Manufacture of Colouring Matters Dyeing Wool Green Black to Blue Black.
Year: 1896

page_text: Date of Application, 10th Jan., 1896-Accepted, 15th Feb., 1896
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, Basle, Switzerland, Chemical Manufacturers.]
Manufacture of Colouring Matters Dyeing Wool Green Black to
Blue Black.
I, OLIVER JMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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 :-
Since the application for Patent No. 15457 of 1895 my foreign correspondents
have found that the unsymmetric disazo colouring matters for wool described in the
said Specification, which directly dye animal fibre in shades varying from violet
black to blue black, can, under the influence of a condensing agent, be transformed
into colouring matters which dye with more blue or more green shades.
This transformation is easily effected by heating, in either a close or an open
vessel, the colouring matters in the acid state with water, or in the state of salts,
with an aqueous solution of certain mineral or organic substances, such, for instance,
as mineral acids (hydrochloric, sulphuric, nitric, phosphoric, boric &c. acids),
organic acids of the fat and aromatic series (oxalic, acetic, benzoic, phthalic &c.
acids), or certain mineral salts especially zinc chloride.
According to the duration of the reaction, the temperature at which it takes
place, and the condensing agent employed, the transformation is effected more or
less quickly, with evolution of ammonia, and so, by stopping the reaction sooner or
later, colouring matters can be obtained which dye from violet black to green
black.
The reaction, which takes place with advantage in aqueous solution or by
suspending the colouring matter in the liquid, can evidently be simplified by
dispensing with separation of the colouring matter described in the previous
Specification, and directly applying to the products obtained by means of the
reactions set forth in that Specification, the process which is the object of the
present invention, as will be understood from the following examples.
EXAMPLE I.
5 kilos. of the colouring matter obtained by the successive combination of
naphthylene-diamine disulpho acid 1. 8. 3. 6 with diazo-benzol and paranitrodiazo-
benzol, are dissolved in 100 litres of water; to the solution thus obtained are
added 5 kilos. of acetic acid, and the whole is then heated on the water bath for
about 8 hours or until a sample taken from the mass does not change or changes
only a little in colour, or, finally, until the mass has attained the desired shade. It
is then neutralised with carbonate of soda, and the new colouring matter is
precipitated by sea salt, filtered, pressed and dried. It forms a powder with
bronze lustre, readily soluble in water with a blue green colour, and it dyes wool
in an acid bath an intense green black.
EXAMPLE II.
20 kilos. of the colouring matter resulting from the combination of naphthylene-
diamine-disulpho acid 1. 8. 3. 6 with paranitro diazo-benzol and paradiazo benzol
sulpho acid are dissolved in 500 litres of water, 20 kilos. of zinc chloride are added
whole in than booted to hailin
The colour of the calution first vialet

page_text: changes gradually to blue, and after 3 to 4 hours boiling, it no longer undergoes
any change on addition of acid or of carbonate of soda. The colouring matter is
collected on precipitation with sea salt.
EXAMPLE III.
10 kilos. of the colouring matter obtained by the combination of naphthylene-
diamine-disulpho acid 1. 8. 3. 6 with paranitrodiazobenzol and the diazo derivative
of naphthylamine-disulpho acid G, are heated to boiling with an aqueous solution
of oxalic acid of 2 per cent. The transformation of the colouring matter into a new
green black colouring matter quickly takes place and is completed at the end of
about half an hour.
The colouring matter thus formed is separated from its intense green solution in
the manner indicated above.
EXAMPLE IV.
20 kilos. of the colouring matter prepared by the combination of naphthylene-
diamine-disulpho acid 1. 8. 3. 6 with the diazo derivative of metanilic acid (meta
sulpho diazo benzol) and paranitrodiazobenzol, are dissolved in 200 litres of water,
40 kilos. of ordinary hydrochloric acid are added, and the whole is then heated to
boiling until the colour of the solution has become pure blue. The colouring
matter is then neutralised and collected in the usual way.
Instead of effecting the reaction in acid solution, there may be added to the
solution of the colouring matter which is to be transformed only the quantity of
acid necessary to transform the colouring matter into an acid, the solution being
then heated to boiling. The transformation into the new colouring matter is thus
completed but somewhat more slowly.
EXAMPLE V.
20 kilos. of the colouring matter prepared by means of naphthylenediamine-
disulpho acid, the diazo derivative of sulphanilic acid (para sulpho diazobenzol)
and the diazo derivative of paranitraniline sulpho acid are dissolved in 200 litres of
water, 5 kilos. of benzoic acid are added, and the whole is then heated to boiling.
In about 4 hours the solution becomes blue black and does not farther change in
colour. The new colouring matter formed is neutralised and separated by
addition of sea salt.
If the other colouring matters described in the previous Specification are
similarly treated, dark transformation products are obtained, forming powders with
bronze lustre, which dye wool shades varying from blue black to green black,
whilst aqueous solutions of the colouring matters, from which the new matters are
produced, give dyes varying from violet black to blue black.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The transformation of the unsymmetric black disazo colouring matters
prepared as set forth in the Specification No. 15457 of 1895, into colouring matters
of more blue or green shades, by heating, in a close or open vessel, the aforesaid
colouring matters in acid state with water, or their solutions with acids, salts or
other suitable condensing agents.
2. The new colouring matters manufactured as above set forth.
10.1
2000
ABEL & IMRAY,
Agents for the Applicant.