Improvements in, and relating to, the Manufacture of Colouring Matters.
Year: 1899

page_text: [Communicated from abroad by the Firm of A. OEHLER, of Offenbach on the
Main, in the Empire of Germany, Manufacturers.]
Improvements in, and relating to, the Manufacture of Colouring
Matters.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, do hereby declare the
nature of this invention to be as follows:-
By the action of diazo compounds in an alkaline solution upon those colouring
matters, which are derived from diazotised amido naphthol sulphonic acids and
meta phenylene diamine or meta toluylene diamines respectively the combina-
tion takes place in the benzene radicle.
Now, my investigations have led to the surprising discovery, that, contrary to
all previous experience, the combination will take place in the naphthalene
radicle, if in the before mentioned action the said meta-diamines are replaced by
those of their sulphonic or carboxylic acids, which are able to combine with
two molecular proportions of a diazo compound.
Thus a great number of new and valuable dyestuffs are obtained both for
cotton and for wool.
By the action of diazo compounds of simple amines or their substitution
derivatives, brown to brown black dyestuffs result; diazotized amido com-
pounds yield brown to greenish black dyestuffs.
Products of a particular value are obtained by using benzidine or similar
bases.
If equimolecular proportions of the base and of the monoazodyestuff enter
into reaction, intermediate products coupled in the naphthalene radicle are
first obtained, which may be combined with a further molecule of the same or of
another monoazodye, or with one molecule of an amine, phenol, amidophenol, or
their sulphonic or carboxylic acids, thus vielding poly azo colouring matters.
The process for the production of the dyestuffs may be carried out also by
first forming an intermediate product from benzidine with one molecule of an
amine, phenol, amidophenol or their sulphonie- or carboxylic acids and then
combining this intermediate product with one molecule of a mono azo colouring
maiter.
These dyestuffs dye cotton without mordants go easily on the fibre, they
possess a considerable colouring power, and, though readily soluble, effectively
resist soaping.
Most of them may be discharged with bisulphite and zinc or with stannous
chloride, pure white discharging effects being obtained: they may also be

page_text: diazotised either in substance or upon the fibre and developed, or combined with
diazocompounds, thus yielding very full and heavy dark shades of a good fastness.
Dated this 15th day of December 1899.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
Improvements in, and relating to, the Manufacture of Colouring
Matters.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake & Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, 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:—
By the action of diazo compounds in an alkaline solution upon those coloring
matters which are derived from diazotized amido naphthol sulphonic acids and
meta-phenylene diamine or meta-toluylene diamine respectively, the combina-
tion takes place in the benzene radicle.
In the course of my investigations I have discovered that, contrary to all
previous experiences, the combination will take place in the naphthalene radicle
if, in the before mentioned action, the said metadiamines are replaced by those
of their sulphonic- or carboxylic acids.
Thus a great number of new and valuable dyestuffs are obtained capable of
dyeing both cotton and wool.
By the action of diazo compounds of simple amines or their substitution
derivatives, brown to brown black dyestuffs are obtained while diazotized
amido compounds yield brown to greenish black dyestuffs.
Products of a particular value are obtained by using benzidine or similar
bases.
If equimolecular proportions of the base and of the monoazodyestuff enter
into reaction, intermediate products coupled in the naphthalene radicle are
first obtained, which may be combined with a further molecule of the same or
of another monoazodve, or with one molecule of an amine, phenol amidophenol,
or their sulphonie- or carboxylic acids, thus yielding poly azo coloring matters.
The process for the production of the dyestuffs may be carried out also by
first forming an intermediate product from benzidine with one molecule of an
amine, phenol, amidophenol, or their sulphonic- or carboxylic acids, and then
combining this intermediate product with one molecule of a mono azo coloring
matter.
These dyestuffs are well adapted for dyeing cotton without mordants, inasmuch
as they go easily on the fibre, possess a considerable colouring power, and,
though readily soluble, effectively resist the action of soap.
Most of them may be discharged with bisulphite and zinc dust or with stannous
chloride, pure white discharging effects being obtained: they may also be
diazotized either in substance or upon the fibre and developed, or combined with
diazo compounds, thus yielding very full and heavy dark shades of a fast
character.
In preparing poly azo dyes of such a kind, all those amido naphthol sulphonic
acids are suitable which are susceptible of being readily diazotized. In a similar
manner. the above mentioned toluylene diamines may be replaced by any

page_text: sulpho conjugated or carboxylated meta-phenylene- or meta-toluylene diamine,
capable of combining twice."
In the following description I shall give an example of the manner in which the
process is to be carried out for obtaining mixed substantive trisazo dyestuffs
from one molecule of a para-diamine, one molecule of a mono azo coloring
matter, and one molecule of an amido maphthol sulphonic acid.
The mono azo coloring matters are prepared in the known manner by com-
bining in an acetic acid or alkaline solution the amido naphthol sulphonic acids,
diazotized as usual, with the sulphonic acids of the meta-diamines.
Proceed as follows, the parts being by weight.
Prepare in the usual way from 18.4 parts of benzidine or from the equivalent
quantity of tolidine or dianisidine a tetrazo compound, and pour it into a strong
soda-alkaline dissolution of 50 parts of the sodium salt of the mono azo coloring
matter, derived from amido naphthol mono sulphonic acid G and toluylene
diamine sulphonic acid: the intermediate product is immediately formed, and
most of it separates as a black precipitate. Upon adding a solution of 26.5 parts
of the sodium salt of the 2:8 amidonaphthol sulphonic acid G, the formation of
the dyestuff begins quickly and is completed after 12 hours. Then heat, pre-
cipitate with common salt. filter, press and dry.
The coloring matter thus obtained forms a brown black powder, easily soluble
in water with a dark blue colour, and dyes unmordanted cotton black.
With tolidine and dianisidine similar dyestuffs are obtained, but of a more
greenish shade, and with 2:8-amidonaphthol disulphonic acid, products of
greater solubility result. By employing 2-amido-5-naphthol-7-sulphonic acid.
products yielding more bluish shades are obtained.
The following is an example for obtaining dyestuffs from para-diamines and
two molecular proportions of the mono azo dyestuffs of 2:8 amido naphtol
sulphonic acids and toluvlene diamine sulphonic acids.
The mono azo dyestuffs are prepared in the usual manner by combining in
an acetic acid or soda-alkaline solution the amido naphtol sulphonic acids,
diazotized in the usual way with the sulphonic acids of the meta-diamiñes.
The parts are by weight.
Prepare in the well known manner from 18.4 parts of benzidine or from the
equimolecular proportion of tolidine or dianisidine, the tetrazo compound and
pour it, whilst keeping alkaline into a dissolution from 100 parts of the sodium salt
of the monoazo dyestuff derived from amido-naphtol monosulphonic acid G and
toluylene diamine sulphonic acid. After 24 hours, when the formation of the
dyestuff is finished, heat to about 80- to 90 degrees Centigrade, precipitate with
common salt. filter, press and dry.
The dyestuff thus obtained, forms a dark grey to black powder with a metallic
lustre which is readily soluble in water with a deep blue black colour and which
dves unmordanted cotton a full black.
By using tolidine or dianisidine, dyestuffs result of similar properties but
of a greenish shade: and by employing 2:8-amido-naphtol disulphonic acid,
products are obtained, being more readily soluble. By using 2-amido-5-naphtol-
7-sulphonic acid products yielding more bluish shades are obtained.
Having now particularly described and ascertained the nature of the 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 manufacture and production of new polyazo-dyestuffs, which consists
in combining the intermediate products, resulting from the reaction of monoazo-
dves, as derive from diazotized amido-naphtol sulphonic acids and meta-phenylene
diamine- or meta-toluylene diamine-sulphonic- or carboxylic acids, upon a para-
diamine, with one molecular proportion of the same or of a different mono azo
dye, or with one molecule of an amine, phenol, amidophenol, their sulphonic or

page_text: carboxylic acids either in the succession cited, or vice versa, substantially as
hereinbefore described.
2. As new articles of manufacture, the new polyazodyestuffs obtained as herein
described and claimed.
Datad this 17th lov of August 1900
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.