The Manufacture or Production of Brown Polyazo Colouring Matters.
Year: 1898

page_text: Date of Application, 9th Mar., 1898
Complete Specification Left, 17th Nov., 1898-Accepted, 7th Jan., 1899
[Communicated from abroad by THE CHEMICAL WORKS, formerly SANDOZ, Basle,
Switzerland, Chemical Manufacturers.]
The Manufacture or Production of Brown Polyazo Colouring Matters.
I, WILLIAM EDWIN HEYS, of 70, Market Street, Manchester, in the County of
Lancaster, Chartered Patent Agent, do hereby declare the nature of this invention
to be as follows:
In the Specification of French Letters Patent No. 243,735, dated the 18th
December 1894, azo colouring matters are described which are produced by com-
bining diazo and tetrazo compounds with the azo compounds derived from diazo-
naphthol sulphonic acids and metadiamines. It is distinctly stated in the specifica-
tion referred to that one molecule of these monoazo compound; has the property
of combining with one molecule of a diazo compound, the new azo group fixing
itself in the radicle of the metadiamine.
But my foreign correspondents have found that one molecule of the above men-
tioned monazo compounds, especially of those derived from diazotised beta,alpha
amidonaphthol beta,beta,disulphonic acid (see Specification of German Letters
Patent No. 53023), and metaphenylenediamine or metatoluylenediamine having the
formula
(which will hereinafter be called "Colour A"), is susceptible of combining with
two molecules of one and the same diazo compound or with one molecule each of
two different diazo compounds.
By combining the "Colour A," first with a diazo compound, as for example with
diazonaphthionic acid, and by then combining the diazo colour thus obtained
with the intermediate product formed by combination of the tetrazo compound of
a paradiamine with one molecule of salicylic acid, new polyazo colouring matters
are obtained which dye cotton dark brown shades without a mordant.
Similar brown dye-stuffs, slightly bluer in shade, are obtained by first com-
bining the "Colour A" with the intermediate product of the tetrazo compound and
salicylic acid, and finally causing the diazo compound, as for example diazonaph-
thionic acid, to act upon the mixed trisazo colouring matter thus formed.
In carrying out this invention the following procedure may be employed:
-

page_text: "
sodium nitrite. The diazonaphthol sulphonic acid, suspended in about 500 litres
of water, is then combined with a solution of 12.2 kilos. of metatoluylenediamine
in about 400 litres of water. After standing for some hours, the combination to
the Colour A" is finished and the brown precipitate is then dissolved by the
addition of 4 kilos. of caustic soda and 48 kilos. of sodium carbonate. After cooling
to 10 deg. C., 23.4 kilos. of diazonaphthionic acid, suspended in about 500 litres
of water, are slowly poured into the solution, the yellow-brown colour of which
is thereby changed into a dark red-brown. The combination being completed
after standing for about three hours, the diazo colour thus obtained is mixed, with
continuous stirring, with the intermediate product formed from the tetrazo com-
pound of 18.4 kilos of benzidine by combination with 15.0 kilos. of salicylic acid
in 700 litres of water, 4 kilos. of caustic soda, and 30 kilos. of sodium carbonate.
After 12 hours, the temperature of the deep brown solution is raised slowly to
about 40 deg. C., which is maintained for about six hours; it is then boiled off
and the new colouring matter is precipitated by the addition of about 500 kilos. of
common salt, filtered, pressed and dried. It dyes unmordanted cotton, in a bath con-
taining salt and rendered slightly alkaline by the addition of sodium carbonate,
deep brown shades of good fastness to light and soap. Shades possessing greater
fastness can be produced by boiling the goods with from 2 to 3 per cent. of
potassium bichromate or of copper sulphate or mixtures of them.
68
EXAMPLE II.
The 'Colour A" obtained from 34.1 kilos. of diazotised beta,alpha
amidonaphthol beta beta,disulphonic acid and 10.8 kilos. of metaphenylenedia-
mine is first combined, at a temperature not exceeding 15 deg. C., with the
intermediate product obtained from the tetrazo compound of 21.2 kilos. of tolidine,
15 kilos. of salicylic acid, 4 kilos. of caustic soda and 30 kilos. of sodium carbonate.
After 12 hours, 18.4 kilos of paradiazobenzole sulphonic acid, diluted with about
300 litres of water are poured into the mixed trisazo colouring matter and this
mixture is well stirred for some hours. The trisazo colouring matter, which was
at first almost entirely precipitated as a dark brown powder, enters, by combination
with the paradiazobenzole sulphonic acid, into solution and the new polyazo
colouring matter thus formed is precipitated at the boiling point by the addition
of about 500 kilos. of salt, and then filtered pressed and dried. It dyes unmor-
danted cotton a good brown having a yellowish shade.
The diazo compound of naphthionic acid or of paradiazobenzole sulphonic acid
specified under Examples I and II may be substituted by equivalent weights of
the diazo compounds of the following substances:-Alpha- or beta-naphthylamine;
alpha or beta-naphthylamine monosulphonic acids; amido-benzole or amido-
toluol monosulphonic acids; amidobenzol carbonic acids; nitraniline and nitroto-
luidine.
Further, in each of the examples, benzidine may be substituted by tolidine;
metaphenylenediamine by metatoluylenediamine; and salicylic acid by orthocreso-
tinic acid.
4
4
The new colouring matters obtained according to this invention as herein before
described, form a brown-black powder sparingly soluble in ethylic alcohol, but
easily soluble in hot water giving a brown solution which is converted into an
intense red-brown by the addition of caustic soda. They dissolve in strong sul-
phuric acid with a blue-violet colour and are thrown down on the addition of
water to the solution, as a brown precipitate. They dye unmordanted cotton
shades varying from yellowish brown to blue-brown, in a salt bath rendered 5
slightly alkaline.

page_text: The Manufacture or Production of Brown Polyazo Colouring Matters.
I, WILLIAM EDWIN HEYS, of 70, Market Street, Manchester, in the County of
Lancaster, 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; -
In the Specification of French Letters Patent No. 243,735, dated the 18th
December 1894, azo colouring matters are described which are produced by com-
bining diazo and tetrazo compounds with the azo compounds derived from diazo-
naphthol sulphonic acids and metadiamines. It is distinctly stated in the specifica-
tion referred to that one molecule of these monazo compounds has the property
of combining with one molecule of a diazo compound, the new azo group fixing
itself in the radicle of the metadiamine.
But my foreign correspondents have found that one molecule of the above men-
tioned monazo compounds, especially of those derived from diazotised beta,alpha,
amidonaphthol beta,beta,disulphonic acid (see Specification of German Letters
Patent No. 53023), and metaphenylenediamine or metatoluylenediamine having the
formula:
(which I will hereinafter call "Colour A"), is susceptible of combining with
two molecules of one and the same diazo compound or with one molecule of
two different diazo compounds.
By combining the colour A, first with a diazo compound, as for example with
diazonaphthionic acid, and by then combining the diazo colour thus obtained
with the intermediate product formed by combination of the tetrazo compound of
a paradiamine with one molecule of salicylic acid, new polyazo colouring matters
are obtained which dye cotton dark brown shades without a mordant.
Similar brown dye-stuffs, slightly bluer in shade, are obtained by first com-
bining the colour A with the intermediate product of the tetrazo compound and
salicylic acid, and finally causing the diazo compound, as for example diazonaph-
thionic acid, to act upon the mixed trisazo colouring matters thus formed.
EXAMPLE I.
34.1 kilos. of the acid sodium salt of beta,alpha,amidonaphthol beta,beta,
disulphonic acid is diazotised in the usual well known manner with 6.9 kilos. of
sodium nitrite. The diazonaphthol sulphonic acid, suspended in about 500 litres
of water, is then combined with a solution of 12.2 kilos. of metatoluylenediamine
in about 400 litres of water. After standing for some hours, the combination of
the colour A is finished and the brown precipitate is then dissolved by the addition
of 4.0 kilos. of caustic soda and 48.0 kilos. of sodium carbonate. "After cooling
to 10° C., 23.4 kilos. of diazonaphthionic acid suspended in about 500 litres
of water, is slowly poured into the solution, the yellow-brown colour of which
is thereby changed to a dark red-brown. The combination being completed
after standing for about three hours, the disazo colour thus obtained is mixed, with
continuous stirring, with the intermediate product formed from the tetrazo com-
pound of 18.4 kilos. of benzidine by combination with 15.0 kilos. of salicylic acid

page_text: in 700 litres of water, 4 kilos. of caustic soda and 30 kilos. of sodium carbonate.
After 12 hours, the temperature of the deep brown solution is raised slowly to
about 40° C., which is maintained for about six hours; it is then boiled off
and the new colouring matter is precipitated by the addition of about 500 kilos. of
common salt, filtered, pressed and dried. It dyes unmordanted cotton in a bath con-
taining salt and rendered slightly alkaline by the addition of sodium carbonate,
deep brown shades of good fastness to light and soap Shades possessing greater
fastness can be produced by boiling the goods with from 2 to 3 per cent. of
potassium bichromate, or copper sulphate or mixtures of them.
EXAMPLE II.
The colour A obtained from 34.1 kilos. of diazotised beta,alpha,
amidonaphthol beta,beta disulphonic acid and 10.8 kilos. of metaphenylenedia-
mine is first combined, at a temperature not exceeding 15° C., with the
intermediate product obtained from the tetrazo compound of 21.2 kilos. of tolidine,
15 kilos. of salicylic acid, kilos. of caustic soda and 30 kilos. of sodium carbonate.
After 12 hours, 18.4 kilos. of paradiazobenzole sulphonic acid, diluted with about
300 litres of water are poured into the mixed trisazo colouring matter and this
mixture is well stirred for some hours. The trisazo colouring matter which was
at first almost entirely precipitated as a dark brown powder enters into solution
and the new polyazo colouring matter thus formed is precipitated at the boiling
point, by the addition of about 500 kilos. of salt and then filtered off, pressed and
dried. It dyes unmordanted cotton a good brown having a yellowish shade.
The diazo compound of naphthionic acid or of paradiazobenzole sulphonic acid
specified under Examples I and II, may be substituted by equivalent weights of
the diazo compounds of the following substances: Alpha- or beta-naphthylamine,
alpha- or beta-naphthylamine monosulphonic acids, amidobenzole monosulphonic
acid, amidotoluol monosulphonic acid, amidobenzole, carbonic acids, nitraniline,
and nitrotoluidine.
Further, in each of the examples, benzidine may be substituted by tolidine;
metaphenylenediamine by metatoluylenediamine; and salicylic acid by orthocreso-
tinic acid.
The new colouring matters obtained according to this invention, as herein before
described, form a brown-black powder sparingly soluble in ethylic alcohol, but
easily soluble in hot water giving a brown solution which is converted into an
intense red-brown by the addition of caustic soda. They dissolve in strong sul-
phuric acid with a blue-violet colour and are thrown down on the addition of
water to the solution, as a brown precipitate. They dye unmordanted cotton
shades varying from yellow-brown to blue-brown, in a salt bath rendered
slightly alkaline.
Having now particularly described and ascertained the nature of my said
invention and in what manner the same is to be performed, as communicated to
me by my foreign correspondents, I declare that what I claim is:
1. The process for the production of substantive brown polyazo colouring mat-
ters which consists in combining one molecule of the azo colour beta,azoalpha
naphthol beta,beta disulphonic acid metaphenylene or metatoluylenediamine
(Colour A), with one molecule of a diazo-compound and combining the thus
obtained disazo colour with one molecule of the intermediate product obtained by
the combination of one molecule of tetrazodiphenyl or tetrazo ditolyl with
one molecule of salicylic acid or of orthocresotinic acid, substantially as herein-
before described.
2. The process for the production of substantive brown polyazo colouring mat-
ters which consists in combining one molecule of the azo colour beta,azoalpha
naphthol beta,beta,disulphonic acid metaphenylene or metatoluylenediamine
(Colour A), with one molecule of the intermediate product obtained by the com-

page_text: bination of one molecule of tetrazodiphenyl or tetrazoditolyl with one molecule of
salicylic acid or orthocresotinic acid and finally acting upon the resulting trisazo
dye-stuffs with one molecule of a diazo compound, substantially as hereinbefore
described.
3. As new articles of manufacture, the new polyazo colouring matters produced
as herein before described by the processes claimed in and by the first and second
claims.
590.
W. E. HEYS & SON,
Agents for the Applicant.