Improvements in the Manufacture and Production of Colouring Matters.
Year: 1891

page_text: Date of Application, 12th Sept., 1891
Complete Specification Left, 18th May, 1892-Accepted, 25th June, 1892
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture and Production of Colouring
Matters.
We THE CLAYTON ANILINE COMPANY LIMITED of Clayton near Manchester
in the County of Lancaster and JOHN HALL of Clayton aforesaid Chemist do
hereby declare the nature of this invention to be as follows :-
It is known that meta-diamines such as meta-phenylene-diamine and meta-
toluylene-diamine combine with one or two molecular proportions of a diazo
compound. Those derived from one molecule of a diazo compound have been
known for a long time under the general name of chrysoidines.
The present
invention is based upon the discovery that meta-phenylene-diamine is capable of
combining three times with a diazo compound or with three different diazo
compounds and also that one molecular proportion of the product of the com-
bination of meta-phenylene diamine with two molecular proportions of a diazo
compound can be combined with a half molecular proportion of a tetrazo com-
pound yielding in each case brown compounds.
In the expression "diazo compounds' we include the bodies obtained by the
action of sodium nitrite and an acid on aromatic monamines, their carboxylic
and sulphonic acids and also on amido-azo compounds or their sulphonic acids
and in the expression "tetrazo compounds" we include the products derived
from certain aromatic diamines such as benzidine, its homologues, sulphonic acids,
and the like.
Certain of the new combinations especially those which do not contain a
sulphonic acid group are insoluble but they can be rendered soluble by sulpho-
nation with fuming sulphuric acid. To illustrate this invention we will describe
as an example a method of preparing a colouring matter from one molecular
proportion of meta-phenylene-diamine, one molecular proportion of naphthionic
acid and two molecular proportions of ortho-toluidine. The parts are by weight.
91 parts of meta-phenylene-diamine hydrochloride are dissolved in water (made
alkaline with sodium carbonate) and to this 'solution is added the diazo compound
obtained by treating 158 parts of naphthionate of sodium dissolved in water with
100 parts of hydrochloric acid and 35 parts of sodium nitrite. After stirring for
a time say 24 hours the diazo-toluol-chloride obtained from 53 parts of ortho-
toluidine is run into the azo compound and after a further stirring (say for
another 24 hours) an equal quantity of diazo-toluol-chloride is added. The
agitation is continued say for another 24 hours and the product is boiled up and
salted out filtered pressed and dried.
•
The colour so obtained dyes animal fibres a deep shade of brown.
During the whole time of combination the mixture is kept alkaline which may
be done with sodium carbonate or caustic soda. We have found that the shade
of brown obtained when caustic soda is used is redder than when sodium carbonate
is employed.
"
A colour is derived from one molecular proportion of meta-phenylene-diamine,
one molecular proportion of naphthionic acid, one molecular proportion of 'ortho-
tolidine and a half molecular proportion of benzidine, when, in a coinbination
made as hereinbefore described in the presence of sodium carbonate, the 53 parts
of ortho-toluidine are replaced by 92 parts of benzidine.
This colour dyes unmordanted cotton brown.

page_text: COMPLETE SPECIFICATION.
Improvements in the Manufacture and Production of Colouring
Matters.
We, THE CLAYTON ANILINE COMPANY LIMITED of Clayton, near Manchester
in the County of Lancaster and JOHN HALL. of Clayton aforesaid Chemist 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:-
It is known that meta-diamines, such as meta phenyline-diamine and meta-
toluylene diamine combine with one or two molecular proportions of a diazo
compound. The products derived from this combination with one molecular
proportion of a diazo compound have been known for a long time under the general
naine of the "chrysoidines." According to this invention it has been found that
meta-phenylene-diamine is capable of combining three times with a diazo compound
or with three different diazo compounds, and also that any one of the three diazo
compounds may be replaced by an equivalent quantity of a tetrazo compound,
yielding in each case, brown compounds, but useful compounds are only obtained, if
the first or second, or both the first and second molecular proportion of the diazo
or the tetrazo compound be in the form of a sulphonic acid thereof.
Under the expression "diazo compounds," we include those obtained by the
action of sodium nitrite and a mineral acid on aniline or its sulphonic acids, or on
homologues of aniline or their sulphonic acids, or on the naphthylamines or their
sulphonic acids, or on amido-azo-benzol, or its sulphonic acids and homologues
thereof or on the amido-azo-naphthalenes or their sulphonic acids.
Under the expression "tetrazo-compounds' we include the products derived
from benzidine, tolidine, dianisidine, diamido-stilbene, disulphonic acid and the
like.
22
To illustrate this invention we give the following as examples, illustrating the
best means with which we are acquainted for carrying the invention into effect.
EXAMPLE 1.
To make a colouring matter from one molecular proportion of meta-phenylene-
diamine, one molecular proportion of naphthionic acid, and two molecular proportions
of ortho-toluidine. (The parts are by weight.) 91 parts of meta-phenylene-diamine
hydrochloride, are dissolved in water (made alkaline with sodium carbonate) and
to this solution is added the diazo compound obtained by treating 158 parts of
naphthionate of sodium dissolved in water with 100 parts of hydrochloric acid and
35 parts of sodium nitrite. After stirring for about 24 hours, the diazo-toluol
chloride (which may be obtained from 53 parts of ortho-toluidine in the usual way)
is run into the azo-compound and after a further 24 hours stirring, a further and
equal quantity of the diazo-toluol chloride is added. During the whole time the
combination is kept alkaline by means of sodium-carbonate or caustic soda.
have found that when caustic soda is employed the shades of the colouring matters
obtained are redder than are those obtained when sodium carbonate is used. After
standing for another day the product is boiled up salted out filtered pressed and
dried. The colouring matter obtained in this way, dyes animal fibre a deep shade
of brown.
EXAMPLE 2.
We
A colouring matter is obtained from one molecular proportion of meta-phenylene
diamine, one molecular proportion of naphthionic acid, one molecular proportion of
ortho-toluidine, and a half molecular proportion of benzidine, when in a com-
bination made as in Example 1 in the presence of sodium carbonate the last mandin

page_text: of diazo-toluol-chloride is replaced by the tetrazo-di-phenyl-chloride obtained from
46 parts of benzidine. The colouring matter thus produced dyes unmordanted
cotton brown.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed we declare that what
we claim is :―
1. The production of colouring matters by combining one molecular proportion
of meta-phenylene-diamine, with three molecular proportions of a diazo compound
or of different diazo compounds, the first or second, or both first and second
molecular proportions of diazo compound combined being in the form of diazo
sulphonic acids.
2. The production of colouring matters by combining one molecular proportion
of meta-phenylene-diamine, with two molecular proportions of a diazo compound,
and a half molecular proportion of a tetrazo compound in any order, the first or
second, or both first and second, of the compounds combined, being in the form of
sulphonic acids.
3. As new articles of manufacture colouring matters such as are produced by
proceeding according to the processes hereinbefore described and claimed.
Dated this 18th day of May 1892.
J. H. JOHNSON & Co.,
Agents.