The Manufacture or Production of Polyazo Colouring Matters.
Year: 1896

page_text: Date of Application, 10th July, 1896
Complete Specification Left, 7th Jan., 1897-Accepted, 27th Feb., 1897
[Communicated from abroad by THE CHEMISCHE FABRIK, vormals SANDOZ, oi
Basel, Switzerland, Chemical Manufacturers.]
The Manufacture or Production of Polyazo Colouring Matters.
I, WILLIAM EDWIN HEYS of 70 Market Street Manchester in the County of
Lancaster, Patent Agent, do hereby declare the nature of this invention to be
as follows:-
The azo compounds formed from diazonaphthol-sulphonic acid and metatoluylene-
diamine have alone hitherto been used for the production of poly-azo colouring
matters, as is described in the Specification of the French Brevet d'Invention
No. 243735 granted to the Aktiengesellschaft für Anilinfabrikation of Berlin.
In this specification, it is distinctly stated that the diazo compounds of
paradiamines combine with the toluyl groups, but not with the naphthalene
group.
My foreign correspondents have found however, that if the azo compounds
formed from diazonaphthol-sulphonic acids and a constituent capable of combining
once only, are used, the further combination of such azo-compound with a diazo
group takes place in the naphthalene ring. The best results have been obtained
by using the azo colour produced in acid solution from diazotised, B₁ a, amido-
naphthol B, B-disulphonic acid (Specification of German Letters Patent No. 53023),
and alpha-naphthylamine. If a molecule of a diazotised paradiamine is permitted
to act upon one molecule of this colour, an. intermediate product is obtained, the
composition of which is expressed by the general formula:
N = NCH_NH,
N = N-.
This intermediate product can be further combined with one molecule of a
phenol, amine, amidophenol or their sulphonic or carbonic acids, producing new and
valuable mixed trisazo colouring matters which dye unmordanted cotton in colours
varying from a brown to a deep blue-black.
Instead of combining the herein before described intermediate product directly, it
may be diazotised once more with one molecule of nitrous acid, and the tetrazo
compound thus prepared can be combined with two-either the same or different-
molecules of a diamine, a naphthol-, dioxynaphthalene-, amidonaphthol-sulphonic
or carbonic acid. The octazo colours thus produced are generally of a bluer or
greener tint than the corresponding trisazo colouring matters and dye unmordanted
cotton violet, greenish-blue, and blue-black.

page_text: archer utazotisation and combination on
the fibre, by which process very dark blue to black shades, fast to washing, are
obtained.
The following examples may serve to illustrate the new process:-
EXAMPLE I.
34.1 kilos, of the acid sodium salt of ẞ, a, amidonaphthol B, B-disulphonic acid
are diazotised in the well known manner with 6.9 kilos. of sodium nitrite, and the
diazonaphthol-disulphonic acid, suspended in about 500 litres of water, is combined
with 143 kilos. of alpha-naphthylamine dissolved in 12 kilos. of hydrochloric
acid of 21° Be. and 300 litres of water. The azo colouring matter separates almost
entirely as a brownish-violet powder which after 24 hours is dissolved by the
addition of 8 kilos. of caustic soda. 24 kilos. of sodium carbonate are added to
this solution, and then, at a temperature of about 10° C., there is also added a
solution of tetrazodiphenyl prepared in the well known manner from 18.4 kilos. of
benzidine. An intermediate product separates immediately as a blackish-violet
precipitate, to which there is added a solution containing 23.9 kilos. of gamma-
amidonaphthol sulphonic acid and 4 kilos. of caustic soda in 300 litres of water.
The combination is finished after about 24 hours and the produced colouring matter
is separated by adding salt to the boiling solution. It dyes unmordanted cutton
from a bath containing soda and salt, a deep violet-black.
EXAMPLE II.
If the colouring matter obtained as described in the preceding example from
34.1 kilos. of B, a, amidonaphthol-ß, a-disulphonic acid and 14.3 kilos. of alpha-
naphthylamine is combined in a solution rendered alkaline by carbonate of soda, with
tetrazoditolyl prepared from 21-2 kilos. of tolidine, an intermediate product is
obtained which separates immediately as a violet-black precipitate. This is
acidulated and gradually treated, at a temperature not exceeding 15° C., with an
aqueous solution of 6.9 kilos. of sodium nitrite. The diazotisation is completed
after from 3 to 4 hours, and the brownish-red tetrazo compound is allowed to run
into a solution of 25 kilos. of meta-toluylenediamine rendered alkaline by carbonate
of soda, care being taken to stir well all the time. After 12 hours, the colouring
matter, which separates as a blueish-black powder, is filtered, pressed and dried.
It dyes unmordanted cotton, from a bath rendered alkaline by sodium carbonate,
a violet-black.
EXAMPLE III.
The tetrazo compound obtained as described under Example II, from the
intermediate product after acidulation, by treatment with sodium nitrite, can also
be combined with two different compounds. For this purpose it is, for instance,
after cooling to 5° C., treated with 40 kilos. of sodiuni carbonaté, and then a
solution of 34.1 kilos. of the acid sodium salt of the amidonaphthol-disulphonic
acid H, in 4 kilos. of caustic soda and 400 litres of water is quickly added to it, and
after a few minutes, a solution of 23.9 kilos. of amidonaphthol-sulphonic acid Y, in
4 kilos. of caustic soda and 300 litres of water. Salt is added to the cold blueish-
black solution and the colouring matter is filtered off. The new octazo colouring
matter dyes unmordanted cotton a blueish-black.
Dated this 6th day of July A.D. 1896.
WILLIAM E. HEYS.

page_text: The Manufacture or Production of Polyazo Colouring Matters.
I, WILLIAM EDWIN HEYS of 70 Market Street Manchester in the County of
Lancaster, Patent Agent, do hereby declare the nature of this invention, and
in what manner the same is to be performed, to be particularly described and
ascertained in and by the following statement :-
The azo compounds formed from diazonaphthol sulphonic acid and metatoluylene-
diamine have alone hitherto been used for the production of poly-azo colouring
matters, as is described in the Specification of the French Brevet d'Invention
No. 243735 granted to the Aktiengesellschaft für Anilinfabrikation of Berlin.
In this specification it is distinctly stated that the diazo compounds of
paradiamines combine with the toluyl groups but not with the naphthalene
group.
My foreign correspondents have found however that if the azo compounds
formed from diazonaphthol sulphonic acids and a constituent capable of combining
once only, are used, the further combination of such azo compound with a diazo
group takes place in the naphthalene ring. The best results have been obtained
by using the azo colour produced in acid solution from diazotised beta-alpha-
amidonaphthol-beta,-beta-disulphonic acid (Specification of German Letters
Patent No. 53023), and alpha-naphthylamine. If a molecule of a diazotised
paradiamine is permitted to act upon one molecule of this colour, an intermediate
product is obtained the composition of which is expressed by the general
formula:-

page_text: one molecule of the simple azo colour obtained in acid solution from diazotised
beta,-alpha-amidonaphthol beta,-betas-disulphonic acid and alpha-naphthylamine,
with one molecule of the tetrazo compound of a paradiamine, in acidulating and
diazotising this intermediate product and combining it with two (either the same
or different) molecules of a meta-diamine, phenol, amidophenol, or their sulphoniq
or carbonic acid compounds, substantially as set forth.
3. As new substances, the new poly-azo colouring matters produced by the
process claimed by the first claim, substantially as hereinbefore described.
4. As new substances, the new poly-azo colouring matters produced by the
process claimed by the second claim, substantially as hereinbefore described.
Dated this 5th day of January A.D. 1897.
WILLIAM E. HEYS.