Manufacture of New Violet, Blue, Grey, and Black Substantive Colouring Matters for Dyeing Cotton.
Year: 1894

page_text: Date of Application, 19th May, 1894-Accepted, 23rd June, 1894
COMPLETE SPECIFICATION.
Manufacture of New Violet, Blue, Grey, and Black Substantive
Colouring Matters for Dyeing Cotton.
We, JEAN CLAUDE LOUIS DURAND, DANIEL EDOUARD HUGUENIN, and
ADOLPHE JEAN JAMES D'ANDIRAN, constituting the Firm of L. Durand
Huguenin & Co., of Basle, Switzerland, Manufacturers, 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 to Patent No. 8511 of 27th April 1893 it was shewn that the
tetrazo compounds of the condensation products, from formaldehyde on the one
hand, and benzidio tolidin or dianisidin on the other hand, if brought together in
the proportion of equal molecules, for example, with naphthyl-amin sulpho acids,
form insoluble intermediate products which still contain a free diazo group, and
which can be used for the manufacture of tetrazo colouring matters. In the course
of further experiments we have found that also the unsymmetrically constituted
bases described in the Specification to Patent 12,704 of 28th June 1893 form
analogous insoluble intermediate products which can combine with a second
molecule of an amine or a phenol or their sulpho acids.
In using the unsymmetrical bases however the sequence of the combinations' is
not immaterial; there are produced, according to these, two isomeric colouring
matters which often differ considerably in their tints.
Furthermore, we have found that by combination of amidonaphthol disulpho
acid 1.3. 6. 8, or amidonaphtholmono sulpho acid 2. 6. 8 with the tetrazo derivatives
of the diamido bases from formaldehyde and tolidin or dianisidin, or from
formaldehyde, tolidin or dianisidin and anilin, ortho amidophenol, or meta or
para-phenylen diamin (described in the Specifications Nos. 9360 of 1892, 12704 of
1893, 20,301 of 1893 and 20790 of 1893) very important blue and grey tetrazo
colouring matters are produced, which can be further diazotised, and whose diazo
compounds, when combined with metaphenylendiamin, give grey and black
polyazo-colouring matters.
1.
As examples we give the manufacture of the following commercially important
I. COLOURING MATTER FROM FORMALDEHYDE-DIANISIDIN, NAPHTHYLAMIN-
SULPHO ACID 14, AND NAPHTHOL SULPHO ACID 1.4.
5 kilos. of the condensation product from formaldehyde and' dianisidin are
diazotised in the known manner by means of 7 kilos. hydrochloric acid of 21° Bè.
and 14 kilos. nitrite.
.
The tetrazo compound is then poured under stirring into a solution of 25 kilos.,
naphthionate of soda and 4 kilos, acetate of soda.
After a short time the formation of the above mentioned intermediate product,
in the form of a black-brown precipitate, is completed.
If now there be poured into the reaction mass a solution of 2.5 kilos. naphthol
sulphonate of soda and 5 kilos. carbonate of soda, there is formed a mixed tetrazo"
colouring matter.
$
After standing for 12 hours, the mass is filtered, pressed, and dried; the new
colouring matter then appears as a black-brown powder soluble in hot water, which
dyes unmordanted cotton violet in an alkaline bath. The solution of the colouring
matter in concentrated sulphuric acid is blue-grey.

page_text: The polyazo colouring matters thus obtained dye unmordanted cotton in the
tints set forth in the following table, which also gives the tints of their solutions
in concentrated sulphuric acid.
Having now particularly described and ascertamed the nature of this inven-
tion and in what manner the same is to be performed we declare that what
we claim is :—
1. Manufacture of a violet substantive colouring matter for cotton by the
combination of one molecule of the tetrazo compound of the condensation
product from dianisidin and formaldehyde described in the Specification to
Patent 9360, with one molecule of napthylamin sulpho acid 1-4 and with one
molecule of naphtholsulpho acid 1.4.
2. Manufacture of a blue-violet substantive colouring matter for cotton by
the combination of one molecule of the tetrazo compound of the condensation
product from formaldehyde dianisidin and anilin described in the Specification
to Patent 127043 with one molecule naphthylamine sulpho acid 14 to form an
intermediate product that is afterwards combined with one molecule of naphthol-
sulpho acid 1.4.
3. Manufacture of a red-violet substantive colouring matter for cotton by the
combination of one molecule of the tetrazo compound of the condensation product from
formaldehyde dianisidin and anilin, described in the Specification to Patent 127049
with one molecule of naphtholsulpho acid 14 to form an intermediate product,
that is afterwards combined with one molecule of naphthylaminsulpho acid 14.
4. Manufacture of blue-violet to green-blue substantive colouring matters for
cotton by the combination of two molecules of amidonaphtholdisulpho acid 1. 3.
6.8 with one molecule of the tetrazo compounds of the condensation product of
formaldehyde with tolidin (Patent No. 9360) or tolidin and ortho amidophenol
(Patent No. 20790%) or of formaldehyde with dianisidin and anilin, or
m. phenylendiamin (Patents 12704 and 20301).
5. Manufacture of grey to grey-violet substantive colouring matters for cotton

page_text: by combination of 2 molecules of amido-naphtholmonosulpho acid 2. 6. 8 with
one molecule of the tetrazo compounds of the condensation products from form-
aldehyde with tolidin (Patent "No. 9360%) or tolidin and orthoamidophenol
(Patent No. 20790°) or formaldehyde with dianisidin and anilin or m. pheylen--
diamin (Patents No. 12704 and 20301°*).
6. Manufacture of grey and black polyazo colouring matters by combination:
of metaphenylendiamine with the diazo compounds of the tetrazo colouring matters
referred to in Claims 4 and 5 which are produced by the combination of two
molecules of amidonaphtholmonosulpho acid 2. 6. 8 or of amidonaphtholdi--
sulpho acid 1. 3. 6. 8. with one molecule of the tetrazo compound of the con-
densation product from formaldehyde with tolidin and orthoamidophenol or
formaldehyde with dianisidine and anilin or metaphenylendiamine.
7. As new articles of manufacture, the substantive colouring matters for cotton
herein described and referred to in the preceding claims.
Dated this 19th day of May 1894
ABEL & IMRAY,
Agents for the Applicants..