Improvements in the Treatment and Preparation of Naphthazarine (Dioxynapthaquinone) and the Production of a Soluble Derivative thereof and the Application of the same in Dyeing and Printing.
Year: 1887

page_text: Date of Application, 28th May, 1887
Complete Left, 20th Feb., 1888
Complete Accepted, 29th Mar., 1888
Improvements in the Treatment and Preparation of Naphthazarine
(Dioxynapthaquinone) and the Production of a Soluble
Derivative thereof and the Application of the same in Dyeing
and Printing.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been communi-
cated to me from abroad by The Badische Anilin and Soda Fabrik of Ludwigshafen
on-the-Rhine in the Empire of Germany to be as follows:-
Naphthazarine (Dioxynaphthaquinone) the coloring matter discovered by Roussin
in 1861 and originally described by him under the name of "artificial Alizarine"
(Chemical News, Vol. III. 329) has hitherto yielded only sombre shades unfitted for
practical application in the arts [Watts Dict. Chem. Vol. IV. 16] and notwithstanding
the process of soaping [Calvert dyeing and Calico printing, ed. Stenhouse & Groves
p. 55.] and superseded by ordinary dyewoods from which the shades could be produced
at a much cheaper rate, and of the same degree of fastness as regards the action of
light and air.
My foreign Correspondents have ascertained that the want of success in these
experimental trials with Naphthazarine have been partly owing to the insolubility of
the colouring matter in water and partly to the fact that no appropriate mordants
had been employed by former investigators, and this invention relates to the conversion
of Naphthazarine into a new soluble derivative and to the application of the hitherto
unknown chromium-compounds or chrome-lakes of Naphthazarine to dyeing and
printing.
The said chrome-lakes of Naphthazarine if produced within or upon the textile fibre
are chiefly distinguished by their valuable coloring properties, their shades varying
from an intense black to a most delicate grey or slate colour and resisting remarkably
well the action of light air, soap and acids. They can also be associated with the
chrome-lakes of other fast coloring matters and are therefore particularly serviceable
for shading or saddening the dyes produced by the corresponding employment of
I will first describe the manner
alizarine, alizarine blue coeruleine and the like.
in which the chrome-lakes of naphthazarine may be produced within or upon animal
гр
"

page_text: fibre. For this purpose naphthazarine is employed by preference in the state of a
paste containing about ten per cent. of the dry colouring matter and the dyeing is
effected with the aid of the ordinary chrome mordants such for instance as chrome-
alum, or the goods to be dyed are first prepared or mordanted by a treatment with
bichromate of potash and acids and afterwards dyed in a separato bath with
naphthazarine.
As an example of the manner in which a fast and deep black may be produced upon
woollen goods I give the following:
About one hundred pounds of well washed and cleansed wool, either in the state of
loose wool or of woollen yarn or cloth are hoiled during one and a half hours with
about three pounds of bichromate of potash and two and a half pounds of bitartrate
of potash. The wool is then well rinsed and washed and placed in a cold dye-bath
containing about forty pounds of a naphthazarine-paste of the above named strength
[equal to four pounds of dry naphthazarine] In order to neutralize the carbonate of lime
contained in the water about one part by measure of acetic acid of 1043 spec. gravity
(or correspondingly more in the case of a very calcareous water) is added to every
thousand parts by measure of the water used in dyeing. The temperature of the
dye-bath is then gradually raised to the boiling point and is maintained thereat for say
from two to three hours.
In the same manner grey or slate shades are obtained by employing proportionately
smaller amounts of naphthazarine.
Whilst in the described manner satisfactory results are obtained in the dyeing of
animal fibre the known insoluble naphthazarine cannot be conveniently employed for
producing fast and bright colours upon vegetable fibre, and more especially they
cannot be conveniently employed for printing upon cotton goods previously prepared
with the so-called Turkey-red oil, a preparation now frequently used by Calico printers.
In order to obviate this defect, which as my Foreign Correspondents have discovered,
is owing to the insolubility of naphthazarine, this colouring matter has to be employed
in the condition of its before mentioned new soluble derivative, the preparation of
which I shall now proceed to describe by way of an example.
About one hundred parts by weight of a paste containing 20 per cent. of dry
naphthazarine are intimately mixed with 35 parts by weight of a solution of bisulphite
of soda, gauging from thirty eight to forty degrees of Beame's scale or possessing a
specific gravity of from 1.357 to 1.383.
This mixture is then digested in closed vessels at a temperature ranging say from
about fifty to seventy degrees centigrade until the colouring matter has been rendered
soluble in water or nearly so which will usually be in about eight days. The
product thus obtained is then ready for use. I will hereafter term it "soluble
naphthazarine."
In order to prepare the said soluble naphthazarine in the mercantile form of a dry
powder, its aqueous solution is either evaporated to dryness, or it is saturated with
common salt, whereby a precipitate is formed which is then collected upon a filter,
pressed and dried.
An analogous result is obtained by the employment of equivalent proportions of the
bisulphites of potash or ammonia in place of the above named bisulphite of soda.
The neutral sulphites of the alkali-metals likewise effect a similar conversion of
naphthazarine into its soluble derivative.
The soluble naphthazarine" obtained in the manner described, presents the
following characteristic properties.
In the dry state it has the appearance of a dark brown powder, which is readily
soluble both in cold and hot water, and which can thus be distinguished from the
original insoluble Naphthazarine. Its aqueous solutions possess a brown colour and
exhibit a strong blueish green fluorescence.
The said new compound is furthermore characterised by its extreme stability in the
presence of acids, whilst caustic or carbonated alkalies most readily effect its decom-
position, naphthazarine being thus regenerated. The aqueous solutions of "soluble
Naphthazarine resist even the action of boiling strong hydrochloric acid or of

page_text: COMPLETE SPECIFICATION.
Improvements in the Treatment and Preparation of Naphthazarine
(Dioxynaphthaquinone) and the Production of a Soluble
Derivative thereof and the Application of the same in Dyeing
and Printing.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex,
Gentleman do hereby declare the nature of this Invention which has been com-
municated to me from abroad by the Badische Anilin & Soda Fabrik of Ludwigshafen-
on-the-Rhine in the Empire of Germany and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
11
Naphthazarine (Dioxynaphthaquinone) the colouring matter discovered by Roussin
in 1861 and originally described by him under the name of "artificial Alizarine'
(Chemical News, Vol. III., 329.) has hitherto yielded. only sombre shades unfitted for
practical application in the arts (Watts' Dict. Chem. Vol. IV, 16) and notwith-
standing the process of soaping (Calvert, Dyeing & Calico-Printing, ed. Stenhouse
& Groves p. 55) and superseded by ordinary dyewoods, from which the shades could
be produced at a much cheaper rate and of the same degree of fastness as regards
the action of light and air.
My foreign correspondents have ascertained, that the want of success in these experi-
mental trials with Naphthazarine has been partly owing to the insolubility of the colouring
matter in water and partly to the fact, that no appropriate mordants had been employed
by former investigators, and this Invention relates to the conversion of Naphthazarine
into a new soluble derivative and to the application of the hitherto unknown chromium-
compounds or chrome-lakes of Naphthazarine to Dyeing and Printing.
The said chromium-compounds or chrome-lakes of Naphthazarine, if produced
within or upon the textile fibre, are chiefly distinguished by their valuable colouring
properties, their shades varying from an intense black to a most delicate grey or slate
colour and resisting remarkably well the action of light, air, soap and acids. They
can also be associated with the chromium-compounds or chrome-lakes of other fast
colouring matters, and are therefore particularly serviceable for shading or saddening
the dyes produced by the corresponding employment of alizarine, alizarineblue,
coeruleine and the like.
I will first describe the manner, in which the chromium-compounds or chrome-lakes
of naphthazarine may be produced within or upon animal fibre. For this purpose
naphthazarine is employed, by preference in the state of a paste or pulp containing
about ten per cent. of the dry colouring matter, (and ninety per cent. of water), and
the dyeing is effected with the aid of the ordinary chrome-mordants, such for instance
as chrome-alum, or the goods to be dyed are first prepared or mordanted say by a
treatment with bichromate of potash and acids, and afterwards dyed in a separate
bath with naphthazarine.
As an example of the manner in which a fast and deep black may be produced
upon woollen goods I give the following
]
One hundred parts by weight of well washed and cleansed wool, (either in its loose
or in its spun, woven or felted state) are taken and boiled for one hour and a half
with the requisite amount of water, to which previously about three parts by weight

page_text: of bichromate of potash and about two and a half parts by weight of bitartrate of
potash have been added.
In order to
The wool, which has thus fixed the chromium-mordant, is then well washed and
placed in a dye-bath containing the requisite amount of cold water in which are
suspended about forty parts by weight of a naphthazarine-paste of the above named
strength (equal to about four parts by weight of dry naphthazarine).
neutralize the carbonate of lime usually contained in the water about one part by
weight of acetic acid of about 1.043 spec. gravity, (or correspondingly more in the
case of a water possessing an unusual degree of hardness) is added to every thousand
parts by weight of the water used in dyeing. The temperature of the dye-bath is
then gradually raised to the boiling point and is maintained thereat for say from two
to three hours or until the bath has become practically exhausted.
The above-described mordanting process can he varied by the application of other
known chromium-mordants, such for instance as chrome-alum or bichromates of
potash or soda in combination with sulphuric, tartaric or oxalic acids, and as before-
mentioned the production of the chromium-lakes of naphthazarine within or upon
the animal fibre may also be effected in one operation by dyeing in a bath containing
naphthazarine jointly with the adequate amount of a chromium-mordant, but I
generally prefer to operate substantially in the manner described in the above
example.
In a similar manner grey or slate shades are obtained by employing proportionately
smaller amounts of naphthazarine in dyeing.
Whilst in the manner hereinbefore described satisfactory results are obtained in the
dyeing of animal fibre, the known insoluble naphthazarine, cannot be conveniently
employed for producing fast and bright colours upon vegetable fibre, and more
especially unsatisfactory results are obtained with the employment of the said insoluble
naphthazarine in the printing of cotton goods previously prepared with the so-called
"Turkey-red oil," a preparation now frequently used by calico printers. In order to
obviate this defect, which as my foreign correspondents have discovered-is owing
to the insolubility of naphthazarine, this colouring matter has to be employed in the
condition of its before-mentioned new soluble derivative, the preparation of which I
shall now proceed to describe by way of an example.
About one hundred parts by weight of a paste containing twenty per cent. of dry
naphthazarine are intimately mixed with about thirty five parts by weight of a solution
of bisulphite of soda, gauging from thirty eight to forty degrees of Beaume's scale
(or possessing a specific gravity of from 1357 to 1.383.)"
This mixture is then digested in closed vessels at a temperature ranging say from
about fifty to seventy degrees Centigrade until the colouring matter has been rendered
soluble in water or nearly so, which will usually be in about eight days. By operating
at a more elevated temperature the duration of the process may however be considerably
shortened. For instance, by digesting the above mixture at about one hundred
degrees Centigrade the desired conversion of the insoluble Naphthazarine into its new
soluble derivative will be arrived at in about half a days time.
The product obtained in the before described manner may then without any further
preparation be employed for its principal industrial purposes. It shall hereafter be
termed "Soluble Naphthazarine."
:
In order to prepare the said soluble naphthazarine in the mercantile form of a dry
powder, its aqueous solution is either evaporated to dryness, or it is saturated with
common salt, whereby a precipitate is formed, which is then collected upon a filter,
pressed and dried.
An analogous result is obtained by the employment of equivalent proportions of
the bisulphites of potash or ammonia in place of the above named bisulphite of soda.
The neutral sulphites of the alkali-metals likewise effect a similar conversion of
Naphthazarine into its soluble derivative.
The soluble Naphthazarine,” obtained in the manner described, presents the
following characteristic properties :
In the dry state it has the appearance of a dark brown powder, which is readily

page_text: soluble both in cold and hot water, and which can thus be distinguished from the
original insoluble Naphthazarine. Íts aqueous solutions possess a brown colour and
exhibit a strong blueish-green fluorescence.
"
The said new compound is furthermore characterised by its extreme stability in the
presence of acids, whilst caustic or carbonated alkalies most readily effect its decom-
position, naphthazarine being thus regenerated. The aqueous solutions of "soluble
Naphthazarine resist even the action of boiling strong hydrochloric acid or of
moderately diluted sulphuric acid, whereas the addition of caustic soda in sufficient
excess to render the solutions alkaline rapidly, and even in the cold, develops a green
colour, which quickly changes into the blue colour of alkaline naphthazarinates.
Acids will then throw down naphthazarine. The same changes take place, if a
solution of "soluble naphthazarine" be boiled with an excess of carbonate of soda.
The aqueous solution of "soluble naphthazarine" can be mixed with acetate of
chrome or with analogous metallic mordants, without suffering any decomposition,
but upon impregnating cotton or similar vegetable fibre with such mixture and
steaming the same, naphthazarine will become fixed within the fibre in combination
with the metallic base.
Upon the last named property of "soluble naphthazarine" is based its application
to the production of the before described fast chrome-lakes of naphthazarine in the
printing of vegetable fibres, as is illustrated by the following examples:
I. BLACK PRINTING COLOUR.
Dissolve eighty parts by weight of dry "soluble Naphthazarine," (prepared as
above described, by treating naphthazarino with a solution of bisulphite of soda and
precipitating the solution thus obtained by common salt,) in a mixture of fifty parts
by weight of acetate of chrome solution of 1.162 specific gravity and fifty parts by
weight of acetic acid of 1.043 specific gravity, and then add eight hundred and
twenty parts by weight of starch thickening.
II. GREY OR SLATE PRINTING COLOUR.
Reduce two parts by weight of the above Black Printing Colour by eight parts by
weight of Starch-thickening.
The above Black and Groy or Slate Printing Colours are printed as usual, steamed
during from one to two hours at a pressure of about an atmosphere, washed and
soaped well.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, declare that what I
claim is :-
1. The herein before described improved application of Naphthazarine (Dioxy-
naphthaquinone) to the production of fast and useful colours in the printing and
dyeing of animal and vegetable fibres by the production of the chromium-compounds
or chrome-lakes of naphthazarine within or upon the fibre, to be dyed or printed, by
means of chromium-mordants and of either naphthazarine or of "soluble naph-
thazarine," whether the mordant and dye be applied together or separately all
substantially in the manner hereinbefore described.
2. The production and use of a derivative of naphthazarine soluble in water and
hereinbefore termed "soluble naphthazarine " by treating naphthazarine with sulphites