The Manufacture of New Polyazo Dyestuffs.
Year: 1898

page_text: Date of Application, 12th Nov., 1898
Complete Specification Left, 1st Aug., 1899-Accepted, 23rd Sept., 1899
PROVISIONAL SPECIFICATION.
The Manufacture of New Polyazo Dyestuffs.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of
London, Patent Agent, do hereby declare the nature of this invention (which has
been communicated to me from abroad by Kalle & Co., of Biebrich-on-Rhine, in
the German Empire,) to be as follows:-
Primary disazo colouring matters having the property of forming lakes with
metallic salts, have not hitherto been prepared. It has hitherto been impossible
to combine amidonaphtolsulpho acids with diazo compounds containing two acid
groups, like the hydroxyl and the carboxyl-group in ortho-position. Even the
amido naphtolsulpho acid K, the combining energy of which is so much greater
than that of the isomere compounds, scarcely enters into reaction in acid solution
with diazosalicylic acid, and it is also impossible to unite the latter compound
with the monoazo colours obtained by combination of amidonaphtolsulpho acids
with diazo compounds in acid solution.
My foreign correspondents have now found that with certain amidonaphtols-
sulpho acids, this difficulty can be overcome by introducing alpha-naphtylamine,
or 1.6 or 1.7-naphtylaminesulpho acid; that is to say, if diazosalicylic acid be
first combined with either of these three bodies, and if the so called amidoazo color
be diazotized again, the resulting diazoazo compound can be combined with amido-
naphtoldisulpho acid K and with amidonaphtolsulpho acid S, in the first, as well
as in the second place, yielding azo dyestuffs of great technical value. Besides
the valuable properties generally appertaining to primary disazo colours these
dyestuffs have the advantage of forming very fast lakes, when treated on the fibre,
with chromium salts. The lakes differ very little in shade from the original dyes.
The new dyestuffs are brown powders with metallic lustre, easily soluble in
warm water, soluble in concentrated sulphuric acid forming a blue to greenish
blue solution. By diluting with water the solutions in concentrated sulphuric
acid the free sulpho acids of the colouring matters are precipitated. The new
dyestuffs dye dark green to greenish-black shades on wool.
EXAMPLE I.
15.5 kilos. of amidosalicylic acid are diazotized in the usual manner, and com-
bined in the presence of sodium carbonate, with 24.5 kilos. of 1.7 naphtylamine-
sulphonate of soda. After the formation of the intermediate product is finished
it is transformed into the diazoazo body by acidulating with hydrochloric acid
and adding 7 kilos. of sodium nitrite. The mass so obtained is run into an alkaline
solution containing the ortho-amidoazo colouring matter formed by combining
14.5 kilos. of alpha-naphthylamine with 34.1 kilos. of amidonaphtoidisulpho
acid K. After stirring the combination is completed. The mass is then heated
and the dyestuff precipitated by adding common salt and the said precipitate
separated from the mother liquor by filtration, and dried. It dyes a blackish-
green on wool from an acid bath. Chroming alters the shade only very little,
but it increases the fastness considerably.

page_text: EXAMPLE II.
The amidoazo colouring matter, obtained from 15.5 kilos. amidosalicylic acid
and 14.5 kilos. of alpha-naphthylamine, is diazotised by adding an excess of hydro-
chloric acid and 7 kilos. of sodium nitrite. The diazoazo compound is put into
reaction, in the presence of alkali, with the orthoamidazo colour prepared from
9.3 kilos. of aniline and 34.1 kilos. of amidonaphtoldisulpho acid K. After
stirring, by which the combination is completed, the mass is heated. The dye-
stuff is then salted out, separated from the mother liquor, by filtration, pressed,
and dried. It dyes green on wool from an acid bath. By subsequent treatment
with a chromium salt the fastness of the dye is considerably increased.
EXAMPLE III.
The amidoazo colouring matter, obtained from 15.5 kilos. of amidosalicylic
acid and 24.5 kilos. of 1.7-naphtylaminesulphonate of soda, is transformed into
the diazoazo compound by means of 7 kilos. of sodium nitrite and 40 kilos. of
hydrochloric acid. This diazoazo body is put into reaction, in the presence of
an excess of sodium carbonate, with the monoazo colour obtained by combining
9.3 kilos. of aniline and 24 kilos. of amidonaphtolsulpho acid S, in the presence of
free hydrochloric acid. After stirring the mass is heated up. The dyestuff is
then salted out, filtered, pressed, and dried. It dyes a greenish-black on wool
from an acid bath. By subsequently treating the dye with a chromium salt the
fastness and depth is materially increased.
EXAMPLE IV.
The amidoazo colouring matter, prepared from 15.5 kilos. of amidosalicylic acid
and 24.5 kilos. of 1.7 naphtylaminesulphonate of soda, is transformed into the
diazoazo compound. A solution of 24 kilos, of amidonaphtolsulpho acid S and
5.3 kilos, of sodium carbonate is then run into the acid liquid containing the
diazoazo body in suspension. In order to finish the combination, a quantity of
sodium acetate, corresponding to the free acid present, is added.
After some
hours stirring the mass is neutralized by means of caustic soda. An excess of
sodium carbonate is then added to the solution so obtained and a diazo solution,
prepared in the usual manner, from 10.7 kilos. of paratoluidine, is run into it.
The dyestuff is then isolated as described in the previous examples. It dyes a
greenish-black on wool, from an acid bath. By subsequently treating the dye
with a chromium salt the fastness is materially increased.
Dated this 12th day of November 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
I, GEORGE WILLIAM JOHNSON, of 47, Lincoln's Inn Fields, in the County of
London, Chartered Patent Agent, do hereby declare the nature of this invention
(which as been communicated to me from abroad by Kalle & Co., of Biebrich-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 :-
-
Primary disazo colouring matters having the property of forming lakes with
metallic salts, have not hitherto been prepared. It has hitherto been impossible
to combine amidonaphtol-disulpho acids with diazo compounds containing the
hydroxyl and the carboxyl-group in ortho-position. Even the amidonaphtol-

page_text: disulpho acid K, the combining energy of which is so much greater than that of
the isomeric compounds, scarcely enters into reaction in acid solution with diazo-
salicylic acid, and it is also impossible to unite the latter compound with the
monoazo colours obtained by combination of amidonaphtoldisulpho acids with
diazo compounds in acid solution.
My foreign correspondents have now found, that with certain amidonaphtol-
sulpho acids this difficulty can be overcome by introducing alphanaphtylamine
or 1.6 or 1.7-naphtylaminesulpho acid; that is to say, if diazosalicylic acid be
first combined with either of these three bodies, and if the amidoazo colour so
obtained be diazotised again, the resulting diazoazo compound can be combined
with amidonaphtoldisulpho acid K and with amidonaphtolsulpho acid S in the
first, as well as in the second place, yielding azo dyestuffs of great technical value.
Besides the valuable properties generally appertaining to primary disazo colours
these dyestuffs have the advantage of forming very fast lakes, when treated, on
the fibre, with chromium salts. The lakes differ very little in shade from the
original dyes.
The new dyestuffs are brown powders with metallic lustre, easily soluble in
warm water, soluble in concentrated sulphuric acid forming a blue to greenish
blue solution. By diluting with water the solutions in concentrated sulphuric
acid, the free sulpho acids of the colouring matters are precipitated. The new
dyestuffs dye dark green to greenish-black shades on wool.
EXAMPLE I.
15.5 kilos. of amidosalicylic acid are diazotised in the usual manner,
and com-
bined, in the presence of sodium carbonate, with 24.5 kilos. of 1.7-naphtylamine-
sulphonate of soda. After the formation of the intermediate product is finished
it is transformed into the diazoazo body by acidulating with hydrochloric acid
and adding 7 kilos. of sodium nitrite. The mass so obtained is run into an
alkaline solution containing the orthoamidoazo colouring matter formed by com-
bining the diazo compound obtained from 14.5 kilos. of alpha-naphtylamine
with 34.1 kilos. of amidonaphtoldisulpho acid K. After stirring the combination
is completed. The mass is then heated, and the dyestuff precipitated by adding
common salt and the said precipitate separated from the mother liquor by filtration,
pressed and dried. It dyes a blackish-green on wool from an acid bath. Chrom-
ing alters the shade only very little, but it increases the fastness considerably.
EXAMPLE II.
The amidoazo colouring matter, obtained from 15.5 kilos. of amidosalicylic
acid and 14.5 kilos. of alpha-naphtylamine, is diazotised by adding an excess of
hydrochloric acid and 7 kilos. of sodium nitrite. The diazoazo compound is put
into reaction in the presence of alkali, with the ortho-amidoazo colour prepared
from the diazo compound obtained from 9.3 kilos. of aniline with 34.1 kilos of
amidonaphtoldisulpho acid K. After stirring, by which the combination is com-
pleted, the mass is heated, The dyestuff is then salted out, separated from the
mother liquor by filtration, pressed and dried. It dyes green on wool from an
acid bath. By subsequent treatment with a chromium salt the fastness of the
dye is considerably increased.
EXAMPLE III.
The amidoazo colouring matter obtained from 15.5 kilos of amidosalicylic acid
and 24.5 kilos. of 1.7-naphtylaminesulphonate of soda, is transformed into the
diazoazo compound by means of 7 kilos. of sodium nitrite and 40 kilos. hydro-
chloric acid. This diazoazo body is put into reaction, in the presence of an excess
of sodium carbonate, with the monoazo colour obtained by combining the diazo
compound obtained from 9.3 kilos. of aniline with 24 kilos. of amidonaphtolsulpho
acid S in the presence of free hydrochloric acid. After stirring the mass is
heated up. The dyestuff is then salted out, filtered, pressed and dried. It dyes

page_text: a greenish-black on wool from an acid bath. By subsequently treating the dye
with a chromium salt the fastness and depth are materially increased.
EXAMPLE IV.
The amidoazo colouring matter, prepared from 15.5 kilos. of amidosalicylic
acid and 24.5 kilos. of 1.7 naphtylaminesulphonate of soda, is transformed into the
diazoazo compound. A solution of 24. kilos. of amidonaphtolsulpho acid S and
5.3 kilos. of sodium carbonate is then run into the acid liquid containing the
diazoazo body in suspension. In order to finish the combination, a quantity of
sodium acetate, corresponding to the free acid present, is added. After some
hours stirring the mass is neutralised by means of caustic soda. An excess of
sodium carbonate is then added to the solution so obtained and a diazo solution,
prepared in the usual manner, from 10.7 kilos. of paratoluidine, is run into it. The
dyestuff is then isolated as described in the previous examples. It dyes a
greenish-black on wool, from an acid bath. By subsequently treating the dye
with a chromium salt the fastness is materially increased.
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. The manufacture of polyazo colouring matters, having the property of form-
ing fast lakes when treated on the fibre with chromium salts, by acting in the
presence of an excess of soda with a diazotised amidoazo compound obtained by
combining diazosalicylic acid with alpha-naphtylamine, or 1.6 or 1.7 naphtylamine-
sulpho acid, upon a molecular proportion of a monoazo colour, prepared by the
combination of amidonaphtoldisulpho acid K, or amidonaphtolsulpho acid S, with
a suitable diazo body in acid solution, substantially as herein before described.
2. The manufacture of polyazo colouring matters, having the property of form-
ing fast lakes when treated on the fibre with chromium salts, by acting with a
diazotized amidoazo compound, obtained by combining diazosalicylic acid with
alpha-naphtylamine, or 1.6 or 1.7 naphtylaminesulpho acid, upon a molecular pro-
portion of amidonaphtoldisulpho acid K, or of amidonaphtolsulpho acid S, in acid
solution and by acting upon the intermediate product, so obtained, in alkaline
solution with a suitable diazo body substantially as hereinbefore described.
3. The new polyazo colouring matters such as can be obtained by the processes
claimed in the preceding first and second claiming clauses and having the pro-
perty of forming fast lakes when treated on the fibre with chromium salts.
Dated this 31st day of July 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.