Manufacture of Black-blue to Black Disazo Colouring-matters for Wool.
Year: 1895

page_text: Date of Application, 16th Aug., 1895
Complete Specification Left, 18th Sept., 1895-Accepted, 2nd Nov., 1895
PROVISIONAL SPECIFICATION.
Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, Basle, Switzerland, Chemical Manufacturers.]
Manufacture of Black-blue to Black Disazo Colouring-matters
for Wool.
I, OLIVER IMRAY of No. 28 Southampton Buildings, Chancery Lane in the
County of London, Chartered Patent Agent do hereby declare the nature of this
invention to be as follows:-
--
It is well known that naphthylenediamine disulpho acid 1. 8. 3. 6 can be easily
converted into mono-azo-colouring-matters by the action of one molecule of any
diazo-body. These dye-stuffs however have no technical value more especially
because they are very sensitive to acids.
Para nitro diazobenzol produces when combined in the second place with red to
brown mono-azo colouring matters derived from naphthylenediamine disulpho
acid 1. 3. 8, new disazo colouring matters yielding black-blue to black tints.
These dye-stuffs correspond to the following formula:
(where X means the radicle of an aromatic amine or its substitution products)..
They are preferably produced by the action of 1 molecule of para nitro-diazo
benzol (preferably in acetic solution) upon mono-azo colouring matters resulting
from 1 molecule naphthylenediamine disulpho acid 1. 8. 3. 6 and 1 molecule of a
diazotised aromatic amine or its sulpho-, nitro-, chloro-, amido-, hydroxylic-,
alkyl hydroxylic-, carboxylic- and sulpho-carboxylic derivatives.
These colouring matters form powders of a black or bronze-like hue. They
dissolve in water with a blue-violet to green-blue, in concentrated sulphuric acid
with a green coloration.
Their tints on wool vary from black-blue to dark black according to their
intensity and distinguish themselves by their great tinctorial power, fastness
against light and especially fulling.

page_text: thus obtained is combined directly (or after having been isolated and re-dissolved
in water) with a solution of diazotised para nitraniline in presence of sodium
acetate or carbonate of soda.
The orange-brown solution turns into. blue-black and after having been agitated
during some hours, the formation of the new disazo colouring matter is completed.
The dried dye-stuff is a black brown powder which dissolves easily in water
with a violet coloration and dyes intense blue-black shades on wool in an acid
bath.
Similar dye-stuffs are produced, if in this example metanilic acid is replaced
by the equivalent quantity of one of the following components: aniline,
orthotoluidine, para-toluidine, xylidine, ortho-anisidine, ortho-phenetidine, para-
anisidine, para-phenetidine, meta-amido-para-cresol-ether, alpha- and beta-
naphthylamine, para-amido-diphenylamine and the nitro and chloro derivatives of
all of these bodies, para-amido-acetanilid, amido-azo benzol, amido-azo toluol,
sulphanilic acid, sulphanil-disulpho acid, metanil-disulpho acid, toluidine įmono-
and disulpho acids, xylidine sulpho acids,

page_text: This process is practically carried out as follows :.
EXAMPLE II.
13.8 kilos. of para-nitraniline are diazotised with 7. kilos. of sodium nitrite in
the usual manner and the resulting diazo solution is mixed with a solution of
32. kilos. of naphthylenediamine-disulpho acid 1. 8. 3. 6 containing sodium acetate
in excess.
After standing during several hours the red-violet solution of the mono-azo
is mixed with para-diazo-benzol-sulpho acid, resulting from 19.5 kilos. of soda-salt
of sulphanilic acid. The red-violet solution turns gradually into blue-violet and
after agitating during 12 hours the combination is complete. The mass is heated
to 80° C. and the colouring matter is precipitated with common salt, filtered,
pressed and dried.
Similar results are obtained if in this example, the sulphanilic acid is replaced
by other components enumerated under Example I.
Dated this 16th day of August 1895.
ABET & IMKAI,
Agents for the Applicant.
CUMI DETECT MOITICATIO
Manufacture of Black-blue to Black Disazo Colouring-matters
for Wool.
I, OLIVER IMRAY, 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 :-
It is well known that naphthylenediamine disulpho acid 1.8.3. 6 can be easily
converted into mono-azo-colouring matters by the action of one molecule of any
diazo-body. These dye-stuffs in general have no technical value more especially
because they are very sensitive to acids.
My foreign correspondents have observed that these colouring matters varying
from brown to red and violet may be converted into very useful new asymmetric
colouring matters, which dye on wool in an acid bath blue-black to intense black
tints.
These drestuiffs correspond to the following formula:

page_text: The diazo compound resulting from 19.5 kilos. of the soda salt of metanilic acid
according to the usual method is first united with 32 kilos. of naphthylenediamine
disulpho acid 1.8.3.6 in acetic solution. Some hours after the colouring matter
thus obtained is combined directly (or after having been isolated and re-dissolved
in water) with a solution of diazotised para-nitraniline in presence of sodium
acetate or carbonate of soda.
The orange-brown solution turns into blue-black and after having been agitated
during some hours, the formation of the new disazo colouring matter is completed.
The dried dye-stuff is a black brown powder which dissolves easily in water with
a violet coloration and dyes intense blue-black shades on wool in an acid bath.
Similar dye-stuffs are produced, if in this example metanilic acid is replaced by
the equivalent quantity of one of the following components: aniline, ortho-toluidine,
para-toluidine, xylidine, ortho-anisidine, ortho-phenetidine, para-anisidine, para-
phenetidine, meta amido para cresol ether, alpha- and beta-naphthylamine,
dinitraniline, nitrotoluidines, para-amido-acetanilid, amido-azo benzol, amido azo-
toluol, amido-azo xylol, sulphanilic acid, sulphanil disulpho acid, metanil disulpho
acid, toluidine mono and disulpho acids, xylidine sulpho acids,

page_text: 13.8 kilos. of para-nitraniline are diazotised with 7 kilos. of sodium nitrite in the
sual manner and the resulting diazo solution is mixed with a solution of
2 kilos. of naphthylenediamine disulpho acid 1. 8. 3. 6 containing sodium acetate
excess.
After standing during several hours, the red-violet solution of the mono-azo
olouring matter is mixed with para-diazo-benzol-sulpho-acid resulting from
9.5 kilos. of soda-salt of sulphanilic acid. The red-violet solution turns gradually
to blue-violet and after agitating during 12 hours the combination is complete.
The mass is heated to 80° C. and the colouring matter is precipitated with common
alt, filtered, pressed and dried. It forms a bronze-like powder and dyes blue-
lack on wool in an acid bath, or mordanted with a chrome salt.
Similar results are obtained if in this example the sulphanilic acid is replaced
y other components enumerated under Example 1.
Having now particularly described and ascertained the nature of my said inven-
ion and in what manner the same is to be performed I declare that what I
laim is:
1. The manufacture of new asymmetric disazo colouring matters derived :
a. By the action of 1 molecule of a diazotised aromatic nitro-amine preferably
para-nitro-diazo benzol on mono-azo colouring matters resulting from
1 molecule naphthylenediamine disulpho acid 1. 8. 3. 6 and 1 molecule of a
diazotised aromatic amine or its sulpho-, nitro-sulpho-, chloro, amido-,
bydroxylic-, alkyl-hydroxylic-, carboxylic-, or sulpho-carboxylic derivatives
as described.
b. By the action of 1 molecule of a diazotised aromatic amine or its sulpho-,
nitro-sulpho-, chloro-, amido-, hydroxylic-, alkyl-hydroxylic-, carboxylic-
or sulpho carboxylic derivatives on 1 molecule of the mono-azo colouring
matters resulting from 1 molecule of naphthylenediamine disulpho acid 1.8.3.6
and 1 molecule of a diazotised aromatic nitroamine preferably para-nitro-
diazo-benzol.

page_text: 2. The new
forth.
asymmetric diazo colouring matters manufactured as above set
Dated this 18th day of Sentember 1895
ABEL & IMRAY,
Agents for the Applicant.