IMPROVEMENTS IN THE PREPARATION OF PRODUCTS OF ANILINE AND MATTERS FROM WHICH ANILINE IS OR MAY BE DERIVED, SUITABLE TO BE USED IN DYEING AND PRINTING, AND IN THE PREPARATION OF COLOURING MATTERS."
Year: 1874

page_text: LETTERS PATENT to John Casthelaz, of Crumpsall Vale Chemical
Works, near Manchester, in the County of Lancaster, Manu-
facturing Chemist, for the Invention of "IMPROVEMENTS IN THE
PREPARATION OF PRODUCTS OF ANILINE AND MATTERS FROM WHICH ANILINE IS
OR MAY BE DERIVED, SUITABLE TO BE USED IN DYEING AND PRINTING, AND IN
THE PREPARATION OF COLOURING MATTERS."
PROVISIONAL SPECIFICATION left by the said Jolin Casthelaz at the
Office of the Commissioners of Patents, with his Petition, on the
10th June 1874.
I, JOHN CASTHELAZ, of Crumpsall Vale Chemical Works, near Man-
chester, in the County of Lancaster, Manufacturing Chemist, do
hereby declare the nature of the said Invention for "IMPROVEMENTS IN
THE PREPARATION OF PRODUCTS OF ANILINE AND MATTERS FROM WHICH ANILINE IS
OB MAY BE DERIVED, SUITABLE TO BE USED IN DYEING AND PRINTING, AND IN THE
PREPARATION OF COLOURING MATTERS," to be as follows:-..
The principal object of my said Invention is to obtain aniline blacks

page_text: and aniline products for dyeing black, and to this end I in the first place
dissolve aniline in an excess of sulphuric acid, and I add to the solution
bi-chromate of potash or other oxydising agent.
"
In some cases the rise in temperature is sufficient to effect the object
of my Invention, but it will generally be advisable or necessary to main-
tain the mixture at a temperature, say for example, of one hundred to
one hundred and fifty degrees centigrade," until the oxidation is com-
pleted, the temperature suitable in each case varying according to the
selection of reagents and the proportions of the ingredients. Tho
resultant product of this operation I consider to be an entirely new
substance, and may serve as a basis from which other useful products or
colouring matters may be derived. From this crude product the useful
colouring matter may be extracted by dissolving the said product in
water, alcohol, methylene, or other suitable solvent, and by separating
the impurities or foreign matters from the said solution by filtration,
precipitation, or crystallisation, or by two or more of these operations,
the said soluble product or colouring matter when suitably neutralised
and employed as a dye bath will impart to animal matters or materials
brown or maroon tints more or less dark in shade.
To obtain a black colour matters so dyed are immersed in a solution,
of bi-chromate of potash or chromic acid, or in an ammoniacal solution
of copper or of an analogous metal, or of salts of copper, chrome, or
mercury, followed by an alkaline bath. This method of obtaining a
black colour I consider to be an important feature in my Invention.
Other substances than those enumerated above may be found to be
suitable to be used in effecting the change of the dyed matters to a
black colour. The said product or colouring matter may be employed
in the production of black in the dyeing of tissues or materials which
have been mordanted with bi-chromate of potash in the usual or in a
suitable manner, or with other mordants which may be found to be
suitable, or the mordant selected may be applied along with the said
product or colouring matter.
When an acid aqueous solution of the said product is treated with an
oxidising agent, such for example, as bi-chromate or chlorate of potash,
a black precipitate is obtained which is soluble in an alkaline solution,
and is reprecipitated on the addition of acid to the solution so formed.

page_text: By using an excess of oxydising agent in the manufacture of the product
a black product is obtained, which may be employed in some cases in
dycing and colouring.
Oxydising agents other than those herein-before mentioned may be
employed, as for example, chromic acid, chlorate of potash, bi-oxyde of
manganese, nitro-benzine, azoxyde-benzide, or other product of the
incomplete reduction of nitro-benzine, nitro-phenil sulphurous acid,
nitro-phenil, sulphuric acid, nitro-phenic acid, emeraldine, or other
insoluble aniline blacks. I also obtain a product having the same
tinctorial properties as the product herein-before referred to by treating
nitro-benzine with a reducing agent, such for example, as powdered zinc,
with the aid of concentrated sulphuric acid and heat.
In the second place I obtain a colouring matter capable of dycing
black without the hercin-before mentioned treatment of the goods in an
oxydising bath. I heat the product prepared as herein-aforesaid and
separated from foreign matters, or emeraldine or other aniline black
insoluble in water, with an excess of aniline, and with or without chlor-
hydrate of aniline or other aniline salt, but preferably with such salt.
The operation may be performed at a temperature varying from one
hundred and twenty to two hundred degrees centigrade, the duration of
the operation varying according to the temperature, for instance, with a
temperature of one hundred and seventy degrees centigrade I heat the
mixture during twelve hours. I then remove the excess of aniline by
distillation with the aid of steam or by washings with hydrocarbons or
acidulated water. The resultant will be a black colouring matter soluble
in alcohol, and which may be rendered soluble in water by treatment
with two to ten times its weight of sulphuric acid at temperatures of
thirty to one hundred and twenty degrees centigrade, being rendered
soluble in water or in alkaline solutions, according to the temperature
and the proportion of acid employed.
According to the nature of the alkaloid, as for example, pure aniline,
commercial aniline, or toluidine employed in the preparation of the said
product or colouring matter, or of the said product and colouring matter,
shades of colour varying from black to maroon may be obtained.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said John Casthelaz in the Great Seal Patent Office
on the 9th December 1874.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JOHN
CASTHELAZ, of Crumpsall Vale Chemical Works, near Manchester, in the.
County of Lancaster, Manufacturing Chemist, send greeting.
'
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent bearing date the Tenth day of June, in the year of
our Lord One thousand eight hundred and seventy-four, in the thirty-1
eighth year of Her reign, did, for Herself, Her heirs, and suc-
cessors, give and grant unto me, the said John Casthelaz, Her special
licence that I, the said John Casthelaz, my executors, administrators,
and assigns, or such others as I, the said John Casthelaz, 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
THE PREPARATION OF PRODUCTS OF ANILINE AND MATTERS FROM WHICH ANILINE IS
OR MAY BE DERIVED, SUITABLE TO BE USED IN DYEING AND PRINTING, AND IN THE
PREPARATION OF COLOURING MATTERS," upon the condition (amongst others)
that I, the said John Casthelaz, my executors, or adminisirators,
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 per-
formed, 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 John Castlelaz, do hereby declare
the nature of the said Invention, and in what manner the same is to be a
performed, to be particularly described and ascertained in and by the
following statement, that is to say :-
The principal object of my said Invention is to obtain aniline blacks
and aniline products for dyeing and producing black, and to this end I

page_text: in the first place dissolve aniline in an excess of sulphuric acid and I
add to the solution bi-chromate of potash or other oxydising agent.
In some cases the rise in temperature is sufficient to effect the object
of my Invention, but it will generally be advisable or necessary to main-
tain the mixture at a temperature, say for example, of one hundred to
one hundred and fifty degrees centigrade, until the oxidation is com-
pleted, the temperature suitable in each case varying according to the
selection of reagents and the proportions of the ingredients. As an
example I state that I dissolve one hundred parts of aniline in three
hundred to six hundred parts of sulphuric acid of a gravity indicated
by sixty-six degrees Baumé, and I add eighty to one hundred and sixty
parts of bi-chromate of potash, stirring the contents of the pan or
vessel in which the operation is conducted whilst the bi-chromate of
potash is being added. I maintain the mixture during three to five
hours at a temperature of about one hundred and ten to one hundred
and twenty degrees "centigrade." The proportion of sulphuric acid in
excess may be greatly varied, and other oxydising agents may be
employed in lieu of bi-chromate of potash if preferred, as for example,
chromic acid, chlorate of potash, bi-oxyde of manganese, nitro-benzine,
azoxyde-benzide, or other product of the incomplete reduction of nitro- .
benzine, nitro-phenil sulfurous acid, nitro-phenil sulphuric acid,
nitro-phenic acid, or emeraldine, or other insoluble aniline black. The
resultant product of this operation I consider to be an entirely new
substance, and may serve as a basis from which other useful products
or colouring matters may be derived. From this crude product the
useful matter may be extracted by dissolving the said product in water,
alcohol, methylene, or other suitable solvent, and by separating the
impuritics or foreign matters from the said solution by filtration, pre-
cipitation, crystallisation, or by two or more of these operations, the
said soluble product or matter when suitably neutralised and employed.
as a dyc bath will impart to animal substances or materials brown or
maroon tints more or less dark in shade.
When substances or materials so dyed are immersed in a solution of"
bi-chromate of potash or chromic acid, or in an ammoniacal solution of
copper, or of salts of copper, chrome, or mercury, and are subsequently
treated with an alkaline bath, the colour of such substances or materials

page_text: is changed to black. This method of obtaining a black colour I con-
sider to be one of the important features in my Invention.
Other agents than those enumerated are or may be found to have the
desired effect in changing the dyed substances or materials to a black
colour, but those I have named include such as I now consider to be the
most suitable. The said product or colouring matter may be employed
in the production of black in the dyeing of tissues or materials which
have been previously mordanted with bi-chromate of potash in the
usual or in a suitable manner, or with other mordants as herein-before
indicated, or which may be found to be suitable, or the mordant selected
may be applied along with the said product or colouring matter, that is
to say, the tissues or materials may be treated with a bath containing
solutions of the product and of bi-chromate of potash, ammoniacal
copper, or other suitable mordant or agent.
When an acid aqueous solution of the said product is treated with an
oxydising agent, such for example, as bi-chromate or chlorate of potash,
a black precipitate is obtained which is soluble in an alkaline solution,
and is reprecipitated on the addition of acid to the solution so formed.
By using an excess of oxydising agent in the manufacture of the
product a black product is obtained which may be employed in some
cases in dyeing and colouring.
In the second place I obtain a colouring matter capable of dyeing.
black without the herein-before mentioned treatment of the goods in an
oxydising bath. I heat the product prepared as herein-aforesaid and
separated from foreign matters and preferably in a dry state, or I heat
emeraldine or other aniline black insoluble in water with an excess of
aniline, and with or without chlorhydrate of aniline or other aniline salt,
but preferably with such salt. The operation may be performed at a
temperature varying, say for example, from one hundred and twenty to
two hundred degrees centigrade, the duration of the operation varying
according to the temperature, as for example, I may take two parts of
the product prepared in accordance with the foregoing instructions and
indications, or two parts of emeraldine, four to eight parts of aniline,
and one to two parts of chlorhydrate of aniline. These proportions are
not necessarily to be adhered to, but are given as an example for the
guidance of the operator. The mixture is heated for a period depending'

page_text: upon the temperature employed, as for example, when employing a tem-
perature of one hundred and seventy degrees centigrade I continue the
operation for a period of about twelve to eighteen hours, that is to say,
until the operator considers the reaction to be completely effected. I.
then remove the excess of aniline by disstillation with the aid of steam
or by washings with hydrocarbon, or with acidulated water, or by other
suitable means. The resultant will be a black colouring matter soluble
in alcohol and in some other solvents. This black colouring matter, or
the alcoholic or other solution which may be prepared from it, may be
employed in the dyeing, staining, or printing of some substances or
materials, or may be otherwise used. The said colouring matter may be
rendered soluble in water or in alkaline solutions by treatment with two
to ten times its weight of concentrated sulphuric acid at temperatures of
thirty to one hundred and twenty degrees "centigrade," being rendered
soluble in water or in alkaline solutions, according to the temperaturo
and proportions of acid employed.
Aniline in its various qualities or conditions, such for example, as pure
aniline, commercial aniline, and toluidine, and also naphitylamine may
be employed in the operations herein-before mentioned. The shades of
colour vary according to the nature of the alkaloid employed in the pre-
paration of the first crude product, and in the preparation of the
emeraldine or other aniline black, and also to some extent, according to
the alkaloid employed in the treatment under the second part of my
Invention. I am thus enabled to obtain different shades of black, such
as jet-black, blue-black, and green-black, and also maroon, and other
shades of colour.
Having now described and indicated the nature of my said Invention
and means whereby the same may be carried into effect, I would in
conclusion have it to be understood that I claim,—
First. The preparation of products resulting from the action of an
oxydising agent upon aniline or other cognate alkaloid with the aid of
an excess of cencentrated sulphuric acid, and with the aid of artificial
heat in all cases wherein such heat may be necessary to the success of
the operation.
Secondly. The preparation of the product resulting from the action
aided by heat of aniline or other cornato alkaloid
either unon the

page_text: product which is the subject of my first claim, or upon emeraldine or
other aniline black soluble in water.
And, Lastly. The employment of the said products in the printing
and dyeing of yarns, cloth tissues, fibrous materials, wool, skins, feathers,
and other substances, matters, and materials, and in the preparation of 5
inks, varnishes, coloured lakes, and other useful matters.
In witness whereof, I, the said John Casthelaz, have hereunto
set my hand and seal, this Seventh day of December, in the year
of our Lord One thousand eight hundred and seventy-four.