The Manufacture or Production of Dye-stuffs for Cotton.
Year: 1895

page_text: [Communicated from abroad by FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany, Manufacturers.]
The Manufacture or Production of Dye-stuffs for Cotton.
I HENRY EDWARD NEWTON of The Office for Patents 6 Bream's Buildings,
Chancery Lane in the County of London Patent Agent do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have discovered that on heating amido-sulphonic
acids, amido hydroxy sulphonic acids, hydroxysulphonic acids or dihydroxy-
sulphonic acids of the benzene or naphthalene series, or salts or derivatives of these
sulphonic acids with sulphur and alkaline sulphides or with substances or mixtures
acting in the same or a similar manner dye-stuffs are obtained which possess the
valuable property of dyeing unmordanted cotton not only in a boiling but also in a
cold bath, brown, dark brown, green, olive-green, olive black, grayish-black,
brownish-black, deep black, and the like shades being thus obtained which are fast
against the action of acids and alkalies and especially against washing.
.
In carrying out the process my foreign correspondents heat, at higher
temperatures mixtures containing the above defined sulphonic acids or salts or
other derivatives thereof and sulphur and alkaline sulphides or the like. The
reaction in most cases begins at from about 150 to 170 degrees Centigrade and is
finished after heating the mixtures during several hours at from about 200 to
270 degrees Centigrade. The resulting melts after being pulverised may be used
at once for dyeing purposes, or they may be purified by dissolving them in hot
water, filtering and evaporating the filtrates thus obtained to dryness. The dye
stuffs dissolve with readiness in water and as herein before mentioned may be
employed at once for dyeing cotton in cold or hot dye baths. According to the
researches of my foreign correspondents it is more profitable to dissolve the dye
stuffs in alkaline sulphides, alkalies or alkaline sulphites or the like, and to place
the cotton in these solutions for some time at ordinary temperature intense dark
shades in general being thus produced.
The purification of the dye stuffs may also be carried out in any other manner
for instance by dissolving the melt in hot water, filtering if necessary acidulating
the solution or filtrates, filtering off and washing the precipitates thus obtained
and redissolving them in alkaline sulphides, alkalies, alkaline sulphites or
the like.
My foreign correspondents give the following examples which are merely
typical, in order to illustrate the process for preparing the new. dye stuffs. The
parts are by weight.

page_text: in a vessel by means of an oil bath. At about 150 degrees Centigrade a violent
action begins whilst the original brownish-yellow colour of the heated mixture
gradually turns to dark-brown. When the first violent action shews signs of
stopping the mass is then heated during about four hours at from 200 to
250 degrees Centigrade and is afterwards allowed to cool. The melt thus
obtained is dissolved in hot water, and the resulting solution is filtered and
evaporated. The dye-stuff thus produced forms a black mass which dissolves with
readiness in water. It dyes unmordanted cotton in a cold dye bath darkish olive
green, in a hot bath gray black. A solution of the dye stuff in alkaline sulphide
or the like, dyes unmordanted cotton at ordinary temperature deep black fast
shades.
The analogous dyestuffs are obtained in the same or a similar manner on
employing other mono- or poly sulphonic acids of alpha or beta naphthylamine, or
amido-sulphonic acids of the benezene series instead of the alpha, naphthylamine
beta, sulphonic acid used in the preceding example.
The researches of my foreign correspondents have also shewn that amidohydroxy
sulphonic acids of the benzene or naphthalene series or salts or other derivatives
of amido hydroxy sulphonic acids, can also be employed in the process illustrated
by the preceding example, dye-stuffs being thus produced which dye unmordanted
cotton in a cold or a hot bath and produce fast shades. For instance, on heating
alpha, alpha, amidonaphthol beta, beta, disulphonic acid or salts thereof with
sulphur and alkaline sulphides a product is obtained which when dissolved in
alkaline sulphide yields on unmordanted cotton in a cold bath blackish shades of
high intensity and fastness.
COLOURING MATTER OBTAINED FROM ẞ₁ NAPHTHOL ( MONO-SULPHONIC
ACID.
1 part of B, naphthol ẞ, sulphonate of sodium 2 parts of sulphur and 4 parts of
sodium sulphide are thoroughly mixed; and the resulting mixture is heated by
means of an oil bath, gradually raising the temperature. At about 140 degrees
Centigrade (temperature of the oil) the mass begins to effervesce which can be
lowered by stirring. As soon as the first violent action stops the temperature is
raised to about 250 degrees Centigrade, and the mass is kept at from 250 to
260 degrees Centigrade during about 4 hours. After cooling the mass is dissolved
in hot water and the resulting solution is filtered. The dye stuff, which is
obtained by evaporating the filtrate to dryness forms a brownish black mass which
can be readily powdered. It yields on unmordanted cotton in cold baths containing
sodium sulphide black shades, whilst it produces brownish black shades in hot baths
containing for instance soap and potassium carbonate.
DYE STUFF PRODUCED FROM a₁ α DIHYDROXYNAPHTHALENE ẞ, ßs
DISULPHONIC ACID.
A thorough mixture prepared from 1 part of a₁ α dihydroxynaphthalene-
BB, disulphonate of sodium 2 parts of sulphur and from 4 to 5 parts of sodium
sulphide is gradually heated by ineaus of an oil bath to 250 degrees Centigrade,
and the mass is kept at this temperature during about 4 hours. The original

page_text: reddish brown colour gradually turns to bluish black. After cooling the resulting
solid mass is powdered and the dye stuff thus obtained may be used at once for
dyeing purposes. It yields on unmordanted cotton in cold baths containing a small
quantity of sodium sulphide brownish black shades, and the same shades result on
using hot baths, containing soap and potassium carbonate, or the like or not
containing such or the like substances.
In a manner analogous to that described in the preceding examples two and
three other colouring matters can be obtained, if on the one hand the ẞ, naphthol
B. sulphonic acid is replaced by equivalent quantities of other a or B-naphthol-mono
or polysulphonic acids or salts or derivatives thereof or if on the other hand other
dihydroxynaphthalene sulphonic acids are used in place of the a, a, dihydroxy-
naphthalene B, B, disulphonic acid. The researches of my foreign correspondents
have also shewn that similar results are obtained, if hydroxysulphonic acids or
dihydroxysulphonic acids of the benzene series are used, colouring matters being
thus produced which likewise possess the remarkable property of dyeing cotton in
cold and hot baths.
My foreign correspondents have described in the preceding examples some
methods of practically producing some of the dye stuffs hereinbefore defined. Of
course they do not limit themselves to the particulars given therein, as the processes
can be varied.
Thus, for instance, the sodium sulphide used in the preceding examples may be
replaced by other alkaline sulphides; or alkaline polysulphides or mixtures
prepared from sulphur and alkalies or the like substances acting in the same or a
similar manner may be employed in place of mixtures prepared from sulphur and
sodium sulphide.
The quantity of sulphur and of alkaline sulphide, or the proportions of the
analogous bodies or mixtures to be used in these processes may be varied within
certain limits.
The process may also be carried out by introducing the aforesaid sulphonic acids
or salts or derivatives thereof into a heated mixture prepared from sulphur aud
alkaline sulphide or the like.
According to the researches of my foreign correspondents nitrosulphonic acids
and nitrohydroxysulphonic acids may also be used respectively in place of the
amidosulphonic acids and amidohydroxysulphonic acids.
Such and similar variations do not alter the nature of this invention which in
general relates to the production of valuable dye stuffs by heating amidosulphonic
acids or nitrosulphonic acids amidohydroxysulphonic acids or nitrohydroxysul-
phonic acids, hydroxysulphonic acids, dihydroxysulphonic acids of the benzene or
naphthalene series or salts or other derivatives of these sulphonic acids with
sulphur and alkaline sulphides or with substances or nixtures acting in the same
or a similar way as herein before defined.
Dated this 23rd September 1895.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Dye-stuffs for Cotton.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, 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 :-
My foreign correspondents have discovered that on heating amido-sulphonic

page_text: acids, amidohydroxy-sulphonic acids, hydroxy sulphonic acids, or dihydroxy-
sulphonic acids of the benzene or naphthalene series, or salts or derivatives of
these sulphonic acids, with sulphur and alkaline sulphides, or with substances or
mixtures acting in the samne or a similar manner, dye-stuffs are obtained which
possess the valuable property of dyeing unmordanted cotton in cold as well as in
boiling baths.
The shades produced are principally brown, dark brown, green, olive green,
olive black, grayish black, brownish black, deep black, and the like, and they
withstand the action of acids and alkalies, and especially washing.
In carrying out the process, my foreign correspondents heat mixtures of the
above-defined sulphonic acids, or salts or other derivatives thereof, and sulphur,
and alkaline sulphides or the like. Action in most cases begins at from about 150
to 170 degrees Centigrade, and is at an end after heating during several hours, at
from about 200 to 270 degrees Centigrade. The melts may be at once used for
dyeing purposes, or they may be purified by dissolving them in hot water, filtering,
and evaporating the filtrates to dryness. The dye-stuffs readily dissolve in water,
and, as hereinbefore mentioned, may be at once used for dyeing cotton in cold or
hot baths. In some cases, it has been found to be advantageous to dissolve the
dye-stuffs in alkaline sulphides, alkalies, or alkaline sulphites, or the like, and to
keep the cotton immersed in these solutions for some time at the ordinary
temperature. Intensely dark fast shades are thus produced.
The purification of the dye-stuffs may be carried out, if desired, for instance, by
dissolving the melt in hot water, filtering if necessary, acidulating the solutions or
filtrates, filtering off, and washing the precipitates thus obtained, redissolving them
in alkaline sulphides, alkalies, alkaline sulphites, or the like, and subsequently
evaporating the solutions.
My foreign correspondents give the following typical examples in illustration of
the process of preparing the new dye-stuffs. The parts are by weight.
DYE-STUFF FROM ALPHA₁ NAPHTHYLAMINE BETA SULPHONIC ACID.
A thorough mixture of one part of alpha, naphthylamine beta, sulphonate of
sodium, 2 parts of sulphur, and 4 parts of sodium sulphide, is heated by means of
an oil bath.
Violent action sets in at about 150 degrees Centigrade, the color
of the heated mixture changing gradually from brownish-yellow to dark-brown.
After the first violent action is at an end, the mass is heated during about four
hours at from 200 to 250 degrees Centigrade. When cold, the melt is dissolved
in hot water, and the solution is filtered and evaporated. The dye-stuff thus
produced is a black mass which readily dissolves in water.
cotton in a cold bath a darkish olive color; in a hot bath, gray-black. A solution
It dyes unmordanted
of the dye-stuff in alkaline sulphide or the like, produces olive-black fast shades
on unmordanted cotton at ordinary temperatures.
Analogous dye-stuffs are obtained in the same or a similar manner, by using
other mono- or poly-sulphonic acids of alpha or betanaphthylamine, or amido-
sulphonic acids of the benzene series, instead of the alpha, naphthylamine beta
sulphonic acid prescribed in the preceding example.
The following table is given in further illustration of the results obtainable by
the process herein before defined. The ingredients used in preparing the coloring
matters are stated in the first column; the shades produced at ordinary
temperatures, in baths containing sodium sulphide being indicated in the secon‹i
column.

page_text: As above mentioned, amidohydroxy-sulphonic acids of the benzene or naphtha-
lene series, or salts or other derivatives of amidohydroxy sulphonic acids, can also
be used in the process illustrated by the preceding example. They give rise to
coloring matters which produce fast shades on unmordanted cotton in cold as well
as in hot baths. For instance, on heating alpha, alpha, amidonaphthol beta, beta,
disulphonic acid, or salts thereof, with sulphur and alkaline sulphides, a product is
obtained which, when dissolved in alkaline sulphide, produces blackish shades of
-great intensity and fastness on unmordanted cotton in a cold bath; amidonaphthol-
monosulphonic acid G yields a greyish-black dye stuff.
The production of dye-stuffs from hydroxy sulphonic acids of the naphthalene
or benzene series is illustrated by the following example. The parts are by
weight
EXAMPLE B.
COLORING MATTER OBTAINED FROM BETA NAPHTHOLBETA MONOSULPHONIO
ACID.
1 part of beta, naphthol beta, sulphonate of sodium, 2 parts of sulphur, and
4 parts of sodium sulphide, are thoroughly mixed, and the mixture is heated by
means of an oil bath, the temperature being gradually raised. At about
140 degrees Centigrade (temperature of the oil), effervescence sets in, which cau
be diminished by stirring. As soon as the first violent action is at an end, the
temperature is raised to about 250 degrees Centigrade, and the mass is kept at
from 250 to 260 degrees Centigrade during about 4 hours. When cold, the melt
is dissolved in hot water, and the solution is filtered. The dye-stuff obtained on
evaporating the filtrate to dryness, is a brownish-black mass. It produces black
shades on unmordanted cotton in cold baths containing sodium sulphide, and
brownish-black shades in hot baths in which soap and potassium carbonate are
present.
The following example illustrates the production of the dye-stuff's from
dihydroxy sulphonic acids. The parts are by weight.
DYE-STUFF PRODUCED
FROM ALPHA ALPHA DIHYDROXY-NAPHTHALENE
BETA, BETA; DISULPHONIC ACID.
A thorough mixture of 1 part of alpha, alpha, dihydroxynaphthalenebeta,
beta, disulphonate of sodium, 2 parts of sulphur, and from 4 to 5 parts of sodium
sulphide, is gradually heated by means of an oil bath to 250 degrees Centigrade,
and the mass is kept at this temperature during about 4 hours. The original
reddish-brown color gradually changes to bluish-black. The pulverised product
may be used in its crude state for dyeing purposes. In cold baths containing a
small quantity of sodium sulphide, it dyes unmordanted cotton a brownish-black
color, and the same shades are obtained on using hot baths, whether these contain
soap and potassium carbonate or the like, or not.
Following the directions given in the preceding examples B and C, other
coloring matters can be obtained, on the one hand, by substituting for beta₁
naphthol beta, sulphonic acid, equivalent quantities of other alpha or beta naphthol-
mono or polysulphonic acids, or salts or derivatives thereof, and, on the other
hand, by using other dihydroxynaphthalene-sulphonic acids in place of alpha,
alpha dihydroxynaphthalene beta, beta, disulphonic acid. The researches of my
foreign correspondents have also shown, that similar results are obtained if
hydroxysulphonic acids, or dihydroxysulphonic acids, of the benzene series are
used, coloring matters being thus produced which also possess the remarkable
property of dyeing cotton both in cold and hot baths.

page_text: A number of typical dye-stuffs, derived from hydroxy or dihydroxy sulphonic
acids are enumerated in the following table :-
Although my foreign correspondents have described in the preceding examples
several methods of producing the dye-stuffs hereinbefore detined, they do not
limit themselves to the particulars given therein, as the processes can be varied.
Thus, for instance, in place of the sodium sulphide used in the preceding
examples, other alkaline sulphides may be taken, or alkaline polysulphides, or
mixtures prepared from sulphur and alkalies, or the like substances acting in the
same or a similar manner, may be used in place of mixtures prepared from sulphur
and sodium sulphide. The quantity of sulphur, and of alkaline sulphide, or the
proportions of the analogous substances or mixtures to be used in these processes,
may be varied within certain limits, the effect of varying the proportions of these
ingredients being that dye-stuffs are obtained which produce slightly different
shades on cotton. The process may also be carried out by introducing the afore-
said sulphonic acids, or salts or derivatives thereof, into a heated mixture prepared
from sulphur and alkaline sulphide or the like.

page_text: According to the researches of my foreign correspondents, nitrosulphonic acids,
and nitrohydroxysulphonic acids, may also be used in place of the amidosulphonic
acids and amido hydroxy sulphonic acids respectively.
Such and similar variations do not alter the nature of this invention, which,
in general terms, relates to the production of valuable dye-stuffs by heating
amidsulphonic acids, or nitrosulphonic acids, amidohydroxysulphonic acids, or
nitrohydroxysulphonic acids, hydroxysulphonic acids, dihydroxysulphonic acids of
the benzene or naphthalene series, or salts or other derivatives of these sulphonic
acids, with sulphur and alkaline sulphides, or with substances or mixtures acting
in the same or a similar way, as hereinbefore defined.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
1. The production of coloring matters capable of dyeing cotton in hot and cold
baths from amidosulphonic acids, nitrosulphonic acids, amidohydroxysulphonic
acids, nitrohydroxysulphonic acids, hydroxysulphonic acids, or dihydroxysulphonic
acids of the benzene or naphthalene series, which process consists in heating the
said sulphonic acids, alkaline salts, or other derivatives thereof, either with sulphur
and alkaline sulphides, or with sulphur and alkalies, or with alkaline polysulphides,
or with substances or mixtures which act in the same or a similar manner, and
subsequently isolating the dye-stuffs so formed in a suitable manner, if desirable.
2. In the process defined by the foregoing first claim:
(a) The use of alpha, naphthylamine alpha, monosulphonic acid, alpha-
naphthylamine beta, monosulphonic acid, alpha, naphthylamine beta, mono-
sulphonic acid, alpha, naphthylamine alpha, monosulphonic acid, alpha,
naphthylamine beta, alpha disulphonic acid, alpha, naphthylamine beta,
alpha disulphonic acid, alpha, naphthylamine alphas alpha, disulphonic
acid, beta, naphthylamine beta; monosulphonic acid, beta, naphthylamine
beta, monosulphonic acid, beta, naphthylamine alpha, monosulphonic acid,
beta, naphthylamine beta, alpha, disulphonic acid, parasulphanilic acid; or
the like amidosulphonic acids of the naphthalene or benzene series, or the
corresponding nitrosulphonic acids or alkaline salts, or other derivatives of
these sulphonic acids; or
(b) The use of amidonaphtholmonosulphonic acid G, alpha, alpha, amido
naphthol betas beta, disulphonic acid, or the like amidehydroxysulphonic
acids of the naphthalene or benzene series, or the corresponding nitro-
bydroxysulphonic acids or alkaline salts or other derivatives of such
amidohydroxy- or nitrohydroxy-sulphonic acids.
(c) The use of alpha, naphthol-alpha, alpha, disulphonic acid, beta, naphthol
heta, monosulphonic acid, beta, naphthol beta, monosulphonic acid, beta,
naphthol-beta, beta, disulphonic acid, beta, naphthol beta, beta, disulphonic
acid, alpha, alpba, dihydroxynaphthalene alpba monosulphonic acid,
dihydroxynaphthalenemonosulphonic acid G, dihydroxynaphthalenemono-
sulphonic acid R, alpha, alpha, dihydroxynaphthalene beta, beta, disulphonic
acid, paracresolmetasulphonic acid, or the like hydroxy- or dihydroxy-
sulphonic acids of the benzene or naphthalene series, or alkaline salts or
other derivatives thereof.
3. As new products of manufacture, the new dye-stuffs produced by the process
hereinbefore defined, or by any other means affording the same result.
Dated this 23rd day of June 1806
NEWTON & SON,
Agents for the Applicant.