IMPROVEMENTS IN THE PRODUCTION AND TREATMENT OF COLORING MATTERS
Year: 1873

page_text: LETTERS PATENT to John Henry Johnson, of 47, Lincoln's Inn Fields,
in the County of Middlesex, Gentleman, for the Invention of
"IMPROVEMENTS IN THE PRODUCTION AND TREATMENT OF COLORING MATTERS."
-
-A communication from abroad by Edward Croissant and Louis
Marie François Bretonnière, both of Paris, in the Republic of
France.
Sealed the 20th June 1873, and dated the 24th April 1873.
PROVISIONAL SPECIFICATION left by the said John Henry Johnson
at the Office of the Commissioners of Patents, with his Petition,
on the 24th April 1873.
I, JOHN HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the
County of Middlesex, Gentleman, do hereby declare the nature of the said
Invention for "IMPROVEMENTS IN THE PRODUCTION AND TREATMENT OF COLORING
MATTERS," a communication to me from abroad by Edward Croissant
and Louis Marie François Bretonnière, both of Paris, in the Republic of
France, to be as follows:-
-
This Invention relates to a mode of obtaining coloring matters soluble
in water suitable for dycing textile fibrous substances of all kinds from

page_text: organic substances not hitherto employed for that purpose by a simple
and economical process, which process is also applicable to the treatment
of known coloring matters with a view to improving the quality of the
coloring matter so treated.
The sources from which the new coloring matters are obtained by the
improved process herein-after described embrace almost all organic
substances, amongst which I may mention more particularly wood saw-
dust of all kinds, humus and vegetable detritus, lichens and mosses,
bran, farina, gluten, starch, fecula, sugar, glucose, cellulose, paper and
cotton waste, tannin, gallic acid, gelatine, caseine, fibrine, albumine,
blood, horn, feathers, excrement of animals, soot, tartaric, citric, and
formic acids, and their alkaline salts; resins, such as galipot; aloes,
guaiacum, dragon's blood; gum resins, such as gum lac; gums, such as
gum tragacanth, gum arabic.
The improved process consists in the direct treatment of the organic
body to be operated upon with alkaline sulphides or poly-sulphides at a
more or less elevated temperature, which may range from 100° centigrade
to say 350°, according to the nature of the substance under treatment
and the tint required, the more elevated the temperature the darker
being the tint obtained.
Amongst the known coloring matters which may be advantageously
treated by the above described process I may mention logwood, Brazil
wood, chestnut, guaiac and sandal wood either as extracts or in powder,
catechu, madder, the waste of powdered madder already boiled, sumac,
and arnotto.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said John Henry Johnson in the Great Seal Patent
Office on the 24th October 1873.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, JOHN
HENRY JOHNSON, of 47, Lincoln's Inn Fields, in the County of 3
Middlesex, Gentleman, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Twenty-fourth day of April, in the year of our
Lord One thousand eight hundred and seventy-three, in the 36th

page_text: year of Her reign, did, for Herself, Her heirs and successors, give.
and grant unto me, the said John Henry Johnson, Her special license
that I, the said John Henry Johnson, my executors, administrators, and
assigns, or such others as I, the said John Henry Johnson, my executors,
administrators, or 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 PRO-
DUCTION AND TREATMENT OF COLORING MATTERS,” a communication to me from
abroad by Edward Croissant and Louis Marie François Bretonnière, both
of Paris, in the Republic of France, upon the condition (amongst others)
that I, the said John Henry Johnson, my executors or administrators,
by an instrument in writing under my hand and seal, 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 John Henry Johnson, 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:-
The said Invention relates to a mode of obtaining coloring matters
soluble in water suitable for dyeing textile fibrous substances of all kinds
from organic substances not hitherto employed for that purpose by a
simple and economical process, which process is also applicable to the
treatment of, known coloring matters with a view to improving the
quality of the coloring matter so treated.
.
The essential principle on which this process is based consists in the
direct treatment of organic bodies by alkaline sulphides and poly-
sulphides with the intervention of heat at temperatures which may vary
from 100° to about 350° centigrade, according to the nature of the
substances to be modified and the tint that it is desired to obtain, and in
their conversion by this treatment into coloring matters. Thus in this
process the organic bodies to be converted into coloring matters are
placed directly, that is to say, without any intermedium and without
preliminary preparation or conversion in contact with the sulphides and

page_text: poly-sulphides in solution, and under the influence of a suitably regulated
temperature they are converted into definite products resulting from
chemical combinations, such products constituting coloring matters, the
tint of which varies according to the conditions of manufacture which
may be determined by the operator.
It is believed that the combination which is developed in this operation
'constitutes an organic sulphide. The products obtained by this process
are in fact the result of a real combination. Thus if wood sawdust for
example be mixed with a solution of sulphide of potash, and the tempe-
rature be raised, it will be observed that sulphuretted hydrogen is 1
abundantly evolved, especially when a temperate of about 300° centigrade
is attained. The alkaline sulphide has therefore become decomposed; a
portion of its sulphur has taken possession of the hydrogen of the
organic body, and the carbon which remains is in a state of particular
combination. The matters thus treated yield coloring substances of 1
very great power, all of which are readily and perfectly soluble in
water.
It should also be observed that the same body is capable of yielding
different tints, according to the degree of temperature, the duration of
the operation, and the proportion of sulphides employed, and it may be 2
stated generally that the higher the temperature and the longer the
duration of the heating process the more nearly does the product
approach a black color and the greater is its solubility.
. Thus the reaction is produced at the simple boiling point with the
extract of cuba or of chestnut for example, and the simple mixture of 2
the liquid sulphide, and these extracts dissolved in water evolve hydrogen,
whilst other substances, such for example as wood sawdust and humus,
require a temperature of 200° centigrade and upwards in order to
produce the reaction.
Among the numerous organic bodies which are converted by this 3
process into coloring matters the following may be mentioned as examples
which have been frequently experimented upon with the same success,
viz., wood sawdust, humus and vegetable detritus, lichens and mosses,
bran, farina, gluten, starch, fecula, sugar, glucose, cellulose, waste paper,
cotton waste and the like, tannin, gallic acid and the like, gelatine, 3
caseine, fibrine, albumen, blood, horn, feathers, as well as animal excre,

page_text: ment, soot, tartaric, citric, formic acids and their alkaline salts; resins,
such as galipot, aloes, guaiacum, and dragon's blood; gum resins, such
as gum lac and the like; gums, such as gum tragacanth, gum arabic,
and the like. In a word the majority if not all organic bodies may be
treated by this process.
It will be understood from the foregoing description, which may be
thus briefly recapitulated, that this process admits of the direct pro-
duction at a cheap rate of an almost unlimited series of entirely new
coloring products, imparting the most varied tints, and that with the aid
of substances widely distributed in nature, and the majority of which are
destitute of any real value in the face of the importance of the result
obtained, the reaction or combination being effected by the simple heating
to the desired temperature of these substances with alkaline sulphides
and poly-sulphides, that is to say, with very common and cheap bodies.
Special attention is directed to this point, which is one of the distinctive
characteristics of this process, that the substances treated are primary
matters, the majority of them inert with regard to the coloring action,
and which taken in this condition and treated directly with alkaline
sulphides or their elements are converted into new definite coloring
products. This process is applicable not only as herein-before described
to the obtaining of new dyeing products resulting from non-coloring
organic bodies, but it also yields coloring substances of great power, all
soluble in water by the treatment of certain substances already employed
in dyeing, and the dyeing properties of which may then be very usefully
modified. Amongst the substances so treated I may mention logwood,
Brazil wood, Cuba wood, chestnut, guaiac, and sandal in powder or as
extracts; catecha, madder, the waste of powdered madder already boiled,
fustet, arnotto, and the like. To these, according to this Invention, new
properties have been imparted by modifying their composition. The
colors furnished by the various substances treated by this process impart
alone or by their mixtures intense black greys of all kinds, violets,
yellows, maroons, and other tints, and when suitably applied and fixed
(by bichromate of potash for example) are for the most part remarkably
fast or permanent under the action of the air, acids, alkalies, and soap.
They may moreover be modified in tone according to the nature of the
mordants employed in order to cause them to adhere to the fibre.
The mode of operation employed in order to carry out the process
which I have herein-before described, and the commercial advantages

page_text: and results of which I have enumerated is most simple, may be carried
out with great facility, and requires but small expenditure to put it
commercially in practice.
The degree of temperature, the duration of the operation, and the
proportions of the matters employed, may as before stated be varied to
an unlimited extent, according to the matters treated and the tints that
it is desired to obtain. In all cases moreover, whatever may be the
matter treated, the essential bases of the process are the same, and its
simplicity admits of its being employed with the greatest facility.
It is not possible to give doses and formula for each of the tints that
may be produced with each of the organic matters which may be con-
verted into coloring products by this process. The operator being aware
as has been stated that the higher the temperature the more nearly does
the tint produced approach a black, or at least a dark color, he will
simply have to vary his proportions and the temperature according to
the result that he desires to obtain.
I may however mention certain results and give some rules which will
serve as a guide, the general method of treatment being the same in all
cases. Thus when but little heat is required to effect the combination,
as is the case of treating aloes for example, the matters are boiled in a
large cast iron pan. If there be thus dissolved for example as a labora-
tory experiment three grammes (say 10th of an ounce) of soccotrine
aloes in ten cubic centimetres (say %ths of a cubic inch) of caustic
soda marking 40°, to which are added ten cubic centimetres (say %ths
of a cubic inch) of water, and if there be added at the simple boiling
temperature three grammes (1/10th of an ounce) of flour of sulphur the
combination is effected immediately. If by means of the product
obtained, which is of a greenish black tint, thread or cotton skeins be
dyed, and the color be then fixed with bichromate of potash, and the
operation finished with boiling carbonate of soda, good lilac greys are
obtained. If the heating be continued to dessication, and even beyond
that, the product no longer yields these greys, but violets and browns,
the tint of which is darker according as the temperature is higher and
more prolonged. When on the contrary the temperature has to be more
elevated in order that the reaction may be produced, and these are the
more numerous cases, especially when wood sawdust, humus, bran, and
the like are to be treated, the substances to be converted are introduced
°

page_text: along with the solution of alkaline sulphide into covered sheet metal
receptacles in order to prevent the ignition of the sulphuretted hydrogen
gas, and such receptacles are placed in a stove, where they are subjected
to dessication at the degree of temperature necessary for the perfect
combination of the elements.
I shall now refer to the proportions necessary to obtain a good brown
tint from oak humus. These proportions are 20 grammes (say 10ths of
an ounce) of oak humus and 20 cubic centimetres (say 2½ cubic inches)
of normal sulphide. This mixture is dessicated in the stove at 210° centi-
grade in order to effect the combination. The normal sulphide which
is employed, and which is previously prepared, is composed of 70 cubic
centimetres. (say 4 cubic inches) of soda marking 40° and 30 grammes
(say 1 ounce) of flour of sulphur, to which are added after combination
65 cubic centimetres, say 4 cubic inches of water. The products
obtained are preserved in boxes from the influences of the atmosphere
and damp.
In recapitulation, whatever may be the proportions for a given organic
substance of the sulphides employed, the mixture being subjected to a
progressive temperature, forms a combination the commencement of
which is shewn by the evolution of sulphuretted hydrogen, and the
matter, the result of the combination produced, constitutes a coloring
product, imparting a tint relatively to the proportion of the matters,
the temperature attained, and the time during which the mixture has
been subjected to that temperature. The same conditions as regards
proportions of the matters and temperature produce always a similar
product, imparting the same tint. The nature, tone, and value of the
tints are therefore in the hands of the operator and at his disposal.
It will have been seen by the foregoing that the combination is
obtained either by first treating the matters with the alkali and then
adding the sulphur, or by treating direct with the alkaline sulphide
itself; it is therefore evident that any other means which in any manner
whatever places the matter to be converted in the presence of sulphur
and an alkali would be covered by this process.
The coloring matters obtained by this process may be applied to the
dyeing of all textile substances. In the case of wool and silk care
should be taken to neutralize the excess of alkali which might be
injurious by any suitable acid, such as acetic acid for example. The

page_text: products dissolved in water may also be precipitated by an acid, such as
sulphuric acid for example, and the precipitate collected, washed, and
re-dissolved for dyeing in a weak ammoniacal solution which could not
injure the animal fibres. Sulphides and poly-sulphides only have been
referred to in this Specification, but it is understood that the congeners
of sulphur, and especially of brome and iodine, may also be employed.
After the description herein-before given it will be seen that this
process admits generally of obtaining with indigenous substances, many
of which are not used and may be had at an insignificant price, as may
be judged of by the list given, new coloring products, which are cheap
and of great power, and the majority of which are fast or permanent;
also that this process admits of a great number of ordinary dyeing
matters being modified by consolidating them in the majority of cases.
Having now described and particularly ascertained the nature of the
said Invention, and the manner in which the same is or may be used or
carried into effect, I would observe in conclusion that what I consider
to be novel and original, and therefore claim as the Invention secured to
me by the herein-before in part recited Letters Patent is,―
First. The herein described, new coloring products obtained in the
manner herein-before specified.
Second. The peculiar process for obtaining new coloring matters as
herein-before described.
Third. The application of this process to the modification of various
dyeing matters as herein-before described.
In witness whereof, I, the said John Henry Johnson, have to this
my Specification set my hand and seal, the Twenty-fourth day
of October One thousand eight hundred and seventy-three.