The Production of Azocolors in Substance or on the Fibre.
Year: 1890

page_text: Date of Application, 27th Sept., 1890
Complete Specification Left, 27th June, 1891-Accepted, 8th Aug., 1891
PROVISIONAL SPECIFICATION.
The Production of Azocolors in Substance or on the Fibre.
I, SYDNEY PITT of Sutton in the County of Surrey, Gentleman, (a com-
munication from Leopold Cassella and Company of Frankfort-on-Main, Germany)
do hereby declare the nature of this invention to be as follows:-
This invention relates to coloring matters producing brown and violet to black
shades. These dyestuffs are derived from a compound herein termed naphtylene-
violet and which I have described in another Provisional Specification of this
date. It is formed by the combination of one molecule of the tetrazocompound
from diamidonaphtalene ẞ disulphonic acid with 2 molecules of a naphtylamine.
Naphtylene-violet has a great affinity both for animal and vegetable fibres. It
produces on the animal fibre in a neutral bath containing salt, and on the vegetable
fibre in the same manner or in an alkaline bath, a bloomy violet shade. As a
violet color it has no technical value, being very unstable against acids, but
diazotized either in solution or upon the fibre by the action of acidulated nitrite of
sodium, it forms a quite insoluble brown diazoazo-compound, which easily combines
in aqueous or alcoholic solutions with amines, diamines, phenoles, their substituted
derivatives, their sulpho- or carbo- or sulpho-carbo acids, forming a series of brown,
violet, olive, blue and black coloring matters.
I shall first describe the way of preparing these colors in substance suitable for
the market. This process is in some respects analogous to that of the British
Patent 921485.
EXAMPLE.
67 kilos. of naphtyleneviolet are dissolved in 5000 litres hot water and pre-
cipitated by addition of 100 kilos. chlorhydric acid; after cooling to 15° C.,
15 kilos. of nitrite of sodium are added. After several hours, the violet coloring
matter is entirely transformed into a brown tetrazocompound insoluble in water.
If the latter is added to an alkaline solution of 29 kilos. a or ẞ naphtol coloring
matters dyeing a blueish black shade and difficultly soluble are formed; if the
naphtoles are replaced by their mono- or disulpho-acids, the coloring matters
which result, are of similar shade but of greater solubility.
Difficultly soluble coloring matters of deep black shade are obtained by the use
of chlorhydric solution of a or ẞ naphtylamine or dimethyle, a or naphtylamine,
the free acid ought to be neutralized by carbonate or acetate of soda.
The sulpho-acids of the naphtylamines yield coloring matters from violet to
black;
black colors are also obtained with dimethylaniline, metaphenylenediamine,
alkylized metaphenylenediamine, diphenylemetaphenylenediamine and their homo-
logues, the naphtylenediamines and their sulphoacids.
Phenole, resorcine, dioxynaphtaline as well as their sulpho- and carboacids
form red, brown, violet and black colors. Metaamidophenole, phenylmetaamido-
phenole and amidonaphtolsulphonic acids combine to colors of reddish violet to
greenish black shades.
II. COLORS FORMED ON THE FIBRE.
If the fibre dyed with naphtylene-violet is passed through a weakly acidulated
bath containing nitrite of soda, the violet shade changes first into blue and then
into brown of a shade similar to cutch brown. This tetrazo compound is solidly
attached to the fibre; when treated in hot alkaline or acid bath the tetrazo
compound changes its chemical nature, without changing its shade and then forms

page_text: a very fast brown tint. The shade is slightly changed, if the latter bath contains
a chromate, alum or a salt of zinc, copper, iron, nickel or cobalt.
If the fibre impregnated with undecomposed tetrazo compound is passed through
aqueous or alcoholic solutions of monamines, diamines, phenoles, their products of
substitution, sulpho- or carbo- or sulpho-carbo acids, which contain (according to
circumstances) free or carbonated alkali or acetate of sodium, shades which are
very similar to those, which are described above are obtained.
EXAMPLE 1. BROWN COLOR FROM THE TETRAZO COMPOUND.
Wool is dyed with 2.5 %, or cotton with 4% of naphtylene-violet; for both
there is added per 100 kilos. of the material to be dyed 20 kilos. of Glauber's salt
to the dye-bath and for cotton 5 kilos. of soda ash in addition. The dyeing is
performed at the boil; the baths are almost exhausted; the colored fibre is passed
during a quarter of an hour through a bath containing nitrite of soda and
chlorhydric acid. The fibre is wrung and then passed during half an hour through
a bath containing 3% sulphuric acid and having a temperature of 60 to 100° C.
For cotton instead of sulphuric acid 5% of carbonate of soda may be used. Silk
and jute are treated in the same way.

page_text: Tetramethylmetatoluylenediamine
Diphenylmetaphenylenediamine
Dinaphtylmetaphenylenediamine
Dinaphtylmetaphenylenediamine
Triamidobenzol
Diphenylamine
Phenole
Orthocresole
Salicylic acid -
Metaamidophenole
Diethylemetaamidophenole
Diethyleamidoorthotoluole
Phenyleamidophenole
Metatoluylenediamine
Paratoluylenediamine
blue
brow
Metaphenylenediaminesulphonic acid
Metatoluylenediaminesulphonic
viole
acid
brow
Diethylemetaphenylenediamine
gree
-
gree
-
dead
a
-
blue
blue
-
brow
-
brov
-
red-
red-
red-
viole
blue
blac
-
blue
"
viol
->>
viol
α
-
blac
dea
gree
dee
gree
gree
blac
-
bro
-
bro
-
blac
-
blu
->
blac
-
bla
Resorcine
Orcine
Naphtylamine
B Naphtylamine
Dimethyle a naphtylamine
Dimethyle ẞ naphtylamine
Phenyle a naphtylamine
Tolyle ẞ naphtylamine
a
a
a
Naphtylaminesulphonic acid (Piria)
Naphtylaminesulphonic acid (Landshoff)
Naphtylaminesulphonic acid (Laurent)
B Naphtylamine ẞ sulphonic acid (Brönner)
B Naphtylamine y sulphonic acid (Dahl)
Naphtylamine & sulphonic acid F.
-
Ethyle naphtylamine & sulphonic acid F.
Naphtylaminedisulphonic acid (Schöllkopf)
a
a Naphtylaminedisulphonic acid (Berlin)
ẞ Naphtylaminedisulphonic acid (from R salt)
y Amidonaphtolsulphonic acid
B Amidonaphtolsulphonic acid
Naphtylenediamine ẞ B
Diphenylnaphtylenediamine
18 Naphtylenediamine
Naphtole
a
B Naphtole
a Oxynaphtole acid
-
a Naphtole a monosulphonic acid
Naphtolemonosulphonic acid (Schäffer)
ẞ Naphtolemonosulphonic acid F.
B Naphtolemonosulphonic acid (Bayer)
ẞ Naphtoledisulphonic acid R
a Naphtoledisulphonic acid (Schöllkopf)
Naphtoledisulphonic acid zeta
a
Dioxynaphtaline
a a
Dioxynaphtaline
"
-
grey
gre
gre
grej
gre
-
bla
-
bla
-
bla
-
bla
blu
dea
grey
blu
bla
blu
-
blac
-
gre
gre
ww
bla
-
gre
-
gre
Dioxynaphtaline from ẞ Naphtolmonosul-
phonic acid (Bayer)
Dioxynaphtalinemonosulphonic acid (from
Rid
cre

page_text: The above described reaction with the tetrazotized naphtyleneviolet may be
obtained with other substances of analogous chemical constitution and properties
as the combinations of a naphtylamine with the tetrazotized mono- and disulphonic
acids of paradiamines such as benzidine, methylbenzidine, tolidine, ethoxydiamido-
diphenyle, diphenoleethers, diamidostilbene and of benzidinesulphone of which the
diamidostilbenedisulphonic acid gives the best results.
COMPLETE SPECIFICATION.
The Production of Azocolors in Substance or on the Fibre.
1, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a communication
from Leopold Cassella and Company, of Frankfort-on-Main, Germany,) 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:-
This invention relates to coloring matters producing brown and violet to black
shades. These dyestuffs are derived from a compound herein termed naphtylene-
violet and which I have described in another Specification of this date. It is
formed by the combination of one molecule of the tetrazocompound from diamido-
naphtalene ẞ disulphonic acid with 2 molecules of a naphtylamine.
Naphtylene-violet has a great affinity both for animal and vegetable fibres. It:
produces on the animal fibre in a neutral bath containing salt, and on the vegetable
fibre in the same manner or in an alkaline bath, a bloomy violet shade. As a violet
color it has no technical value, being very unstable against acids, but diazotized
either in solution or upon the fibre by the action of acidulated nitrite of sodium, it
forms a quite insoluble brown diazoazo compound which easily combines in aqueous
or alcoholic solutions with amines, diamines, phenoles, their substituted derivatives,
their sulpho- or carbo- or sulpho-carbo acids, forming a series of brown, violet, olive,
blue and black coloring matters.
I shall first describe the way of preparing these colors in substance suitable for
the market.
This process is in some respects analogous to that of the British Patent
921485.
EXAMPLE.
67 kilos. of naphtyleneviolet are dissolved in 5000 litres hot water and precipitated
by addition of 100 kilos. hydrochloric acid; after cooling to 15° C., 15 kilos. of
nitrite of sodium are added. After several hours, the violet coloring matter is
entirely transformed into a brown tetrazocompound insoluble in water. If the latter
is added to an alkaline solution of 29 kilos. a or ẞ naphtol coloring matters dyeing a
blueish black shade and difficultly soluble are formed; if the naphtoles are replaced
by their mono- or disulpho-acids, the coloring matters which result, are of similar
shade but of greater solubility.
Difficultly soluble coloring matters of deep black shade are obtained by the use
of hydrochloric solution of a or ẞ naphtylamine or dimethyle, a or ẞ naphtylamine,
the free acid ought to be neutralized by carbonate or acetate of soda.
The sulpho-acids of the naphtylamines yield coloring matters from violet to black;
black colors are also obtained with dimethylaniline, metaphenylenediamine, alkylized

page_text: metaphenylenediamine, diphenylemetaphenylenediamine and their homologues the
naphtylenediamines and their sulphoacids.
Phenole, resorcine, dioxynaphtaline as well as their sulpho- and carbo-acids form
red, brown, violet and black colors. Metaamidophenole, phenylmeta amidophenole
and amidonaphtolsulphonic acids combine to colors of reddish violet to greenish
black shades.
II. COLORS. FORMED ON THE FIBRE.
If the fibre dyed with naphtylene violet is passed through a weakly acidulated
bath containing nitrite of soda, the violet shade changes first into blue and then into
brown of a shade similar to cutch brown. This tetrazo compound is solidly attached
to the fibre; when treated in hot alkaline or acid bath the tetrazo compound changes
its chemical nature, without changing its shade and then forms a very fast brown
tint. The shade is slightly changed, if the latter bath contains a chromate, alum,
or a salt of zinc, copper, iron, nickel or cobalt.
If the fibre impregnated with undecomposed tetrazo compound is passed through
aqueous or alcoholic solutions of monamines, diamines, phenoles, their products of
substitution, sulpho- or carbo- or sulpho-carbo acids, which contain (according to
circumstances) free or carbonated alkali or acetate of sodium, shades which are very
similar to those which are described above are obtained.
EXAMPLE 1. BROWN COLOR FROM THE. TETRAZO COMPOUND.
Wool is dyed with 2.5 %, or cotton with 4% of naphtylene-violet; for both
there is added per 100 kilos. of the material to be dyed 20 kilos. of Glauber's salt
to the dye-bath and for cotton 5 kilos. of soda ash in addition. The dyeing is
performed at the boil; the baths are almost exhausted; the colored fibre is passed
during a quarter of an hour through a bath containing nitrite of soda and hydro-
chloric acid. The fibre is wrung and then passed during half an hour through a
bath containing 3% sulphuric acid and having a temperature of 60 to 100° C. For
cotton instead of sulphuric acid 5% of carbonate of soda may be used. Silk and
jute are treated in the same way.

page_text: inex a table indicating the more imp
and the shades which they produce
Aniline
Orthotoluidine
Paratoluidine
Xylidine
Cumidine
Sulfanile acid
-
Metaamidobenzolsulphonic acid
Metaamidobenzoe acid
Monomethyleaniline
Dimethyleaniline
Benzylemethyleaniline
Metaphenylenediamine
-
Metatoluylenediamine -
Paratoluylenediamine -
Metaphenylenediaminesulphonic
Metatoluylenediaminesulphonic a
Diethylemetaphenylenediamine
Tetramethylmetatoluylenediamin
Diphenylmetaphenylenediamine
a Dinaphtylmetaphenylenediami
B Dinaphtylmetaphenylenediami
Triamidobenzol
Diphenylamine
Phenole
Orthocresole
Salicylic acid
Metaamidophenole
Diethylemetaamidophenole
Diethyleamidoorthotoluole
Phenyleamidophenole
Resorcine
Orcine
α Naphtylamine
a
a
Naphtylamine
Dimethyle a naphtylamine
Dimethyle ẞ naphtylamine
Phenyle a naphtylamine
Tolyle ẞ naphtylamine
Naphtylaminesulphonic acid
Naphtylaminesulphonic acid
a Naphtylaminesulphonic acid (
ẞ Naphtylamine ẞ sulphonic acid
B Naphtylamine y sulphonic acid
Naphtylamine & sulphonic aci
Ethyle naphtylamine & sulpho
Naphtylaminedisulpohnic acid
a Naphtylaminedisulphonic acid
Naphtylaminedisulphonic acid
y Amidonaphtolsulphonic acid
Amidonaphtolsulphonic acid
Naphtylenediamine ß¹ B
Diphenylnaphtylenediamine
1.8 Naphtylenediamine
a
Nanhtola
-

page_text: IV.
The above described reaction with the tetrazotized naphtyleneviolet may be
obtained with other substances of analogous chemical constitution and properties as
the combinations of a naphtylamine with the tetrazotized mono- and disulphonic
acids of paradiamines such as benzidine, methylbenzidine, tolidine, ethoxydiamido-
diphenyle, diphenoleethers, diamidostilbene and of benzidinesulphone of which the
diamidostilbenedisulphonic acid gives the best results.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1st. The process of producing coloring matters by combining the tetrazoderivative
of naphtylene violet with phenols or amines.
2nd. The process of producing fast colors on animal or vegetable fibres which
consists in first dyeing the material with naphtylene violet, then treating the thus
dyed material with nitrous acid and then either treating the same in an alkaline or
acid bath at ordinary or higher temperature or passing the same through a bath
containing an amine or a phenol.
3rd. The new coloring matters obtained according to the 1st Claim substantially
as herein described.
Dated this 27th day of June 1891.
CARPMAEL & Co.,
Agents for the Applicant.