety-two pounds of crystallized sulphite of soda, forty pounds of sulphuric
acid, specific gravity 1-85, eighty gallons of boiling water; dissolve and add
a solution of arseniate of soda till all the chromium is precipitated as arseniate,
wash with hot water and filter till it is a stiff paste.
1
Paste C., or Oxide of Chromium and Arseniate of Iron.-Thirty pounds of
bichromate of potash, ninety-two pounds of crystallized sulphite of soda, forty
pounds of sulphuric acid, specific gravity 1.85, eighty gallons of boiling water:
dissolve and add caustic soda solution till all chromium is précipitated as
oxide. In another vessel dissolve sixty pounds of protosulphate of iron in'
eighty gallons of boiling water, and add a solution of arseniate of soda till all s
iron is precipitated as arseniate. Mix the two precipitates together, wash'
with boiling water, and filter to a thick paste.
:
Pasto D., or Chromite of Copper.-Thirty pounds of bichromate of potash,"
ninety-two pounds of crystallized sulphite of soda, forty pounds of sulphuric
acid, specific gravity 1.85, one hundred gallons of hot water; dissolve and
add sixty pounds of crystallized sulphate of copper; dissolve and add caustic
soda solution until all chromium and copper are precipitated; wash with hot
water, and filter to a thick paste.
To make a black color for printing I take seven pints of water, one pint
of any of the pastes B., C., or D., one and a half pounds of starch; beat up
fine and boil well, cool a little, and add four ounces of chlorate of potash;
when nearly cold add one pound of hydrochlorate of aniline of the sort usually
employed for black, dissolve, and strain the color through a fine cloth.
When the paste A. is used, on account of its greater density, only one-half

page_text: the above-named quantity need be taken; for example, seven and a half pints
of water, one half pint of A. paste, and the rest as above.
After printing hang up the pieces in a moderately warm room for two or
three days, or till a dark sombre green is produced, and then pass them
through hot milk and lime or any cheap alkaline liquor. When lead orange
is printed along with the black the raising usual for orange may be employed.
When madder mordants are printed along with the black the ordinary
dunging process to fix the madder colors will raise the black.
Having thus described the way in which I carry out my Invention, I do
not confine myself to the precise details herein set forth, as they may be
modified without departing from the spirit of my Invention; for instance,
variations may be made in the composition of the oxide of chromium
mixtures; or the cloth may be prepared by precipitating similar mixtures
upon it, and afterwards printing on a solution of hydrochlorate of aniline
mixed with chlorate of potash; or the cloth may be prepared with an alkaline
chlorate and a color composed of one of the pastes above named mixed with
hydrochlorate of aniline may be printed upon it. Other salts of aniline may
be also employed, such as the nitrate or the sulphate if mixed with an
alkaline chloride, but these modifications come within the scope of my
Invention, which is the gradual production of chromic acid or its salts by
means of mixtures of oxide of chromium with oxides of arsenic, iron, or copper,
such mixtures being used in conjunction with an alkaline chlorate and a salt:
of aniline to produce aniline black. I therefore claim the mixture of oxide
of chromium and an alkaline chlorate along with the oxides of arsenic, copper
or iron to produce from hydrochlorate or nitrate of aniline a black color upon
cotton fabrics or yarns.
In witness whereof, I, the said James Higgin, have hereunto set my
hand and seal, this Twenty-fifth day of September, in the year of our
Lord One thousand eight hundred and sixty-six.
Signed, sealed, and delivered by
the within-named James Higgin
in the presence of
G. SEPTIMUS HUGHES,
Patent Agent, Manchester.
JAMES HIGGIN. (L.B.)