Improvements in the Production of Black Coloring Matters.
Year: 1891

page_text: Date of Application, 6th Apr., 1891
Complete Specification Left, 1st Jan., 1892-Accepted, 6th Feb., 1892
PROVISIONAL SPECIFICATION..
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, of Hoechst a Main, Germany, Chemical Manufacturers.]
Improvements in the Production of Black Coloring Matters.
1, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Fellow of the Institute of Patent Agents, do hereby declare
the nature of this invention to be as follows:-
The azo coloring matters mostly used for dyeing black are almost without
exception diazo coloring matters, prepared by diazotising the corresponding amido
azo sulphonic acid, of which the following is an example:-
-
The acid obtained by combining a diazonaphthalinsulphonic acid with alpha-
naphthylamine or by sulphonizing amido azo benzene and causing the diazo body
thus obtained to act upon a condensable component such as the beta naphthol-
disulphonic acid R or tolyl-naphthylamine.
The foreign communicators of this invention have discovered a novel process
quite different from that sketched above, for producing new coloring matters
dyeing shades ranging from violet black to blue black. Their process is based on
the fact, that the dioxynaphthalindisulphonic acid, which is obtained by melting
together with caustic alkali the naphtholtrisulphonic or the naphtho sulton-
disulphonic acid described in the German Letters Patent No. 56058 is capable
of combining with two molecules both of the same diazo compound or with two
molecules each of a different diazo compound.
.
It is thus that the azo coloring matters prepared from one molecule of the
dioxynaphthalindisulphonic acid above referred to and one molecule of a diazo
compound, which coloring matters generally produce shades ranging from red to
violet red, also when isolated by themselves, combine with a second molecule of the
diazo compound used in their preparation, or with a further molecule of another
diazo compound to form azo coloring matters dyeing black shades.
In both cases the combination proceeds quite smoothly when strong alkalies are
employed, such as caustic potash, caustic soda, aminonia, concentrated soda solution
and the like in presence of an excess of these bodies.
When two molecules of one and the same diazo compound are employed, the
simplest way is to bring them conjointly into action; but when two different diazo
compounds are employed the best manner of carrying out the combination is to
prepare first the coloring matter from one molecule of diazo compound with. one
molecule of the dioxynaphthalindisulphonic acid and then to combine this coloring
matter, isolated by itself, or in the state in which it is obtained, that is to say
without previously isolating it, with the second molecule of diazo compound.
It is to be understood that the operation may thus be divided when two molecules
of one and the same diazo compound are employed.
The process for preparing the novel colouring matters is more fully described in
the following examples:
a.) One molecule of dioxynaphthalindisulphonate of soda by means of an ample
quantity such as 4 molecules of caustic soda dissolved in water, is brought into a
state of solution of 15 to 20 per cent. strength and to this kept in agitation are
added successively two molecules of a diazo benzene chloride solution prepared in
the usual manner. After standing for 12 hours, the combination is complete,
whereupon the coloring matter is precipitated by means of common salt and
obtained in well known manner.
b.) One molecule of the coloring matter prepared from one molecule of diazo

page_text: benzene chloride and one. molecule of dioxynaphthalindisulphonic acid mixed with
one and one fifth molecule of caustic soda dissolved in water, is brought to the
state of a solution of from 10 to 15 per cent. strength, then one molecule of
diazonaphthalinsulphonic acid (1-4) is added and the treatment is continued as set
forth in the preceding example:
c.) One molecule of dioxy-naphthalin-disulphonate of soda by means of one and
a half molecule of soda dissolved in water, is brought into the state of a solution of
from 10 to 15 per cent. strength, then there is added one molecule of the diazo
compound prepared from the beta naphthylamine disulphonic acid Y, and the
mixture at a temperature from 0° to 6° C. is kept agitated for 6 hours. After this
period the coloring matter which dyes a bluish red tint is formed. There is then
added another quantity of soda as above and afterwards, under active agitation,
one molecule of alpha diazonaphthalin chloride and at the temperature above
named. The further treatment is as set forth in example a.).
Of the great number of compounds that can be prepared by the process described,
the following may be mentioned as examples
Compound prepared by the action of:

page_text: The coloring matters possessing the most valuable qualities are those in the
preparation of which there are employed: a molecule of a sulphonised and one of a
non-sulphonised diazo body.
The coloring matters formed by the action of two molecules of sulphonised diazo
compounds dye less uniform shades.
Those coloring matters which, besides the sulpho groups of the dioxy-
naphthalindisulphonic acid, do not contain other sulpho groups, tend in heavy
shades to bronze and rub off.
The coloring matters to which this invention relates possess further the quality
of producing still deeper black shades on being dyed in an acid bath with or
without addition of alkali chromates; the shades produced in this way range from
blue black to green black.
Dated this 6th day of Anil 1901
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Black Coloring Matters.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane in the
County of London, Fellow of the Institute of Patent Agents, 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 coloring matters mostly used for dyeing black are almost without
exception diazo coloring matters, prepared by diazotising the corresponding amido
azo sulphonic acid, of which the following is an example
The acid obtained by combining a diazonaphthalin-sulphonic acid with alpha-
naphthylamine or by sulphonizing amido azo benzene and causing the diazo body
thus obtained to act upon a condensable component such as the beta naphthol-
disulphonic acid R or tolyl-naphthylamine.
The foreign communicators of this invention have discovered a novel process
quite different from that sketched above, for producing new coloring matters
dyeing shades ranging from violet black to blue black. Their process is based on
the fact, that the dioxynaphthalindisulphonic acid, which is obtained by melting
together with caustic alkali the naphtholtrisulphonic or the naphtho sulton-
disulphonic acid described in the German Letters Patent No. 56058 is capable
of combining with two molecules both of the same diazo compound or with two
molecules each of a different diazo compound.
It is thus that the azo colouring matters prepared from one molecule of the
dioxynaphthalin disulphonic acid above referred to and one molecule of a diazo
compound, (which coloring matters generally produce shades ranging from red to
violet red) also when isolated by themselves, combine with a second molecule of the
diazo compound used in their preparation, or with a further molecule of another
diazo compound to form azo coloring matters dyeing black shades.
In both cases the combination proceeds quite smoothly when strong alkalies are
employed, such as caustic potash, caustic soda, ammonia, concentrated soda solution
and the like in presence of an excess of these bodies.
When two molecules of one and the same diazo compound are employed, the
simplest way is to bring them conjointly into action; but when two different diazo
compounds are employed the best manner of carrying out the combination is to
prepare first the coloring matter from one molecule of diazo compound with one
molecule of the dioxy-naphthalindisulphonic acid and then to combine this colouring
matter, isolated by itself, or in the state in which it is obtained, that is to say
without previously isolating it, with the second molecule of diazo compound.
It is to be understood that the operation may thus be divided when two molecules
of one and the same diazo compound are employed.

page_text: The process for preparing the novel colouring matters is more fully described in
the following examples:
a.) One molecule of dioxynaphthalindisulphonate of soda by means of an ample
quantity such as 4 molecules of caustic soda dissolved in water, is brought into a
state of solution of 15 to 20 per cent. strength, and to this kept in agitation are
* added successively two molecules of a diazo benzene chloride solution prepared in
the usual manner.
After standing for 12 hours, the combination is complete, whereupon the coloring
matter is precipitated by means of common salt and obtained in well known
manner.
b.) One molecule of the colouring matter prepared from one molecule of diazo
benzene chloride and one molecule of dioxynaphthalindisulphonic acid mixed with
one and one fifth molecule of caustic soda dissolved in water, is brought to the
state of a solution of from 10 to 15 per cent. strength, then one molecule of
diazonaphthalinsulphonic acid (1-4) is added and the treatment is continued as set
forth in the preceding example.
c.) One molecule of dioxynaphthalindisulphonate of soda by means of one and a
half molecule of soda dissolved in water, is brought into the state of a solution of
from 10 to 15 per cent. strength, then there is added one molecule of the diazo
compound prepared from the betanaphthylamine disulphonic acid Y, and the
mixture at a temperature from 0° to 6° C. is kept agitated for 6 hours. After
this period the coloring matter which dyes a bluish red tint is formed. There is
then added another quantity of soda as above and afterwards, under active agitation,
one molecule of alphadiazonaphthalin chloride and at the temperature above named.
The further treatment is as set forth in example a).

page_text: Of the great number of compounds that can be prepared by the process described
he following may be mentioned as examples:
Compounds prepared by the action of:
mol. of diazotised aniline
"
"
"
وو.
naphthionic acid
benzidine
mol. diazot. naphthionic acid and 1 mol. diazot. aniline
"
"
::
22
"
"
33
"
2:
>>
29
::
'
:3
.
p-nitraniline
naphthylamine
1
22
33
23
"
а
"
22
::
::
:2
22
B
"
27
ẞ naphthylamine
sulphonic acid
(Bronner)
"
acct-p-phenylen-diamine
"
دو
"2
22
**
22
22
23
"
22
33
::
"
دو
"
32
:
32
"
23
"
23
23
"
"
"
"
"
"2
ẞ naphthylaminedi-
sulphonic acid G
22
"
"2
22
ẞ naphthylaminedi-
sulphonic acid R
1
22
"
1
"
"
وو
وو
2
::
"
3
::
::
22
32
"
"
1
23
"
22
22
"
33
:
"
22
22
::
::
29
"
22
29
"
A
"
"
"
ẞ naphthylaminetri-
the dioxenanhthal
luhonic acid hereinbefore characterized.
aniline
p-nitraniline
a-naphthylamine
B-
"
acet-p-phenylen-diamine
aniline
p-nitraniline
a-naphthylamine
В
acet-p-phenylen-diamine
aniline
p-nitraniline
a-naphthylamine
β
acct-p-phenylen-diamine

page_text: Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed, 1 declare that what I
claim is :-
1. The herein described process for production of diazo colouring matters dyeing
wool in acid bath with or without the addition of alkali chromates, shades ranging
from violet black to green black, by causing two inolecules of a diazo compound to
act upon one molecule of the dioxynaphthalindisulphonic acid, which is obtained by
melting together with caustic alkalies the naphthol trisulphonic acid or the
naphthosultondisulphonic acid described in the German Letters Patent No. 56058.
2. The diazo colouring matters produced as above described.
Dated this 22nd day of December 1891.
ABEL & IMRAY,.
Agents for the Applicant.