Manufacture of New Substantive Black Colouring Matters.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
Manufacture of New Substantive Black Colouring Matters.
I, JOHN IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent Agent,
do hereby declare the nature of this invention (which has been communicated to
me from abroad by La Société Anonyme des Matières Colorantes et Produits
Chimiques de St. Denis, of 105, Rue Lafayette, Paris, France,) to be as follows:-
Sulphurated colouring matters have been produced by causing sulphur or
sulphur and sodium sulphide to react on hydroxylated, amido-hydroxylated, poly-
amido-, amido-acetylated, &c. aromatic compounds.
My foreign correspondents have since found that the application of this re-
action to mixtures of aromatic compounds of different natures leads to unexpected
results, essentially different from those obtained by treating the compounds
separately.
Thus if mixtures for instance of paramido-phenol and a-naphthol, or of para-
mido-phenol and orthophenylene-diamine, or of paramidophenol and triamido-
benzene, are treated, the colouring matters obtained are different in tint and in
chemical properties from the colouring matters obtained from paramidophenol, or
a-naphthol or ortho-phenylenediamine or triamidobenzene when any one of these
is treated alone.
The colouring matter from paramidophenol is readily soluble in free alkalies
or carbonates and dyes cotton black, the colouring matters from orthophenylene-
diamine and triamidobenzene are insoluble in alkaline carbonates. The colour-
ing matters from a-naphthol, orthophenylenediamine and triamidobenzene dye
cotton brown red, whilst the colouring matters above referred to are clear black
and insoluble or scarcely soluble in alkaline carbonates, but are all soluble in
alkali sulphides.
EXAMPLE I.
There are heated to 200° C. for 3 hours in an iron pan 1 part of para-amido-
phenol, 1.2 parts of a-naphthol, and parts of sulphur; the whole is allowed to
cool and has added to it 8 parts of crystallised sodium sulphide; it is then
gradually heated up and kept for 3 to 4 hours at a temperature of about 180°
to 200° C. The brittle black mass thus obtained dissolves in alkalies or alkali sul-
phides; it dyes a clearer black than the colouring matter derived from para-amido-
phenol treated by itself, and, as is known, a-naphthol gives a weak brown colour-
ing matter.
In this example nitroso-a-naphthols and their reduction products
can be substituted for the a-naphthol.
EXAMPLE II.

page_text: crystallised sodium sulphide and the heat is kept for 3 to 4 hours at 180°
to 210° C. The product, which is scarcely at all soluble in alkaline carbonates,
gives a black dye more clear than the product obtained by treating para-amido-
phenol alone. For the orthonitraniline may be substituted orthophenylenediamine,
and the position of the substitutions may be inverted.
Thus in one of the aromatic nuclei of the substances treated the two substitu-
tions of amine and phenol into para in one of them and amine alone into ortho
in the other might be amine and phenol into ortho in the one and amine into
para in the other, that is to say, para-phenyldiamine may be substituted for
paramidophenol, and ortho-amido-phenol for orthophenylenediamine.
EXAMPLE III.
1 part of paramidophenol and 1 part of triamido-benzene-1:3:4 (or a corre-
sponding quantity of one of its salts set free by soda) are heated with 2 parts of
sulphur, the temperature being raised to 200° C. and kept up for 2 or 3 hours;
8 parts of crystallised sodium sulphide is then made to act on the above, the
temperature being maintained for 3 to 4 hours from 190° to 220° C. The colour-
ing matter thus obtained is insoluble in alkaline carbonates and dyes cotton black.
For the triamidobenzene-1:3:4 may be substituted chrysoidine from aniline,
triamidobenzene-1:2:6, dinitranilines-1:2:4 and 1:2:6 or the bismarck brown
from meta-phenylenediamine.
As in Example II, the arrangement of the substitution may also be inverted;
for para-amidophenol may be substituted paraphenylenediamine and for triamido-
benzene dinitrophenol or diamidophenol.
In the three examples for the para-amidophenol may be substituted any sub-
stance capable of producing it in the reaction medium, such as azo-derivatives of
phenol, paranitrophenol, nitrosophenol, oxyazobenzene, &c.
The methods of operating may also be varied, thus the heating may be first
with sulphur and then with sodium sulphide, or with both together; the tem-
peratures may be at first very high or may be gradually raised at 180°, 210°,
or 220° C.
All the colouring matters obtained as above set forth may be applied without
any further preparation, or they may be freed from accessory substances which
they contain by acidulated boiling water, and the residuary colouring matter may
be prepared for dyeing by bruising it with sodium sulphide or other solvent.
These colouring matters all dye cotton clear black in an alkaline bath with or
without addition of sodium sulphide. The shades obtained on exposure to the
air rapidly become very intense; contrary to those obtained from para-amido-
phenol, they give, without bichromate treatment, stable and definite shades having
great resistance to alkaline washes.
T
11
1
1
1000
ABEL & IMRAY,
Agents for the Applicant.
1, JOHN IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, Chancery 45
Lane, in the County of London, Consulting Engineer and Chartered Patent Agent, do
hereby declare the nature of this invention (which has been communicated to me from
abroad by La Société Anonyme des Matieres Colorantes et Produits Chimiques de

page_text: 1 part of paramidophenol and 1 part of triamidobenzene-1:3:4 (or a corre-
sponding quantity of one of its salts set free by soda) are heated with 2 parts of
sulphur, the temperature being raised to 200° C. and kept up for 2 or 3 hours; 8 parts
of crystallised sodium sulphide is then made to act on the above the temperature

page_text: being maintained for 3 to 4 hours from 1900 to 220° C. The colouring matter thus
obtained in insoluble in alkaline carbonates and dyes cotton black. For the triamido-
benzene-13:4 may be substituted chrysoidine from aniline, triamido-benzene 1:2:6,
dinitranilines-1:2:4 and 1:2:0 or the bismarck brown from meta-phenylene-
diamine.
As in Example II, the arrangement of the substitutions may also be inverted; for
para-amidophenol may be substituted paraphenylenediamine and for triamidobenzene
dinitrophenol or diamidophenol.
In the three examples for the para-amidophenol may be substituted any substance
capable of producing it in the reaction medium, such as azo-derivatives of phenol,
para-nitrophenol, nitrosophenol oxyazobenzene &c.
The methods of operating may also be varied, thus the heating may be first with
sulphur and then with sodium sulphide, or with both together; the temperatures
may be at first very. high or may be gradually raised to 180°, 210°, or 220° C.
All the colouring matters obtained as above set forth may be applied without any
farther preparation, or they may be freed from accessory substances which they
contain by washing with acidulated boiling water, and the residuary colouring matter
may be prepared for dyeing by bruising it with sodium sulphide or other solvent.
These colouring matters all dye cotton clear black in an alkaline bath with or with-
out addition of sodium sulphide. The shades obtained on exposure to the air rapidly
become very intense; contrary to those obtained from para-amidophenol, they give,
without bichromate treatment, stable and definite shades having great resistance to
alkaline washes.
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 herein described manufacture of colouring matters by causing sulphur or
sulphur with sulphides to react on mixtures of
a. paramidophenol and a-naphthol.
b. paramidophenol and orthonitraniline or orthophenylenediamine; or ortho-
amidophenol and paraphenylenediamine.
c. paramidophenol and triamidobenzene or paraphenylenediamine and a diamido-
phenol.
2. The colouring matters manufactured as above set forth.
ABEL & IMRAY,
Agents for the Applicant.