Improvements in the Manufacture, Production, and Application of Colouring Matters.
Year: 1889

page_text: Date of Application, 9th Sept., 1899
Complete Specification Left, 19th June, 1890-Accepted, 2nd Aug. 1890
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture, Production, and Application of
Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this Invention (which has been
communicated to me from abroad by The Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld in the Empire of Germany) to be as follows:-
It has been shown by Erdmann (Annalen der Chemie 247 page 358) that the
1-8 dioxynaphthalene, obtained by melting 1-5 naphthol-sulpho acid, produces
with diazo naphthionic acid in alkaline solution a deep violet turning to a
beautiful cherry-red "on addition of acids," this colouring matter has however but
little value as a dye.
My foreign Correspondent have found that the diazo- compounds of those
amido-azo- bodies which are formed by the action of the diazo- compounds of
aniline, toluidine, xylidine, amido-phenol, amido cresol, alpha or beta naphthylamine-
sulpho acids, benzidine, tolidine, diamido-stilbene sulpho acids upon alpha naphthyl-
amine, form with all the dioxy-naphthalenes, azo colouring matters of great value
varying from violet to dark-blue black. Of these, those prepared from the
1-8 dioxy-naphthalene (Erdmann "Annalen" 247 page 358) and from the beta
beta dioxy naphthalene described by Emmert ("Annalen" 241 page 369) and
obtained from Schaeffer's beta naphthol sulpho acid are distinguished from the
others by their deep black colouring properties, the simplest representative of the
first named series that is to say of the amido azo-bodies being prepared from
sulphanilic acid or para-toluidine-sulpho acid and alpha naphthylamine was first
employed by my foreign Correspondents some years ago in making the azo dyes,
introduced by them into commerce under the name reddish and blueish
"Echtviolett."
Of these colouring matters those which are derived from 1-8 dioxy naphthalene,
are very valuable, possessing as they do the hitherto unknown peculiarity of
forming with salts of chromium, iron or alumina as also with all metallic salts,
lakes capable of withstanding washing and soaping.
The method of producing these colouring matters is to pour the diazo- compounds
of those amido-azo bodies obtained from diazo sulpho acids and alpha naphthyl-
amine into an ice cold solution of the dioxynaphthaline in as little potash or soda
lye as possible with carbonate of soda in excess or the two constituents may be
mixed in acetic acid solution and then warmed.
I give the following as an illustration of my Correspondents method of pro-
cedure.
Colouring matter from alpha diazo naphthalene-azo-benzol disulpho acid and
1-8 dioxy naphthalene. 23-3 kilos of para- amido benzol-disulpho acid (disulph-
anilic acid) are converted into their diazo state in the ordinary way and then
added to a very dilute solution of 20 kilos of alpha naphthylamine in hydro-
chloric acid solution.
To diazotize the amido azo bodies formed the clear deep red coloured fluid is
mixed with a solution of 10 kilos of sodium nitrite in 50 litres of water.
After some hours standing the diazo- compound separates out in bright crystals
which are filtered off and introduced into an ice cold solution of about 26 kilos
of 1-8 dioxy-naphthalene in as little as possible of potash or soda lye with excess
of carbonate of soda.
The colouring matter is formed at once but cannot be separated from the alkaline
solution by saturation or salting out but is obtained in the form probably of an acid

page_text: It is best for printing the nitroso-dioxy-naphthalenes to employ acetate of chromium,
and acetic acid thickening. Then the operator dries, steams (with or without pressure)
and soaps as usual.
The acetates of iron or alumina may be employed instead of acetate of chromium.
Shortly stated the essential features of the present Invention are the manufacture
and production of azo colouring matters from dioxynaphthalenes or their sulpho acids
by the action of the diazo combinations of the amido-azo- compounds obtained from
aniline, toluidine, xylidine, amido-phenol, amido-cresol, alpha or beta naphthylamine,
benzidine, tolidine, diamido-phenyl-tolyl, thio-benzidine (benzidine sulphone), diamido-
stilbene mono- or disulpho acids with alpha naphthylamine or alpha amido naphthol
ethers upon dioxy naphthalenes or their mono- or disulpho acids; the manufacture
and production of nitroso compounds of the dioxy-naphthalenes or their sulpho acids

page_text: by the action of equivalent quantities of nitrous acid or nitrous salts upon the same,
and the employment of the said nitroso-compounds for dyeing and printing by
" 'fixing" them upon fibres in the manner herein before described.
Dated this 9th day of September 1889.
COMPLETE SPECIFICATION.
Improvements in the Manufacture, Production, and Application of
Colouring Matters.
I, BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this Invention which has been
communicated to me from abroad by The Farbenfabriken vormals Friedrich
Bayer & Co. of Elberfeld 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 :-
My Correspondents have found that the dioxynaphthalenes when treated with one
molecular proportion or two molecular proportions of nitrous acid yield nitroso com-
pounds which possess the valuable property of dyeing wool mordanted with metallic
salts a deep dark brown to black colour and when printed on cotton in combination
with metallic salts produce brown to deep black lakes.
"
Of these nitroso compounds that derived from the 1-8 dioxynaphthalene is described
in "Annalen 247 page 358. The action of sodium nitrite and hydrochloric acid
upon this 1-8 dioxynaphthalene produces a yellow flocculent precipitate which is
soluble in soda lye or ammonia producing a bright orange colour. This product and
its production I do not claim as of this present Invention.
If however 1-8 dioxynaphthalene be replaced by other isomeric dioxynaphthalenes,
(which are most readily produced by melting the various naphthalene di-sulphonic
acids or alpha- or beta-naphthol mono-sulphonic acids with alkalies) a series of mono-
or di nitroso compounds of dioxynaphthalene is formed which are distinguished by
their dark shade and their fastness to milling and this especially is the case with those
which have been formed from the beta-beta-dioxynaphthalene obtained by melting the
beta-naphthol-beta mono-sulphonic acids (Schäffer) with caustic potasb.
The following is an example of how the production of these new nitroso compounds
may be performed :-
To a watery solution of ten (10) kilos of dioxynaphthalenes ẞ 1-ẞ 4) dissolved in
diluted alkali and four and a half (4-5) kilos of sodium nitrite cooled with ice, diluted
acetic acid is added till the precipitating dioxynaphthalene is transformed into the
new yellow nitroso compound.
The new compound is salted out filtered and without drying used for dyeing
purposes.
The fixing of these nitroso compounds on fibres is best carried out as follows:-

page_text: It is best for printing the nitroso dioxynaphthalenes to employ acetate of chromium
and acetic acid thickening. The material is then dried, steamed (with or without
pressure) and soaped as usual.
The acetates of iron or alumina may be employed instead of acetate of chromium.
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be performed I declare that what I
claim is―
.1. The manufacture and production of mono- or di-nitroso- derivatives of dioxy-
naphthalenes by the action of nitrous acid or nitrous salts in the presence of acids
upon dioxynaphthalenes or their watery or alkaline solutions, as hereinbefore
explained.
2. As new articles of manufacture products such as are obtained according to the
preceding claim 1.
3. The employment of the nitroso- compounds of dioxynaphthalenes for dyeing and
printing by fixing them upon fibres in the manner hereinbefore described.
Dated this 19th day of June 1890.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.