A Black Cotton Dye-stuff, Combinations of the same, and Processes for the Production thereof.
Year: 1892

page_text: Date of Application, 2nd Mar., 1892
Complete Specification Left, 25th Oct., 1892-Accepted, 7th Jan., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by GUSTAV ADOLF DAHL, of the firm of Dahl and
Company, of Barmen, in the Kingdom of Prussia, Dye-stuff Manufacturers.]
A Black Cotton Dye-stuff, Combinations of the same, and Processes
for the Production thereof.
I ADOLF BANG of Basinghall Street Leeds in the County of York Dye Stuff
Merchant do hereby declare the nature of this invention to be as follows:-
Amongst other disulphonic acids referred to by my communicator in the Specification
of German Letters Patent No. 41957 of 1886, an a-naphtylaminedisulphonic
acid II is described by him, the lime salt of which is readily soluble
in 85% alcohol. In the course of further experiments my communicator has
discovered, that this acid is transformed into a dioxynaphtalinesulphonic acid,
when melted with caustic soda. If this dioxynaphtalinesulphonic acid is heated
with ammonia under pressure, an hitherto unknown B-amido-a-naphtolmonosulphonic
acid is produced. This acid is suitable for the production of a very valuable dye..
stuff. One proceeds as follows:-10.8 kg. (23.8 lbs.) of paraphenylenediamine are
dissolved in 500 litres (110 gallons) of water with the addition of 20 kg. (44 lbs.)
of hydrochloric acid and 20 kg. (44 lbs.) of acetic acid, then cooled with
ice to 3° C. (+ 27° Fht.) and diazotised with 7 kg. (15.4 lbs.) of sodic nitrite.
In this manner only one amido group of the paraphenylenediamine is diazotised.
The paraamidodiazobenzol thus obtained, is now allowed to flow into a solution
of 144 kg. (31-7 lbs.) of a naphtylamine in 12 kg. (26.4 lbs.) of hydrochloric acid
and 200 litres (44 gallons) of water. After several days standing, the paraamido-
benzolazo-a-naphtylamine has formed itself. 40 kg. (88 lbs.) of hydrochloric acid
are added to this, and one again diazotises with a solution of 14 kg. (30.8 lbs.) of
sodic nitrite, and allows this tetrazo compound to flow into a solution of 52 kg.
(1144 lbs.) of the above described ẞ-amido-u-naphtolmonosulphonic acid, made
alkaline with 60 kg. (132 lbs.) of soda. The dye-stuff separates out almost
immediately. It forms a black powder, dissolves in water showing a blackish red.
colour and dyes unmordanted cotton, in a weakly alkaline bath, blue black. The
dye-stuff can be again diazotised on the fibre, and combines with phenols and amines
and their sulphonic acids to new dyestuffs.
Dated this 1st day of March 1892.
J. CLARK JEFFERSON, A.R.S.M., Wh. Sc.,
2, East Parade, Leeds, Agent for Applicant.
COMPLETE SPECIFICATION.
A Black Cotton Dye-stuff, Combinations of the same, and Processes
for the Production thereof.
I ADOLF BANG of Basinghall Street Leeds in the County of York Dye Stuff
Merchant 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 :-
Amongst other disulphonic acids referred to in the Specification of German
Empire Letters Patent No. 41957 of 1886, an a-naphtylaminedisulphonic acid II
is described, the lime salt of which is readily soluble in 85 % alcohol. In the .
course of further experiments my communicator has discovered, that this acid is.
transformed into a dioxynaphtalinesulphonic acid, when melted with caustic soda,
Price d

page_text: If this dioxynaphtalinesulphonic acid is heated with ammonia under pressure, an
hitherto unknown ẞ-amido-a-naphtolmonosulphonic acid is produced. This acid is
suitable for the production of a very valuable dye-stuff. One proceeds as follows:-
10-8 kg. (23-8 lbs.) of paraphenylenediamine are dissolved in 500 litres of water
(110 gallons) with the addition of 20 kg. (44 lbs.) of hydrochloric acid and 20 kg.
(44 lbs.) of acetic acid, then cooled with ice to from 0 to 5° C. (32-40° Fht.) and
diazotised with 7 kg. (15.4 lbs.) of sodic nitrite. In this manner only one amido
group of the paraphenylenediamine is diazotised. The paraamidodiazobenzol thus
obtained is now allowed to flow into a solution of 144 kg. (317 lbs.) of
a-naphtylamine in 12 kg. (26.4 lbs.) of hydrochloric acid and 200 litres (44 gallons)
of water.
After several days standing the paraamidobenzolazo-a-naphtylamine has
formed itself. 40 kg. (88 lbs.) of hydrochloric acid are added to this, and one
again diazotises with a solution of 14 kg. (30.8 lbs.) of sodic nitrite, and allows this
tetrazo compound to flow into a solution of 52 kg. (114.4 lbs.) of the above
described amido-a-naphtolmonosulphonic acid, made alkaline with 60 kg.
(132 lbs.) of soda. The dye-stuff separates cut almost immediately. It forms a
black powder, dissolves in water shewing a blackish red colour, and dyes
unmordanted cotton, in a weakly alkaline bath, blue black. The dyestuff can be
again diazotised on the fibre, and combines with phenols and amines and their
sulphonic acids to new dye stuffs.
The following fuller description will exemplify the mode of producing the ẞ-amido-
anaphtolmonosulpho acid. 50 kg. (110 lbs.) of a naphty laminedisulpho acid
(Dahl & Co.'s acid II see Specification of German Patent No. 41957) of the
SO,H
300 litres of water and acidified with hydrochloric acid; whereupon the dioxy-
naphtalinmonosulpho acid separates out in crystals (see Specification of Dahl
and Co.'s German Patent No. 57014). 50 kg. (110 lbs.) of an aqueous solution of 30
ammonia specific gravity 0.91 are heated with 50 kg. (110 lbs.) of this dioxy-
naphtalinmonosulpho acid in an iron vessel to 180°-190° C. for 20 to 25 hours.
After the vessel has cooled down, the contents are boiled for some time to remove
the superfluous ammonia and then acidified with hydrochloric acid. The new

page_text: The following description will exemplify the process for the production of new
dye-stuffs on the fibre. 10 kg. (22 lbs.) of cotton dyed with the dyestuff' obtained
as above described, and as claimed in the following 1st Claim, are entered into a
cold diazodizing bath, which is obtained by dissolving 200 gr. of sodic nitrite in
30 litres of water and adding thereto 200 gr. of concentrated sulphuric acid. In
this bath the cotton is drawn through for 5 minutes squeezed and again washed
with cold water. To develope the new dye stuff, the cotton is now entered into a
likewise cold solution of 100 gr. of metaphenylenediamine and 100 gr. of soda in
30 litres of water and worked in the bath for hour. The cotton is then squeezed,
rinsed and dried. In this manner a deep blue black is obtained. If instead of
metaphenylenediamine the equivalent quantity of a or ẞ naphtol, amidonaphtol-
aether or resorcin are employed dark colours are likewise obtained but of rather
brownish shades.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
:-
1st. The process for the production of a black cotton dyestuff consisting in,
diazotising one amido group of paraphenylenediamine, combining with a-naphtyl-
amine again diazotising the resulting para-amidobeuzolazo-a-naphty lamine, and
combining with the same: the ẞ-amido-a-naphtolsulphonic acid, which is obtained
when one heats under pressure with ammonia the dioxynaphtalinemonosulphonic
acid, obtained by melting the a-naphtylaminedisulphonic acid II of the German
Empire Letters Patent No. 41957 of 1886 with caustic soda.
2nd. The production of new dyestuffs on the fibre, by again diazotising the dyes
(from the dyestuff's produced according to Claim 1st) and combining with a and
naphtol, amidonaphtolaether, resorcin and metaphenylenediamine.
3rd. The dyes or dyestuffs resulting from the processes claimed in the 1st and
2nd Claims.
Dated this 24th day of October 1892
J. CLARK JEFFERSON, Assoc. R.S.M.,
2, East Parade, Leeds, Agent for Applicant.