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

page_text: Date of Application, 23rd Nov., 1895
Complete Specification Left, 24th Aug., 1896-Accepted, 24th Oct., 1896
[Communicated from abroad by THE FARBENFABRIKEN, Vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
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:-
Some time since my foreign correspondents discovered that valuable dye-stuffs
for cotton are obtained on heating, together with sulphur and alkaline sulphides, or
with substances or mixtures acting in a similar manner, amido sulphonic acids or
nitro-sulphonic acids, amido hydroxy-sulphonic acids, or nitro hydroxy sulphonic
acids, bydroxysulphonic acids, dihydroxy-sulphonic acids of the benzene or
naphthalene series, or salts or other derivatives of these or the like compounds.
The dye-stuffs thus produced dye unmordanted cotton, not only in hot baths, but
also in cold baths, and they are of special value for dyeing purposes, by reason of
their property of yielding very intense and fast shades.
My foreign correspondents have now found, that new valuable dye-stuffs,
possessing properties similar to those of the coloring matters herein before defined,
are obtained if the above named sulphonic acids are replaced by hydroxycarboxylic
acids, amidocarboxylic acids, or nitro carboxylic acids, amido hydroxycarboxylic
acids, nitrohydroxycarboxylic acids of the benzene or naphthalene series, or by
the simple hydroxy compounds of the benzene or naphthalene series (such as
phenol, cresols, xylenols, the analogues or hom logues thereof, alphanaphthol, beta
naphthol, or the like), or by the amido compoun is corresponding to the last
named hydroxy compounds. The dye-stuffs prepared by heating the said compounds
together with sulphur and alkaline sulphides or the like, yield, on unmordanted
cotton, shades from yellow, brown, olive, green, to brownish-black, greyish-black,
and deep black, and are distinguished by reason of their property of dyeing
unmordanted cotton, not only in hot baths, but even in cold baths, shades being
thus obtained which are fast against the action of light, alkalies, and acids, and
especially against washing and fulling.
My foreign correspondents give the following example in order to illustrate the
process for producing dye-stuffs for cotton from the aforesai materials. The parts
are by weight.
EXAMPLE 1.
DYE-STUFF FROM NITROSALICYLIC ACID.
A mixture prepared from I part of nitrosalicylic acid, 2 parts of sulphur, and
6 parts of sodium sulphide, is heated by means of an oil bath (with
ቀለ

page_text: during some hours in watery solutions of this dye, at ordinary temperature,
assumes a greenish-black shade.
Analogous dyestuffs are produced in a similar manner, if the nitrosalicylic acid
used in the foregoing example is replaced by other nitrohydroxycarboxylic acids,
or amidohydroxycarboxylic acids, or by nitrocarboxylic acids, amido carboxylic
acids, or hydroxycarboxylic acids of the benzene or naphthalene series. For
example, on treating salicylic acid in the above described manner with sulphur and
sodium sulphide, a dye-stuff is obtained which dyes unmordanted cotton a bro vn-
yellow; the dye stuff produced from ortho-cresolcarboxylic acid produces on cotton
red-brown shades; the dye-stuff obtained from meta-cresol-carboxylic acid yields
olive-brown shades; the dye-stuff from betanaphtholcarboxylic acid (melting point
216 degrees Centigrade) produces dark brown shades.
Similar dye-stuffs result, if the simple hydroxy compounds of the benzene or
naphthalene series, such as phenol, ortho, meta, or para cresol, or mixtures thereof
(such as raw cresols), xylenols, analogues and homologues thereof, alphanaphthol,
betanaphthol, or the like, are treated with sulphur and alkaline sulphides, or the
like, in the manner defined in the above Example 1. The shades produced with
these dye-stuffs on cotton likewise possess great fastness against alkalies, acids,
washing, and the action of light.
For example, the dye stuffs obtained from cresols produce from dark-brown to
brownish-black, very fast shades.
The following Examples 2 and 3 may serve to illustrate the mode of carrying
out the process for producing these new dye stuffs from cresols. The parts are
by weight.
EXAMPLE 2.
DYE-STUFF FROM RAW CRESOL.
A mixture prepared from I part of raw cresol, 1 part of sulphur, and 3 parts of
crystallized sodium sulphide (Na,S + 9 H₂O) is heated in a vessel provided with a
reflex condenser by means of a water bath, until a darkish-brown uniform liquid
results. The mass is then further heated by means of an oil-bath, during about
four hours, at 170 degrees Centigrade (temperature of the oil), and again during
four hours at about 250 degrees Centigrade. The resulting melt, when cool, is
dissolved in about 10 parts of hot water, and the so-formed blue-black solution is
filtered off. The dye-stuff is precipitated by adding common salt to the filtrate.
When filtered off, pressed, and dried, it forms a greyish-black powder, which
dissolves with readiness in water. By the addition of some alkaline sulphide, the
color of this solution turns into blue.
of
The dye-stuff yields on unmordanted cotton, at ordinary temperatures, in a bath
containing alkaline sulphide, dark-brown shades distinguished by reason
great fastness.
On following the directions given in the Example 2, a small amount of a less
valuable, and yellower dye-stuff is simultaneously produced, which, owing to its
somewhat greater solubility in water, cannot be salted out, and therefore remains
in the filtrate.
EXAMPLE 3.
DYE-STUFF FROM RAW CRESOL.
=
A mixture prepared from one part of raw cresol, one part of sulphur, and
14 parts of caustic soda-lye (specific gravity 1.355) is heated first by means of
a water bath, and then by means of an oil bath, under the conditions described in
the preceding Example 2. A black melt results, which is further treated in the
manner illustrated in the same Example 2. The dye-stuff thus obtained yields on
unmordanted cotton, in cold baths containing a small quantity of sodium sulphide,
or the like, dark-brown or brown-black shades fast against alkalies, acids, washing,
and the action of light.

page_text: Analogous dye-stuffs are produced on melting with sulphur and sodium sulphide,
or with sulphur and caustic soda lye, pure ortho or meta or para cresol, or mixtures
thereof, or ethyl phenyls, xylenols, or the like, or phenol itself, in the manner
described in the foregoing Examples 2 and 3.
For instance, the dye-stuff obtained from phenol yields fast yellowish-brown
shades on unmordauted cotton in cold baths containing a small quantity of
alkaline sulphide.
The production of coloring matters from nanhthol is defined in
EXAMPLE 4.
DYE-STUFF FROM BETA NAPHTHOL.
A mixture prepared from 1 part of betanaphthol, 2 parts of sulphur, and 5 parts
of sodium sulphide (NaS+ 9 H₂O) is heated by means of a water bath until a
uniform melt results. The mass is then heated in a vessel provided with a reflux
condenser, by means of an oil bath, first at 160 degrees Centigrade (temperature
of the oil), and then, after raising the temperature slowly to 200 degrees Centigrade,
at this temperature, during about from 2 to 3 hours, the mass being stirred the
while. The resulting melt, when cool, is dissolved in hot water. After filtration,
this solution is evaporated to dryness. The dye-stuff thus obtained forms a brown-
black mass, which can readily be pulverised.
It dyes unmoidanted cotton, in boiling baths containing soap and potassium
carbonate, a brown; in colds baths mixed with alkaline sulphide, a deep brown
black.
Alphanaphthol, when treated in the same manner, yields a dye-stuff which dyes
cotton a grey-black.
On employing the corresponding amido compounds in the place of the above
named hydroxy compounds, viz, phenol, cresols, xylenols, naphthols, and the like,
dye-stuffs for cotton are also obtained which possess properties similar to those of
the aforementioned coloring matters.
My foreign correspondents have described in the preceding Examples 1, 2, 3,
and 4, distinct methods, of practically producing some of the above defined dye-
stuffs. Of course they do not limit themselves to the particulars given in these
examples, as these may be varied. For instance, other alkaline sulphides may be
used, instead of sodium sulphide, or the mixture prepared from sulphur and caustic
soda-lye used in the above Example 3, may be replaced by alkaline polysulphides
or the like. The production of the herein before defined dye-stuffs from hydroxy-
carboxylic acids, amidocarboxylic acids, amidohydroxycarboxylic acids, or from
phenols and naphthols, or amines and the like, as well as of those prepared from
amidosulphonic acids, amidohydroxysulphonic acids, hydioxysulphonic acids,
dihydroxysulphonic acids of the benzene or naphthalene series, or the like, may be
carried out by heating the said substances with sulphur at elevated temperatures,
and in transforming the so-formed products into the dye-stuffs by a subsequent
treatment with alkalies, alkaline sulphides, or the like. The quantity of sulphur,
and of alkaline sulphide, or of the mixtures acting in the same manner, employed
in the process, may be varied in a suitable manner.
carried out at higher or lower temperatures than those prescribed in the examples,
The process may also he
and in order to isolate the finished dye-stuffs, the melts obtained may be treated
in another manner than that described in the examples.
Instead of dissolving these melts, with or without the addition of alkali, or
alkaline sulphide or the like, and of evaporating the so-formed solutions to dryness,
the solutions of the said melts in pure water may also be neutralized or acidulated
with acids, and the precipitates, if necessary, separated with common salt, or the
like, may be transformed into the dye-stuff's by dissolving the same in alkalies,
alkaline sulphides, or the like, and subsequently evaporating to dryness.
The herein described dye-stuffs are of especial technical value, by reason of

page_text: their property of dyeing unmordanted cotton already at ordinary temperatures,
and yielding thus very fast shades.
NEWTON & SON,
Agents for the Applicant.
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 :-
Some time ago my foreign corespondents discovered that valuable cotton dye-
stuffs are obtained on heating sulphur and alkaline sulphides, or substances or
mixtures acting in a similar manner, together with amidosulphonic acids or nitro-
sulphonic acids, amidohydroxysulphonic acids or nitrohydroxysulphonic acids,
hydroxysulphonic acids, dihydroxysulphonic acids of the benzene or naphthalene
series, or salts or other derivatives of these or similar compounds.
The dye-stuffs thus produced dye unmoidanted cotton not only in hot baths,
but also in cold baths, and are of special value for dyeing purposes by reason of
their property of yielding very inteuse and fast shades.
My foreign correspondents have now found that new valuable dye-stuffs,
possessing properties similar to those of the colouring-matters hereinbetore
defined, are obtained on substituting for the above-named sulphonic acids, hydroxy-
carboxylic acids, amidocarboxylic acids, or nitrocarboxylic acids, amidohydroxy-
carboxylic acids, nitrohydroxycarboxylic acids of the benzene or naphthalene series,
or the simple hydroxy compounds of the benzene or naphthalene series (such as
phenol, cresols, xylenols, esorcinol, the analogues or homologues thereof, alpha
naphthol, beta naphthol, dihydroxynaphthalenes or the like).
The dye-stuffs prepared by heating the said compounds together with sulphur
and alkaline sulphides or the like, yield, on unmordanted cotton, shades varying
from yellow, brown, olive-green, to brownish-black, greyish-black, and deep black,
distinguished by their property of dyeing unmordanted cotton, not only in hot
baths, but even in cold baths, shades being produced which withstand the action
of light, alkalies and acids, and especially washing and fulling.
My foreign correspondents give the following example, in illustration of the
process of producing cotton dye-stuffs from the aforesaid materials. The parts
are by weight.
EXAMPLE A.
DYE STUFF FROM NITROSALICYLIC ACID.
When
A mixture of 1 part of nitrosalicylic acid, 2 parts of sulphur, and 6 parts of
sodium-sulphide, is heated by means of an oil bath to about 160 degrees Centi-
grade, being kept well stured. At first it foams violently. When the foaming
slackens, the temperature is slowly raised to about 250 degrees Centigrade, and
the mass is heated during from about 3 to 4 hours at this temperature.
cool, the black melt is dissolved, together with about 3 parts of sodium sulphide,
in hot water, and the solution is filtered and evaporated to dryness. The dye-stuff
thus produced forms a greenish-black mass, and can at once be used for dyeing.
Cotton, after being kept during several hours in aqueous solutions of this dye at
ordinary temperature, assumes a greenish-black shade.
Analogous dye-stuffs are produced in a similar manner on substituting, for the
nitic salicylic acid used in the foregoing example, other nitrohydroxycarboxylic

page_text: ==
A mixture of one part of crude cresol, one part of sulphur, and 1.4 parts of
caustic soda lye (specific gravity 1-355), is heated first by means of a water
bath, and then by means of an oil bath, in the manner described in the preceding
Example B. A black melt is obtained, which is further used or treated in the
nanner illustrated in the same Example B. The dye-stuff thus obtained dyes
unmordanted cotton in cold baths containing a small quantity of sodium sulphide,
or the like, dark brown or brownish-black shades, which withstand alkalis, acids,
washing, and the action of light.
Analogous dye-stuffs are produced on heating pure ortho-, or meta-, or para-,
cresol, or mixtures thereof, or ethyl, phenols, xylenols, or the like, or phenol itself,
in the manner described in the foregoing Examples B and C, with sulphur and
sodium sulphide, or with sulphur and caustic soda-lye.

page_text: For instance, the dye-stuff obtained from phenol yields fast yellowish-brown
shades on unmordanted cotton in cold baths containing a small quantity of alkaline
sulphide.
The production of colouring matters from naphthol is defined in the following
DYE-STUFF FROM BETANAPHTHOL.
A mixture of 1 part of betanaphthol, 2 parts of sulphur, and 5 parts of sodium
sulphide (Na,S+ 9 H,O), is heated by means of a water bath until it becomes a
uniform liquid. The mass is then heated in a vessel provided with a reflux
condenser, by means of an oil bath, first at 160 degrees Centigrade (temperature
of the oil), and then the temperature is slowly raised to 200 degrees Centigrade,
and kept at this point during about from 2 to 3 hours, the mass being stirred the
while. When cool, the melt is dissolved in hot water. After filtering the
solution, it is evaporated to dryness. The dye-stuff thus obtained forms a brown-
black mass which is readily pulverized.
In boiling baths containing soap and potassium carbonate, it dyes unmordanted
cotton a brown; in cold baths containing alkaline sulphide, a deep brown
black.
Alphanaphthol, when treated in the same manner, yields a dye-stuff which dyes
cotton a grey-black; beta, beta,- or beta₁ beta-dihydroxynaphthalenes yield
dark black colouring matters.
My foreign correspondents have described in the preceding Examples A, B, C,
and D, distinct methods of practically producing some of the above defined dye-
stuffs. Of course they do not limit themselves to the particulars given in these
examples, as these may be varied. For instance, other alkaline sulphides may be
used instead of sodium sulphide, or the mixture prepared from sulphur and
caustic soda-lye used in the above Example C, may be replaced by alkaline poly-
sulphides or the like. The quantity of sulphur and of alkaline sulphide, or of the
mixtures acting in the same manner, used in the process, may be varied in a
suitable manner. The process may also be carried out at higher or lower
temperatures than those prescribed in the examples, and in order to isolate the
finished dye-stuffs, the melts obtained may be treated in another manner than that
described in the examples. Instead of dissolving these melts, with or without the
addition of alkali or alkaline sulphide or the like, and of evaporating the so-formed
solutions to dryness, the solutions of the said melts in pure water may also be
neutralized or acidulated with acids, and the precipitates, if necessary, separated
by means of common salt or the like, may be transformed into the dye-stuffs by
dissolving the same in alkalies, alkaline sulphides, or the like, and subsequently
evaporating to dryness. The herein described dye-stuffs are of special technical
value on account of the property they exhibit of dyeing unmordanted cotton,
even at ordinary temperatures, producing very fast shades.
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 from abroad), I declare that what I claim is :-
:-
1. The production of dye-stuffs capable of dyeing cotton in hot and cold baths,
from hydroxycarboxylic acids, amidocarboxylic acids, nitrocarboxylic acids, nitro-
hydroxycarboxylic acids, or amidohydroxycarboxylic acids of the benzene
or naphthalene series, which process consists in heating together with sulphur
and alkaline sulphides, or with substances or mixtures acting in a similar manner,
the said carboxylic acids, or salts or similar derivatives thereof.
2. The manufacture of colouring matters capable of dyeing cotton in hot and
cold baths from the simple hydroxy compounds of the benzene or naphthalene
series, which process consists in heating together with sulphur and alkaline

page_text: sulphides, or with substances or mixtures acting in a similar manner, phenol, ortho
cresol, metacresol, para cresol, or mixtures of the isomeric cresols (such as constitute
crude cresol), xylenol, resorcinol, alpha naphthol, beta naphthol, beta, beta, or
beta, beta, dihydroxynaphthalenes, or the like.
3. As new products of manufacture, the new dye-stuffs produced by the processes
hereinbefore defined, or by any other process affording the same result.
Dated this 22nd day of August 1896.
NEWTON & SON,
Agents for the Applicant.