UNITED ‘ STATES
IFEicE.
ATENT
FERDINAND PETERSEN, OF BASLE, SWITZERLAND, ASSIGNOR TO FERD.
PETERSEN & (30., OF SCI-lWElZERI-IALLE, NEAR BASLE,’ S‘vVITZERLAND.
SUBSTANTIVE COTTON DYE.
SPECIFICATION’fOrming' part Of Letters Patent No. 578,580, dated March 9, 1897.
Application ?led July 3,1896. Serial No. 597,933. ($pecimens.)
T0 aZZ whont it may concern:
‘
nated benzidin base, so that the dyer using
Be it known that I, FERDINAND PETERSEN, them can employ weaker baths.
manufacturer, a citizen of the Swiss Republic,
These new dyestuffs have the formula
residing at Basle, Switzerland, have invented
certain Improvements in the Manufacture of
Substantive Cotton Dyestuffs, of which the
> following is a clear and complete speci?cation.
\
/OH
NaSOg—O6H3—N:N—O10H4—N:N—R
_
55
\SO3Na
By combination of the sulfo-acids of para
diphenyl bases with the amidonaphthol-sulfo
10
acids by themselves or with other ingredients,
also by diazotizin'g the simple compounds so
_
I
I
/OH
'
6o
NaSO3—OGHS—N:N—O1OH4<N:N—R
.
\SO3Na,
formed and further combining them with in which R indicates any developing agent.
amins, phenols, and their derivatives, an im
With the following developers there are
Inense number of products can be obtained.
It appears, however, to be a rule that the sulfo
groups of the diphenyl bases in the simple as
well as the more complex combinations lessen
and often quite destroy the affinity to vege
table ?ber, so that these derivatives, however
20
many may be imagined, cannot be considered
to be direct-acting coloring-matters.
Hitherto none of the possible dyestuff
groups, nor any number of them, has been
described.
25
-
produced the following tints:
Developers.
'
65
Tint-s.
Anilin _____________ ___.__ Reddish blue.
Orthotoluidin . _ . _
Paratoluidin
. _ __
_________ _ _
Metaphenylenediamin .
Metatoluylenediamin _.
Do.
70
Do.
Blue-black.
'
Do.
Alpha-naphthylamin. _ _
Bluish red.
Beta-naphthylamin ___.
Naphthionate ________ ..
Do.
Blue.
'
‘
75
Numerous experiments now show that it
All the new products are black powders, are
appears quite impossible to obtain so~called quite soluble in both hot and cold water, and
“ directly-dyeing ” coloring-matters by means they dye non-mordanted cotton bluish red to
'of the sulfo-acids of bases such as diamidodi~ blue-black. They are insoluble in alcohol.
phenylaniin and paraphenylenediamin; also,
The dyes can be produced on the ?ber by
the derivatives of the dianisidin and tolidin treating the ?ber ?rst with the dyestu? from
sulfo-acids show in their simple as well as the tetrazo derivative of a Griess benzidinr
in their more complex combinations, except sulfo-acid and gammaamidonaphthol-sulfo
shades of little value, very little or no affinity acid. This dye can then be further diazo~
'
tized on the ?ber, which is?nally treated with .85
The coloring-matters derived from the ben a developing solution.
35
‘
zidinsulfo-acids dye either badly or not at all.
Example-The tetrazo body derived from
I have now found that the benzidinsulfo a quantity of one of the Griess sulfo-acids, or
acids which have been described by P. Griess of a mixture of both acids corresponding'to
to vegetable ?ber.
(Berichte cler Deutschen Chem. Gesellschafé, ten kilos of nitrite, is combined with thirty
four kilos of gammaamidonaphthol - sulfo
duce, with gammaamidonaphtholsulfo-acid, acid in alkaline solution. The new interme
.40 Vol. let, p. 300) as isomeric disulfo-acids pro
9O
new products, which, although of themselves diate body'thus formed is separated or may
of no special advantage as dyestuffs, yet sur be further diazotized in the solution and is
pass the corresponding products of other ben combined with twenty-three kilos of meta
15 zidinsulfo-acids in the peculiarity that when phenylenediamin. The dyestuff thus pro 95
they are diazotized and combined with a cer
tain number of developing agents they pro
duced separates as a black precipitate. It
dyes cotton an intense blue-black and is fast
ducevaluableandsuccessfuldyestuffs. Some to light and washing. It is readily soluble
of these dyestuffs really dye considerably bet
in both hot- and cold water and insoluble in
50 ter than the corresponding derivatives that alcohol. Its solution in concentrated sulfuric
have been produced by means of a non-sulfo acid is bluish green, and when this is diluted
IOO
2
578,580
4. The improvement in the manufacture of
a black precipitate is formed. Its solution in
water is reddish brown, and when hydrochlo substantive cotton dyestuffs consisting in the
ric acid is added there is a reddish-brown pre combination of one molecule of the tetrazo
cipitate. When caustic soda is added to an derivative of the Griess benzidinsulfo-acids 15
aqueous solution of the dyestuff, there is a with two molecules of gammaamidonaphthol
brown precipitate.
sulfo-acid, the further diazotation of the dye
stuff thus obtained and the subsequent com—
What I claim is—
1. The improvement in the manufacture of bination of the diazotized dyestutf with two
substantive cotton dyestuifs consisting in the molecules of an aromatic metadiamin.
combination of a molecule of the tetrazo de
rivative of the Griess benzidinsulfo-acids
with two molecules of gammaamidonaph
thol-sulfo-acid.
2. The improvement in the manufacture of
substantive cotton dyestuffs consisting in the
combination of one molecule of the tetrazo
derivative of the Griess benzidinsulfo-acids
with two molecules of gammaamidonaphthol
sulfo-acid, the further diazotation of the dye
stuff thus obtained and the subsequent com
bination of the diazotized dyestuff with two
molecules of developing agents.
3. The improvement in the manufacture of
substantive cotton'dyestuffs consisting in the
25 combination of one molecule of the tetrazo
derivative of the Griess benzidinsulfo-acids
with two molecules of gammaamidonaphthol
sulfo-acid, the further diazotation of the dye
stui‘f thus obtained and the subsequent com
bination of the diazotized dyestuff with two
molecules of aromatic amido compounds.
5. As a new article of manufacture, the
herein-described blue-black substantive cot
ton'dyestulff derived from a Griess benzidin
sulfo-acid, gammaamidonaphtholsulfo - acid
and paraphenylenedialnin, which constitutes 45
in dry state a black powder, dyes cotton an
intense blue-black fast to light and Washing,
is readily soluble in both cold and hot Water,
insoluble in alcohol, dissolves in concentrated
sulfuric acid with a bluish-green coloration SO
and in water with reddish-brown coloration
and gives when hydrochloric acid is added to I
its aqueous solutions a reddish-brown precipi
tate and when caustic soda is added to its
aqueous solutions a brown precipitate.
55
In witness whereof I have hereunto signed
my name in the presence of tWo subscribing
witnesses.
FERDINAND PETERSEN.
\Vitnesses:
GEORGE GIFFORD,
AMAND RITTER.