Improvements in the Manufacture of Colouring Matters.
Year: 1898

page_text: [Communicated from abroad by FARBWERKE MÜHLHEIM, formerly A. Leonhardt & Co.,
of Mühlheim on the Main, in the Empire of Germany, Manufacturers.]
[Communicated from abroad by FARBWERKE MÜHLHEIM, formerly A. Leonhardt & Co.,
of Mühlheim on the Main, in the Empire of Germany, Manufacturers.]
Improvements in 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:-
In the Specification of former Letters Patent No. 18783 of 1891 a series of
colouring matters is described deriving from 1.4 naphthylenediamine and containing,
as one component, betanaphthol or sulphoacids of betanaphthol, and as second
component, alphanaphthylamine or naphthionic acid..
The use of the alphanaphthylamine sulphoacids of Cleve is not described in the
Specification of this Patent.
Now I have found that such tetrazodyes, containing alphanaphthylamine or
naphthionic acid as one component, when dyed on cotton fibre and diazotized and
developed on the fibre with betanaphthol, yield useless dirty and weak shades. On
the other hand, when Cleve's acids are employed as one component, beautiful and
fast blue shades are obtained by the same treatment.
I have further found that the same is the case regarding dyestuffs deriving, not
from 1.4 naphthylenediamine itself, but from sulphoacids of 1.4 naphthylenediamine.
According to this, the nature of the present invention may be defined as
producing tetrazodyestuffs from diazoderivatives of the following generic formula
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvements in 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:
In the Specification of former Letters Patent No. 18783 of 1891 a series of colouring
matters is described derived from 1.4 naphthylenediamine and containing as one
component naphtholsulphoacids, and as a second component a naphthylamine or
naphthionic acid.
If those tetrazodyestuffs be dyed on cotton fibre and diazotised and developed on
"the fibre with ẞ naphthol useless dirty and weak shades are obtained.
But I have ascertained, that if, in those tetrazodyestuffs the second component,
that is to say the a naphthyl amine, or the naphthionic acid, be replaced by the
so called Cleve's acids (a, naphthylamine 3 or 4 sulphoacids) new colouring
matters result (not described in the above cited Patent) which when treated in quite
an analogous manner yield beautiful and very fast blue shades.
I have further found that the same remarkable difference exists in the colouring
matters which derive instead from the 1.4 naphthylenediamine, from the sulpho-
acids of this colour base. That is to say:
Dyestuffs of the general formula
yield indigo-blue shades of great technical value if treated in the same manner.
Dyestuffs derived from 1.4 naphthylenediamine sulpho-acids have been produced
according to former Letters Patent No. 15444 of 1893, No. 2946 of 1896, and No.
17064 of 1896, but in all these Patents as well as in Letters Patent No. 18783 of
1891 colouring matters containing Cleve's a naphthylaminesulphoacids as a second
component are not described.
According to my experience the dyestuffs forming the subject of the present
Specification and containing Cleve's acids as a second component are best produced
from 1.4 amidoacet naphthalide or its 6 or 7 monosulphoacid (which latter may f. i.
be produced as is well known by sulphonating 1.4 amidoacetnaphthalide). By
diazotizing the 1.4 amidoacetnaphthalide or its sulphoacids combining the diazo body
thus obtained with a suitable naphtholsulphoacid, saponifying the resulting acetyl-
amidoazo colouring matter and diazotizing it again diazo-azobodies are obtained of the
following general formula:

page_text: (wherein x signifies the rest of a naphtholsulphoacid and y signifies hydrogene or the
sulphogroup). I wish it to be understood that I do not claim as my invention the
production of such diazo-azobodies in any way, such production being well known at
the time. What I claim is only the combination of those diazo-azobodies with Cleve's
acids (a, naphthylamine ẞ, or B₁ sulphoacid, or the mixture of both obtained f. i. in
the well known manner by nitrating and subsequent reduction of ẞ naphthalene-
monosulphonicacid) which combination as well as its valuable effect has not yet been
described.
Amongst naphtholsulphoacids the 1 naphthol 4 sulpho acid, the 2 naphthol
6 monosulphoacid and the 2 naphthol 7 monosulphoacid have given the best
results.
The final combination with Cleve's acids is preferably carried out in acetic acid
solution, if therefore free mineral acid be present, it should be neutralized by sodium
acetate and it is also preferable to add some common salt to the solution so that the
dyestuff, when formed, is immediately precipitated.
According to this I proceed f. i. as follows:
2 kilos. of 1.4 amidoacetnaphthalide are diazotized and then combined in an alkaline,
preferably, sodium carbonate solution with 2.5 kilos. of a, naphthol a, sulphoacid
(Neville & Winther acid). The resulting red acetylamidoazo-colouring matter is
salted out hot filtered and pressed. For the saponification of it, it is dissolved in
about 50 litres of hot water, 10 litres of caustic soda lye of 30 % are added and the
whole is boiled, preferably on the reflux cooler, for some time. The reaction is
finished if a sample taken out and diluted with hot water on the addition of hydro-
chloric acid does not yield any more a bluish red solution, but insoluble red
flakes.
If this stage be reached, the whole mass is diluted with hot water, the saponified
dyestuff then precipitated by the addition of a suitable amount of hydrochloric acid
filtered and pressed.
For diazotizing it, the presscake thus obtained, corresponding to about 4.5 kilos.
dry substance, is dissolved in about 100 1. of water and 2 litres of caustic soda
Jye 30%, or the corresponding amount of any other suitable alkali, 0.7 kilos.
of sodium nitrate are added and the solution thus obtained is allowed to run gradually
whilst stirring into dilute hydrochloric acid, consisting of about 200 1. of water and
101. hydrochloric acid 30%.
When after standing for about 12 hours the diazotization is completed the resulting
insoluble brown diazobody is preferably filtered off.
It is then mixed with about 50 kilos. of common salt to a paste, the free mineral
acid present is removed by adding about 4 kilos. of sodium acetate and to the whole
mass is then poured whilst continuously stirring a concentrated aqueous solution
containing 2.5 kilos. of the sodium salt of Cleve's a naphthylaminesulphonic acid.
Stirring is continued for about 12 hours when the combination is finished.
The resulting blue colouring matter is in a precipitated state. For purifying it
the whole mass is diluted with about 400 litres of boiling water and made alkaline by
the addition of sodium carbonate. The colouring matter is then filtered off pressed
and dried. The mother liquor contains a deep red by-product.
If necessary the purification may be repeated, that is to say the pressed dyestuff
may be redissolved in sodium carbonate solution salted out again and worked up in
the usual manner.
The colouring matter thus produced represents in a dry state a dark powder of a
metallic lustre, soluble in hot water or in concentrate sulphuric acid with a blue
colour scarcely soluble in spirit and dyeing unmordanted cotton blue shades the
fastness of which is greatly improved by diazotizing on the fibre and developing with
8 naphthol.
Other dyestuffs containing instead of 1 naphthol 4 sulphoacid, other suitable
naphthol sulphoacids, or such in which the 1.4 naphthylenediamine is replaced by its
6 or 7 sulphoacid can be produced in quite an analogous manner.

page_text: 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 process for the production of mixed tetrazo colouring matters, which process
consists in combining diazoazobodies of the general formula
Dated this 6th day of July 1899.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.