The Manufacture and Production of New Substantive Azo-colouring Matters.
Year: 1898

page_text: Date of Application, 29th Aug., 1898
Date of Application, 29th Aug., 1898
Complete Specification Left, 14th Apr., 1899—Accepted, 17th June, 1899
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Substantive Azo-colouring
Matters.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the German Empire), to be as follows:
In the Specifications of Letters Patent Nos. 14078 and 21753, both of 1893,
granted to me on communications from my foreign correspondents, the manu-
facture of meta-phenylene-diamine disulpho-acid, and its use in the manufacture
of azo-
o-dyes are described. In the Specification of Letters Patent No. 8564
of 1894 also granted to me on a communication from my foreign correspondents.
other new components for azo-dyes are described, namely, nitro-meta-diamines.
The present invention relates to the manufacture of new substantive dyes for
cotton, in which manufacture the components hereinbefore referred to are
used.
The new dyes are mixed disazo dyes, obtained by the combination of the
tetrazo-compound of a diamido-base, such as benzidine, or tolidine, with meta-
phenylene-diamine-disulpho acid and then with the nitro-diamine chosen.
My foreign correspondents have discovered that meta-phenylene-diamine-
disulpho acid behaves in a manner essentially different from meta-phenylene-
diamine itself, on treatment with tetrazo-diphenyl. No process is known whereby
a, so-called, intermediate product can be smoothly obtained by the union of one
molecular proportion of tetrazo-diphenyl with one molecular proportion of meta-
phenylene-diamine, but a finished disazo-dye, incapable of further combination,
appears to result, but such an intermediate product can most readily be obtained
when using meta-phenylene-diamine-disulpho acid. Even if this latter body be
present in considerable excess the combination of the tetrazo-compound with it
does not proceed beyond the formation of the intermediate product.
This intermediate product is a brownish body, difficultly soluble in water, and
it is by the combination of this said product with a nitro-meta-diamine that
the new dyes are produced.
The new dyes are characterized by extraordinary colouring power and a peculiar
fire, or brilliance, and possess great fastness against the action of washing, acids,
and light. They dye unmordanted cotton.
The following example will serve to further illustrate the nature of the inven-
tion. The parts are by weight.
Prepare a solution of tetrazo-diphenyl in the well known way, using about
ninety four parts of benzidine, three hundred and forty five parts of hydrochloric
acid, containing about 28 per cent. real HCI and seventy parts of sodium
nitrite, cool the tetrazo solution by means of ice, and render it alkaline by means
of soda. Run into this solution an aqueous solution of one hundred and fifty six
parts of the sodium salt of meta-phenylene-diamine-disulpho acid. Stir for about

page_text: six hours; after this period the formation of the red-brown intermediate product,
which is hardly at all soluble in water, will usually be complete. Collect this
product by filtering, mix it with water to form a thin paste, and add it to a
solution of about eighty parts of nitro-meta-phenylene-diamine in about thirty
thousand parts of water. This solution should be at a temperature of about
forty-five degrees Centigrade. Stir the mixture for about twelve hours, whilst
maintaining this temperature, then raise the temperature gradually to about
ninety degrees; add soda till alkaline and precipitate whilst hot by means of
common salt. Allow the precipitate to cool, filter press and dry.
In carrying out this invention other diamido bases (for instance tolidine) can
be employed instead of benzidine and nitro-meta-toluylene-diamine can be
employed instead of nitro-meta-phenylene-diamine.
The new colouring matters are slightly soluble in cold water and more soluble
in hot water. The solutions are of an orange colour which is hardly changed
by the addition of caustic soda. Mineral acids give a precipitate when added
to the solutions.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of New Substantive Azo-colouring
Matters.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me from abroad by the Badische Anilin & Soda Fabrik, of
Ludwigshafen on Rhine, in the German Empire), 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 Letters Patent Nos. 14678 and 21753 both of A.D. 1893
granted to me on communications from my foreign correspondents the manu-
facture of meta-phenylene-diamine-disulpho-acid, and its use in the manufacture
of azo-dyes are described. In the Specification of Letters Patent No. 8564
of A.D. 1894, also granted to me on a communication from my foreign corres-
pondents, other new components for azo-dyes are described, namely, nitro-meta-
diamines.
The present invention relates to the manufacture of new substantive dyes for
cotton, in which manufacture the components hereinbefore referred to
used.
are
The new dyes are mixed disazo dyes, obtained by the combination of the
tetrazo compound of a diamido base, such as benzidine, or tolidine, with meta-
phenylene-diamine-disulpho-acid, and then with the nitro-diamine chosen.
My foreign correspondents have discovered that meta-phenylene-diamine-
disulpho-acid behaves in a manner essentially different from meta-phenylene-
diamine itself, on treatment with tetrazo-diphenyl. No process is known whereby
a, so-called, intermediate product can be smoothly obtained by the union of one
molecular proportion of tetrazo-diphenyl with one molecular proportion of meta-
phenylene-diamine, but a finished disazo-dye, incapable of further combination,
appears to result; but such an intermediate product can be most readily obtained
when using meta-phenylene-diamine-disulpho-acid. Even if this latter body be

page_text: present in considerable excess the combination of the tetrazo-compound with it
does not proceed beyond the formation of the intermediate product.
This intermediate product is a brownish body, difficultly soluble in water, and
it is by the combination of this said product with a nitro-meta-diamine that
the new dyes are produced.
The new dyes are characterised by extraordinary colouring-power and a peculiar
fire or brilliance, and possess great fastness against the action of washing, acids,
and light. They dye unmordanted cotton.
The following example will serve to further illustrate the nature of the inven
tion and the manner in which it can be performed. The parts are by weight:
Prepare a solution of tetrazo-diphenyl in the well-known way, using about
ninety-four parts of benzidine, three hundred and forty-five parts of hydrochloric
acid, (containing about 28 per cent. real HCl) and seventy parts of sodium
nitrite. Cool the tetrazo solution by means of ice, and render it alkaline by means
of soda. Run into this solution an aqueous solution of one hundred and fifty-six
parts of the sodium salt of meta-phenylene-diamine-disulpho-acid. Stir for about
six hours after this period the formation of the red-brown intermediate product,
which is hardly at all soluble in water, will usually be complete. Collect this
product by filtering, mix it with water to form a thin paste, and add it to a
solution of about eighty parts of nitro-meta-phenylene-diamine in about thirty
thousand parts of water. This solution should be at a temperature of about
forty-five degrees Centigrade. Stir the mixture for about twelve hours, whilst
maintaining this temperature, then raise the temperature, gradually, to about
ninety degrees; add soda till alkaline, and precipitate, whilst hot, by means of
common salt. Allow the precipitate to cool, filter, press and dry."
In carrying out this invention tolidine can be employed instead of benzidine,
and nitro-meta-toluylene-diamine can be employed instead of nitro-meta-pheny-
lene-diamine.
The new colouring-matters are slightly soluble in cold water and more soluble
in hot water. The solutions are of an orange colour, which is hardly changed
by the addition of caustic soda. Mineral acids give a precipitate when added
to the solutions.
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
1. The manufacture of new substantive azo colouring-matters by the combina
tion of a tetrazo compound hereinbefore defined with meta-phenylene-diamine-
disulpho-acid, and then with a nitro-diamine hereinbefore set forth, all substan-
tially as herein before described.
2. The manufacture of a new orange substantive colouring-matter, substan-
tially in the manner described in the foregoing example.
3. As new articles of manufacture substantive azo colouring-matters such as
can be obtained, substantially as hereinbefore set forth.
Dated this 14th day of April 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.