The Manufacture and Production of a New Azo Colouring matter. and of Lakes therefrom.
Year: 1899

page_text: Date of Application, 23rd Dec., 1899
aboa shamay
Complete Specification Left, 20th Sept., 1900--Accepted, 10th Nov. 1900 w
PROVISIONAL SPECIFICATION.
PROVISIONAL DIECIFICATION.
The Manufacture and Production of a New Azo Colouring matter.
and of Lakes therefrom.
.. 5
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London, Patent
Agent, do hereby declare the nature of this Invention (which has been communi-
cated to me from abroad by the Badische Anilin & Soda Fabrik, of Ludwigshafen-on-
Rhine, in the German Empire) to be as follows:-
The beta 1 naphthylamine alpha 1. sulpho acid has hitherto found no technical
application. It possesses but slight technical interest for the manufacture of azo
dyes for according to the researches of my Foreign Correspondents, the majority of
the colouring matters prepared by its aid appear to be very similar to the correspond=
ing beta naphthylamine combinations and not to possess any special advantages over
these.
"
They have found however that by combining diazotised beta 1. naphthylamine
alpha 1. sulpho acid with beta naphthol a colouring matter is formed which is
distinguished from the isomeric fast red A (from diazotised alpha 1 naphthylamine
alpha 2. sulphoacid and beta naphthol) by the fact that even in the form of its alkali
salts it is almost insoluble in cold water and but sparingly soluble in hot water.
This want of solubility may perhaps interfere with its extended use for dyeing
textile fabrics, but it is of great importance from the fact that its salts with for
instance calcium, barium, aluminium, zinc, and lead, are still more insoluble, these
remaining practically undissolved even in boiling water. They possess a very:
valuable brilliant blueish-red shade and possess an excellent degree of fastness against
the action of acids and light, and they do not sublime on standing or warming as do
many insoluble azo dyes. They are therefore well adapted for the preparation of
colour lakes either alone or in the presence of a suitable substratum for example,
aluminium, hydroxide, calcium sulphate barium sulphate, or mixtures of these.
To obtain the said metallic lakes the sodium or ammonium salt of the dyestuff may,
be partly dissolved and partly suspended in water and by treatment with a soluble
metallic salt or a metallic hydroxide converted into the desired lake but preferably
the free acid of the colouring matter is employed in the place of the salts.
As a general rule it is desirable that the lakes should be prepared in the presence
of substrata, or simultaneously with the latter.
The following examples will serve to further illustrate the nature of the invention
but the invention is not confined to the examples. The parts are by weight.
EXAMPLE 1.
16
1 NADITHVI ART
AT DITA 1
QUI DUO

page_text: and fifty parts of hydrochloric acid, (containing about thirty per cent. HCl), which
has been diluted with about an equal volume of water. The diazo compound, which
separates out as a sulphur-yellow crystalline precipitate, is filtered on the -pump and
mixed with water into a thin paste. Run this paste, while stirring, into a solution
of one hundred and fifty parts of beta-naphthol in one hundred and twenty parts of
caustic soda lye, (containing thirty five per cent. Na OH), and four hundred parts of
water. Combination takes place almost instantaneously.
When finished boil, filter,
press and dry, or make the press-cake into a paste with boiling water, add hydro-
chloric acid, filter and wash with water, till free from hydrochloric acid and preserve
preferably as paste. The free acid of the colouring-matter which is thus obtained
forms brownish-red crystals with a slight green sheen, and, like the sodium salt, it
dissolves in concentrated sulphuric acid forming a bright red-violet solution and is
almost insoluble in cold water, but it is somewhat more soluble in boiling water than
is the sodium salt.
!
PRODUCTION OF A LAKE SUITABLE FOR EMPLOYMENT IN THE MANUFACTURE OF
COLOURED PAPER.
Dissolve ten parts of aluminium sulphate in one hundred parts of water, add a
quantity of milk of lime corresponding to about two and a half parts of caustic lime,
and two parts of the free dyestuff acid which has previously been mixed to a paste
with a little water, heat to boiling, filter and dry.
Other lakes can be prepared in a similar manner by employing corresponding
quantities of other suitable salts soluble in water, such as lead acetate, zinc sulphate
and the like.
Dated this 3rd day of December 1800

page_text: The Manufacture and Production of a New. Azo Colouring matter
and of Lakes therefrom.
I, BENJAMIN WILLCOX, of 47, Lincoln's Inn Fields, in the County of London,
Patent Agent, do hereby declare the nature of this invention (which has been
communicated to mne from abroad by the Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire) and in what manner the same,
is to be performed to be particularly described and ascertained in and by the
following statement :-
The beta-1-naphthylamine-alpha-1-sulphoacid has hitherto found no technical
application. It possesses but slight technical interest for the manufacture of azo
dyes, for, according to the researches of my foreign correspondents, the majority of
the colouring matters prepared by its aid appear to be very similar to the correspond-
ing beta-naphthylamine combinations, and not to possess any special advantage over
these.
They have found, however, that by combining diazotised beta-1-naphthylamine-
alpha-1-sulphoacid with beta-naphthol a colouring matter is formed, which is
distinguished from the isomeric "Fast Red A," (from diazotised alpha-1-naphthyl-
amine-alpha-2-sulphoacid and beta naphthol) by the fact that, éven in the form of..
its alkali salts, it is almost insoluble in cold water and but sparingly soluble in hot
water.
This want of solubility may perhaps interfere with its extended use for dyeing-
textile fabrics, but it is of great importance from the fact that its salts with, for
instance, calcium, barium, aluminium, zinc and lead are still more insoluble, these.
remaining practic ally undissolved even in boiling water. They possess a very
valuable brilliant blueish-red shade, and also an excellent degree of. fastness against
the action of ac ds and light, and they do not sublime on standing, or on warming, as
do many insoluible azo dyes. They are therefore well adapted, for the preparation of--
colour lakes, either alone, or in the presence of a suitable substratum, for example,
aluminium hydroxide, calcium sulphate barium sulphate or mixtures of these.
To obtain the said metallic lakes the sodium, or ammonium, salt of the dyestuff
may be partly dissolved, and partly suspended, in water, and, by treatment with a
soluble metallic salt, or a metallic hydroxide, converted into the desired lake, but
preferably the free acid of the colouring matter is employed in place of the salts.
As a general rule it is desirable that the lakes should be prepared in the presence
of subtsrata, or simultaneously with the latter.
The following examples will serve to further illustrate the nature of the invention
and the manner in which it can be carried into practical effect but it is not confined.
to these examples. The parts are by weight.
PREPARATION OF AN AZO DYESTUFF FROM BETA-1-NAPHTHYLAMINE-ALPHA-1-
SULPHOACID AND BETA NAPHTHOL.
Dissolve two hundred and twenty-three parts of beta-1-naphthylamine-alpha-1--
sulphoacid in one hundred and twenty parts of caustic soda lye (containing about
5 thirty-five per cent. Na OH), and one thousand parts of water.
Add an aqueous
- solution of sixty-nine parts.of. sodium nitrite and run the mixture into three hundred
and fifty parts of hydrochloric acid (containing about thirty per cent. HCl), which has
been diluted with about an equal volume of water. The diazo compound, which

page_text: separates out as a sulphur-yellow crystalline precipitate, is filtered on the pump, and
mixed with water into a thin paste. Run this paste, whilst stirring, into a solution
of one hundred and fifty parts of beta-naphthol in one hundred and twenty parts of
caustic soda lye (containing thirty-five-per cent. Na OH), and four hundred parts
When finished,
of water. Combination takes place almost instantaneously.
boil, filter, press and dry, or make the press-cake into a paste with
boiling water, add hydrochloric acid, filter, and wash
free from hydrochloric acid, and preserve, preferably as paste. The free acid of
the colouring matter which is thus obtained forms brownish-red crystals with a slight
green sheen, and, like the sodium salt, it dissolves in concentrated sulphuric acid,
forming a bright red-violet-solution, and is almost insoluble in cold, water, but it is
somewhat more soluble in boiling water than is the sodium salt.
with
water, till
PREPARATION OF A BARIUM LAKE WITH BARIUM SULPHATE
SUITABLE FOR LITHOGRAPHIC PURPOSES.
AS A SUBSTRATUM
Heat a mixture of five parts of the free dyestuff acid, (in the form of paste) five
parts of calcined sodium sulphate, and chree hundred parts of water, to boiling, and
add a boiling solution of thirteen and one-fifth parts of crystallised barium-chloride
in one hundred and thirty two parts of water. Filter, wash and dry.
EXAMPLE 4.
PREPARATION
OF A
IN
LAKE SUITABLE FOR EMPLOYMENT
COLOURED PAPER.
THE MANUFACTURE OF
Dissolve ten parts of aluminium sulphate in one hundred parts of water, add a
quantity of milk of lime corresponding to about two and a half parts of caustic lime,
and two parts of the free dyestuff acid, which has previously been mixed to a paste
with a little water; heat to boiling, filter and dry.
Other lakes can be prepared in a similar manner by employing corresponding
quantities of other suitable salts soluble in water such as lead acetate, zinc sulphate,
and the like.
Having now particularly described and ascertained the nature of the said Invention
and in what manner the same is to be performed I declare that what I claim is :-
1. The manufacture of
beta-1-naphthylamine-alpha-1-sulpho-acid-azo-beta-
naphthol, substantially as herein before described.

page_text: 2. As a new article of manufacture the azo dyestuff beta-1-naphthylamine-alpha-
1-sulphoacid-azo-beta-naphthol such as can be obtained substantially as herein before
described.
3. The manufacture of lakes of the azo dyestuff herein before described and clained
by treating the sodium salt thereof with a soluble metallic salt, or metallic hydroxide;
substantially as herein before described.
4. The manufacture of metallic lakes of the aforesaid azo colouring matter herein-
before described and claimed by treating the free acid thereof with a soluble metallic
salt, or a metallic hydroxide; substantially as hereinbefore described.
5. The manufacture of lakes of the aforesaid azo colouring matter in the manner
herein before claimed in the third and fourth claiming clauses and in the presence of
substrata substantially as hereinbefore described.
6. The manufacture of the new azo dyestuff and of lakes therefrom in the manners
herein before described in the several Examples.
7. As new articles of manufacture the new lakes of beta-1-naphthylamine-alpha-1-
sulphoacid-azo-beta-naphthol such as can be obtained substantially as herein before
described.
TAL: onth day of Contember 3000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.