Manufacture of Black Colouring Matters Directly Dyeing Cotton.
Year: 1899

page_text: Date of Application, 26th June, 1899
Complete Specification Left, 16th Mar., 1900-Accepted, 21st Apr., 1900
PROVISIONAL SPECIFICATION.
Manufacture of Black Colouring Matters Directly Dyeing Cotton.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, in the County of London, Consulting Engineer and Chartered Patent Agent,
do hereby declare the nature of this invention (as communicated to me from.
abroad by Actien-Gesellschaft für Anilin Fabrikation of Berlin, in the Empire
of Germany, Chemical Manufacturers) to be as follows:-
It is well known that by treating para-amidophenol with sulphur and sulphides
of alkali metals a colouring matter is produced, the so-called vidal-black of com-
This dyestuff dis-
merce, as described in the Specification No. 23578 of 1893.
solves in water with glass-green colour and dyes cotton dark green shades which
only by subsequent oxydation are turned black.
On the other hand it has been shown that by melting with sulphur and sul-
phides of alkali metals certain nitro-oxy-derivatives of diphenylamine there are
obtained colouring matters which directly produce on the fibre black tints without
requiring a subsequent oxidation, as described in the Specification No. 25234 of
1897, and in the French Patent No. 283559 of 1898.
My foreign correspondents have now found that a quite unexpected reaction
takes place if sulphur and sulphides of alkali metals are allowed to act on mix-
tures of equimolecular proportions of para-amidophenol and of nitro-oxy-deriva-
tives of diphenylamine.
This reaction does not lead, as might be expected, either to the formation of a
mixture of vidal-black, (of the Specification No. 23578 of 1893,) and of, immedial-
black, (of the Specification No. 25234 of 1897,) or to the formation of only one of.
these dyestuffs, but there results an entirely new colouring matter which is clearly
distinguished from both the dyestuffs mentioned.
The new product dyes cotton directly deep black shades without requiring, like
vidal-black, a subsequent oxidation.
Also the shades obtained by means of the new colouring matter are different
from those obtained by means of immedial-black, the latter being more blueish-
black, whereas the new product yields green-black shades.
Furthermore it is not possible to produce the shades which are obtained by
means of the new product by simply mixing the colouring matters (vidal-black
and immedial-black) separately prepared by the action of sulphur and sulphides
on para-amidophenol and on nitro-oxy-derivatives of diphenylamine. These
facts clearly indicate that when mixtures of para-amidophenol and of the diphenyl-
6 amine derivatives above mentioned are heated with sulphur and sulphides of
alkali metals the two components simultaneously enter into the reaction, a new
colouring matter being formed which is entirely different from the products
obtained by treating the two components separately with the same agents.
The following example illustrates the invention:-
0
48 parts by weight of sodium sulphide, 17 parts of sulphur and 5 parts of
water are heated together and to this mixture is added at 110° to 120° C. a mix-
ture of 10 parts of dinitro-oxy-diphenylamine and 4 parts of para-amidophenol
(equimolecular proportions). The formation of the colouring matter commences
at about 125° C. The temperature is slowly raised up to 150° to 160° C. main-

page_text: tained at this degree for about 4 to 5 hours. The dry melt is powdered and can
be directly employed for dyeing
The product dyes cotton directly black shades.
If in the preceding example for dinitro-oxy-diphenylamine is substituted the
equivalent quantity of dinitro-oxy-diphenylaminesulphonic acid (obtained by the
action of dinitrochlorobenzene on para-amidophenolsulphonic acid) or of meta-
dinitrophenyl-para-salicylic acid, there are obtained black colouring matters of
character quite similar to that described above.
Instead of para-amidophenol there may be used with like results certain dia-
mines, such for instance as para- or meta-phenylenediamine and para- or meta-
toluylenediamine.
The colouring matters obtained by means of the para-diamines yield blueish-
black shades whereas those obtained from meta-diamines yield more green-black
shades.
Instead of directly introducing para-amidophenol or the diamines mentioned
into the reaction the corresponding nitro-derivatives may be equally well used,
that is to say para-nitrophenol, the nitro-anilines or nitrotoluidines and the dini-
trobenzenes or dinitrotoluenes, these derivatives being converted into the amido-
products by the action of the sulphides.
Dated this 26th day of June 1899.
COMPLETE SPECIFICATION.
Manufacture of Black Colouring Matters Directly Dyeing Cotton.
I, CHARLES DENTON ABEL, of Birkbeck Bank Chambers, Southampton Build-
ings, in the County of London, Consulting Engineer and Chartered Patent Agent,
do hereby declare the nature of this invention (as communicated to me from
abroad by Actien-Gesellschaft für Anilin Fabrikation of Berlin, in the Empire
of Germany, Chemical Manufacturers), 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 by treating para-amidophenol with sulphur and sulphides
of alkali metals a colouring matter is produced, the so-called vidal-black of com-
merce, as described in the Specification No. 23578 of 1893. This dyestuff dis-
solves in water with glass-green colour and dyes cotton dark green shades which
only by subsequent oxidation are turned black.
+
On the other hand it has been shewn that by heating with sulphur and sul-
phides of alkali metals certain nitro-oxy-derivatives of diphenylamine there are
obtained colouring matters which directly produce on the fibre black tints without
requiring a subsequent oxidation, as described in the Specification No. 25234 of
1897, and in the French Patent No. 283559 of 1898.
My foreign correspondents have now found that a quite unexpected reaction
takes place if sulphur and sulphides of alkali metals are allowed to act on mix-
tures of equimolecular proportions of para-amidophenol and of nitro-oxy-deriva-
tives of diphenylamine.
This reaction does not lead, as might be expected, either to the formation of a
mixture of vidal-black, (of the Specification No. 23578 of 1893,) and of immedial-
black, (of the Specification No. 25234 of 1897.) or to the formation of only one of
these dyestuffs, but there results an entirely new colouring matter which is clearly
distinguished from both the dyestuffs mentioned.
The new product dyes cotton directly deep black shades without requiring, like
vidal-black, a subsequent oxidation.

page_text: Also the shades obtained by means of the new colouring matter are different
om those obtained by means of immedial-black, the latter being more blueish-
lack, whereas the new product yields green-black shades.
Furthermore it is not possible to produce the shades which are obtained by
eans of the new product by simply mixing the colouring matters (vidal-black
nd immedial-black) separately prepared by the action of sulphur and sulphides
n para-amidophenol and on nitro-oxy-derivatives of diphenylamine. These
acts clearly indicate that when mixtures of para-amidophenol and of the diphenyl-
mine derivatives above mentioned are heated with sulphur and sulphides of
lkali metals the two components simultaneously enter into the reaction, a new
colouring matter being formed which is entirely different from the products
obtained by treating the two components separately with the same agents.
The following example illustrates the invention :-
'
48 parts by weight of sodium sulphide, 17 parts of sulphur and 5 parts of
water are heated together and to this mixture is added at 110° to 120° C. a mix-
ture of 10 parts of dinitro-oxy-diphenylamine (obtained by the action of dinitro-
chlorobenzene [CH: NO, NO, = 1:2:]on para-amidophenol) and 4 parts of para-
amidophenol (equimolecular proportions). The formation of the colouring matter
commences at about 125° C. The temperature is slowly raised up to 150° to 160°
The dry mass is
C. and maintained at this degree for about 4 to 5 hours.
powdered and can be directly employed for dyeing.
The product dyes cotton directly black shades.
If in the preceding example for dinitro-oxy-diphenylamine is substituted the
equivalent quantity of dinitro-oxy-diphenylaminesulphonic acid (obtained by the
action of dinitrochlorobenzene [CI: NO, NO, 1:2:4] on para-amidophenolsul-
phonic acid) or of meta-dinitrophenyl-para-salicylic acid, there are obtained
black colouring matters of character quite similar to that described above.
Instead of para-amidophenol there may be used with like results certain dia-
mines, such for instance as para- or meta-phenylenediamine and para- or meta-
toluvlenediamine.
The colouring matters obtained by means of the para-diamines yield blueish-
black shades whereas those obtained from meta-diamines yield more green-black
shades.
Instead of directly introducing para-amidophenol or the diamines mentioned
into the reaction the corresponding nitro-derivatives may be equally well used,
that is to say para-nitrophenol, the nitro-auilines or nitrotoluidines and the dini-
trobenzenes or dinitrotoluenes, these derivatives being converted into the amido-
products by the action of the sulphides.
Having now particularly described and ascertained the nature of my said
O invention and in what manner the same is to be performed, I declare that what
I claim is
1. The herein described manufacture of black colouring matters directly dyeing
cotton by heating with sulphur and sulphides of alkali metals an equimolecular
mixture of a nitro-oxy-derivative of diphenylamine-such as for instance, dini-
5 tro-oxydiphenylamine, dinitro-oxydiphenylaminesulphonic acid, meta-dinitro-
phenyl-para-amidosalicyclic acid-and para-amidophenol, para- or meta-phenyl-
enediamine, para- or meta-toluylenediamine or a nitro-compound which yields
one of these when reduced.
2. The products manufactured as above set forth.
14MARY