The Manufacture or Production of Dye Stuffs for Cotton.
Year: 1897

page_text: Date of Application, 19th July, 1897
Complete Specification Left, 15th Apr., 1898-Accepted, 25th June, 1898
[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:-
My foreign correspondents have found that valuable dye-stuffs for cotton are
obtained, if alpha, alpha, amido naphthol, alpha, alpha, dihydroxynaphthalene,
or the sulphonic acids of these two compounds, are heated with sulphur and
alkaline sulphides, or with sulphur and alkalies, or with alkaline polysulphides,
or with mixtures or substances acting in the same or an analogous manner, and
if the dye-stuffs or products thus obtained are subjected to the treatment hereinafter
specified.
The products formed by melting alpha, alpha, amido naphthol, alpha, alpha
dihydroxynaphthalene, or the sulphonic acids thereof, with the above-mentioned
re-agents, yield, when applied to the vegetable fibre, from greyish-blue to black
shades, whilst the shades produced in baths containing alkaline sulphides are
from brown to brownish-black.
According to the researches of my foreign correspondents, the products thus
obtainable are not uniform, as they can be separated into two dye-stuffs, the
one of which is soluble with greater readiness, and has the property of producing
on unmordanted cotton, pure blue, blackish-blue, or bluish-black shades, whilst
the other dissolves less readily, and yields, on the vegetable fibre, from brown to
brownish-black shades.
This method of separation, which is based on the different degrees of solu-
bility of the two components, can be effected in a simple manner; for instance,
by treating with small quantities of hot water the products resulting from the
action of sulphur and alkaline sulphides, or the like, on the aforesaid alpha,
alpha, naphthalene derivatives, filtering off the solutions thus formed, and repeat-
ing this operation until the component soluble with greater readiness, and yielding
from blue, blackish-blue, to bluish-black solutions, has been wholly dissolved
out, subsequently uniting the filtrates, and isolating therefrom the dye-stuff in
a suitable manner, for instance by salting out.
The dye-stuffs thus obtained possess the property of yielding from blue, blackish-
blue, to bluish-black shades, on unmordanted cotton in boiling baths, which
advantageously contain certain reducing agents, such as sodium carbonate, and
grape sugar or the like, and they produce the same shades when used in cold baths
to which suitable reducing agents, such as alkaline sulphides or, the like, are
added. On using alkaline sulphides, or the like reducing agents, the fibres assume,
in general, a brownish color, which slowly turns into a deep blue, blackish-blue,
or bluish-black, if the wet dyed goods are exposed to the air, whereas this change
takes place immediately, if the dyed goods are rinsed.

page_text: DYE-STUFF FROM ALPHA ALPHA AMIDONAPHTHOL.
50. parts of alpha, alpha amidonaphtholsulphate are stirred into a mixture
prepared from 125 parts of sulphur, 90 parts of dry sodium sulphide, and 80 parts
of water. The resulting mass, while being stirred, is slowly heated to 240 degrees
Centigrade, and kept at this temperature for, say, about 2 hours, until test portions
of the melt, when dissolved in water, yield an indigo-blue solution, and the intensity
of the colour no longer increases. After the end of the formation of the dye-stuff
which takes place while ammonia is set free, the mass is allowed to cool, sub-
sequently finely-divided, and repeatedly treated with small quantities of hot water,
until the component part of the melt, which is readily soluble (shewing a greenish-
blue colour) has been wholly dissolved out. From the united filtrates, the finished
dye-stuff is precipitated by means of common salt, and subsequently isolated by
filtration, pressing, and drying.
When pulverized, this dye-stuff represents a bluish-black powder. It yields
pure indigo-blue shades on cotton, in boiling and cold baths containing reducing
agents.
The component part of the melt, which is soluble with less readiness, and
therefore remains on treating the melt with small quantities of hot water, produces
from greyish-brown to brown shades when applied to cotton in baths containing
alkaline sulphide.
SECOND EXAMPLE.
COLOURING MATTER OBTAINED FROM ALPHA ALPILA DIHYDROXYNAPHTHALENE.
50 parts of alpha, alpha dihydroxynaphthalene are introduced into a mixture
prepared from 100 parts of sulphur, 95 parts of dry sodium sulphide, and 95 parts
of water. While being stirred, the mass is slowly heated to about 240 degrees
Centigrade, and kept at this temperature during about 2 hours, until test portions
of the melt dissolve in water with a pure blue or blackish-blue colour, and the
intensity of the coloration no longer increases. When this stage is arrived at,
the melt is allowed to cool, finely divided, and subsequently repeatedly treated
with small quantities of hot water, until the resulting solution no longer exhibits
a blue or blackish-blue colour. Finally, the finished dye-stuff is precipitated from
the united filtrates by the addition of common salt, and isolated by filtration,
pressing, and drying.
When pulverised, the colouring matter forms a bluish-black powder. It pro-
duces from blue to blackish-blue shades on unmordanted cotton in dyeing-baths
containing the aforesaid reducing substances. The shades are fast against the
action of alkalies and light.
T

page_text: beta, disulphonic acid are stirred, and the resulting mass is gradually-heated to
about 240 degrees Centigrade, care being taken that the mass is well agitated.
The mass is kept at the said temperature for about 2 hours, until the formation
of the blue colouring-matter is finished. Then, the melt is allowed to cool,
finely divided, and repeatedly treated with small quantities of hot water, until the
solution, when filtered, no longer exhibits a blue coloration. At this stage the
filtrates are united, and the blue dye-stuff is precipitated therefrom by the addition
of common salt. It is subsequently isolated by filtration, pressing, and drying.
The colouring matter thus obtained yields, on cotton, in baths containing
reducing agents, blue indigo-like shades which are fast against the action of
alkalies and light.
Other blue dye-stuffs are produced in an analogous manner if the alpha, alpha
amidonaphthol alpha, beta, disulphonic acid used in the above third example,
is replaced by other alpha, alpha, amido naphthol disulphonic or mono-sulphonic
acids.
FOURTHI EXAMPLE.
COLOURING-MATTER FROM ALPHA ALPHA DIHYDROXYNAPHTHALENE-ALPHA, BETA¹-
DISULPHONIC ACID
50 parts of alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonic acid
are added to a mixture obtained by dissolving 200 parts of crystallised sodium
sulphide (NaS. 9 aq.), and 100 parts of sulphur. The mixture, which is well
stirred, is heated to from about 240 to 250 degrees Centigrade, and kept at this
temperature, until test portions of the melt, when dissolved in water, yield a pure
blue or bluish-black solution, and the intensity of the coloration no longer increases.
When cool, the finely divided melt is repeatedly treated with small quantities
of hot water, until the solution thus formed no longer exhibits a blue or bluish-
black coloration. From the united filtrates, the finished dye-stuff is subsequently
precipitated by the addition of common salt, filtered off, pressed, and dried.
It forms a bluish-black mass, and produces on cotton, in hot and cold baths
containing reducing agents, from blue to bluish-black shades which are fast
against the action of alkalies and light.
The process proceeds in an analogous manner, if other alpha, alpha, dihydroxy-
naphthalene disulphonic or monosulphonic acids are substituted for the alpha,
alpha, dihydroxynaphthalene-alpha, beta, disulphonic acid used in the preceding
fourth example. Thus, for instance, from alpha, alpha, dihydroxynaphthalene
alpha monosulphonic acid, a colouring matter is obtained, which produces from
blackish-blue to bluish-black shades.
Of course, my foreign correspondents do not limit themselves to the particulars
given in the above examples, which are merely typical, as the directions contained
therein can be varied within certain limits. Thus, for instance, the isolation of the
blue, blackish blue, or bluish-black dye-stuffs from their watery solutions may
be effected in another manner known and in use for similar purposes. Such or
the like modifications do not alter the nature of this invention, which relates to the
production of blue, blackish-blue or bluish-black cotton dyes, from the products
obtained by melting with sulphur and alkaline sulphides, or the like, the said
alpha, alpha, naphthalene derivatives.
1
1011 JT.... 1807
NEWTON & SON,
Agents for the Applicants.

page_text: 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 found that valuable dye-stuffs for cotton are
obtained if alpha, alpha, amidonaphthol, alpha, alpha-dihydroxy naphthalene,
or the sulphonic acids of these two compounds, are heated with sulphur and
alkaline sulphides, or with sulphur and alkalies, or with alkaline polysulphides,
or with mixtures or substances acting in the same or an analogous manner, and
if the dye-stuffs or products thus obtained are subjected to the treatment hereinafter
specified.
The products formed by melting alpha, alpha amidonaphthol, alpha, alpha
dihydroxynaphthalene, or the sulphonic acids thereof, with the above mentioned
reagents, yield, when applied to the vegetable fibre, from greyish-blue to black
shades, whilst the shades produced in baths containing alkaline sulphides, are
from brown to brownish-black.
According to the researches of my foreign correspondents, the products thus
obtainable are not uniform, as they can be separated into two distinct dye-stuffs, the
one of which is soluble with greater readiness than the other, and has the property
of producing, on unmordanted cotton, pure blue, blackish-blue or bluish-black
shades, whilst the other dissolves less readily, and yields on the vegetable fibre
brown to brownish-black shades.
The method of separation which is based on the different degree of solubility of
the two components is of a simple character; thus, for instance, the separation can
be effected by treating, with small quantities of hot water, the products resulting
from the action of sulphur and alkaline sulphides, or the like, on the aforesaid alpha₁
alpha, naphthalene derivatives, filtering off the solutions thus formed, and repeat-
ing this operation, until the component which is soluble with greater readiness, and
yields from blue, blackish-blue to bluish-black solutions, has been wholly dissolved
out, subsequently uniting the filtrates, and isolating therefrom the dye stuff in
a suitable manner, for instance by salting out.
The dye stuffs thus obtained possess the property of yielding from blue, blackish-
blue, to bluish-black shades, on unmordanted cotton, in boiling baths, which
advantageously contain certain reducing agents, such as alkaline sulphide, or
sodium carbonate, together with grape sugar or the like, and they produce the
same shades when used in hot baths containing caustic alkalies, or in cold baths,
to which suitable reducing agents, such as alkaline sulphides or the like, are
added. On using alkaline sulphides, or the like reducing agents, the fibres assume
in general a brownish color, which slowly turns into a deep blue, blackish-blue,
or bluish-black, if the wet dyed goods are exposed to the air, whereas this change
takes place immediately, if the dyed goods are rinsed.
The components which are soluble with greater difficulty differ from the dye-
stuffs above mentioned in a typical manner, by reason of their property of pro-
ducing from brown to brownish-black shades on cotton in baths containing alkaline
sulphides, or other similar reducing agents.
In order to illustrate this new process, my foreign correspondents give the
following examples, in which the action of sulphur and alkaline sulphides, or
the like, on the said alpha, alpha, naphthalene derivatives, and the isolation of
the blue colouring matters from the raw products, are described. The parts are
by weight.

page_text: FIRST EXAMPLE.
DYE-STUFF FROM ALPHA ALPHA AMIDONAPHTHOL.
50 parts of alpha, alpha, amidonaphthol-sulphonate are stirred into a mixture
prepared from 125 parts of sulphur, 90 parts of dry sodium sulphide, and 80 parts
of water. The resulting mass, while being stirred, is slowly heated to 240 degrees
Centigrade, and kept at this temperature for, say, about 2 hours, until test portions,
when dissolved in water, yield an indigo-blue solution, and the intensity of the
colour no longer increases. When the formation of the dyestuff is ended (ammonia
being set free the while), the mass is allowed to cool, is subsequently finely divided,
and is repeatedly treated with small quantities of hot water, until the 'component
part, which is readily soluble (shewing a greenish-blue colour), has been wholly
dissolved out. From the united filtrates, the finished dyestuff is precipitated by
means of common salt, and subsequently isolated by filtration, and is then pressed
and dried.
i
When pulverized, this dye stuff represents a bluish-black powder. It yields'
pure indigo blue shades on cotton in boiling and cold baths containing reducing
agents.
The other component part, which is soluble with less readiness, and there-
fore remains on treating the mass with small quantities of hot water, produces
from greyish-brown to brown shades, when applied to cotton in baths containing.
alkaline sulphide.
SECOND EXAMPLE.
COLOURING MATTER OBTAINED FROM ALPHA ALPHA DIHYDROXYNAPHTHALENE.
50 parts of alpha, alpha, dihydroxynaphthalene are introduced into a mixture
prepared from 100 parts of sulphur, 95 parts of dry sodium sulphide, and 95 parts
of water. While being stirred, the mass is slowly heated to about 240 degrees
Centigrade, and kept at this temperature during about 2 hours, until test portions
dissolve in water with a pure blue or blackish-blue color, and the intensity of the
colour no longer increases. When this stage is arrived at, the mass is allowed to
cool, is finely divided, and is subsequently repeatedly treated with small quantities
of hot water, until the resulting solution no longer exhibits a blue or blackish-
blue colour. Finally, the finished dye-stuff is precipitated from the united filtrates
by the addition of common salt, and isolated by filtration, and is then pressed and
dried.
When pulverised, the colouring matter forms a bluish-black powder. It pro-
duces from blue to blackish-blue shades on unmordanted cotton in dyeing baths
containing the aforesaid reducing substances. The shades are fast against the
action of alkalies and light.
THIRD EXAMPLE.
DYE-STUFF PRODUCED FROM ALPHA ALPHA AMIDONAPIITHOL-ALPHA BETAL
DISULPIIONIC ACID.
Into a solution of sodium polysulphide obtained from 67 parts of soda, 127 parts
of sulphur, and 50 parts of water, 50 parts of alpha, alpha, amidonaphthol-alpha,
beta, disulphonic acid are stirred, and the resulting mass is gradually heated to
about 240 degrees Centigrade, care being taken that the mass is well agitated.
The mass is kept at the said temperature for about 2 hours, until the formation
of the blue colouring matter is finished. Then the mass is allowed to cool, is
finely divided, and is repeatedly treated with small quantities of hot water, until the
solution, when filtered, no longer exhibits a blue colour. At this stage, the
filtrates are united, and the blue dye-stuff is precipitated therefrom by the addition
of common salt. It is subsequently isolated by filtration, and is then pressed and
dried.
The colouring matter thus obtained yields on cotton in baths containing

page_text: COLOURING-MATTER FROM ALPHA ALPHA-DIHYDROXYNAPIITHALENE-ALPILA
DISULPHONIC ACID
BETA1
50 parts of alpha, alpha, dihydroxynaphthalene alpha, beta, disulphonic acid
are added to a mixture obtained by dissolving 200 parts of crystallized sodium
sulphide (NaS 9 aq.) and 100 parts of sulphur. The mixture, which is well
stirred, is heated to from about 240 to 250 degrees Centigrade, and kept at this
temperature, until test portions when dissolved in water, yield a pure
blue or bluish-black solution, and the intensity of the color no longer increases.
When cool, the finely divided melt is repeatedly treated with small quantities
of hot water, until the solution thus formed no longer exhibits a blue or bluish-
black colour. From the united filtrates, the finished dye-stuff is subsequently
precipitated by the addition of common salt, filtered off, pressed, and dried.
It forms a bluish-black mass, and produces on cotton, in hot and cold baths
containing reducing agents, from blue to bluish-black shades, which are fast
against the action of alkalies and light.
The process proceeds in an analogous manner, if other alpha, alpha, dihydroxy-
naphthalene disulphonic or monosulphonic acids are substituted for the alpha,
alpha, dihydroxynaphthalene-alpha, beta, disulphonic acid. Thus, for instance,
from alpha, alpha, dihydroxynaphthalene alpha monosulphonic acid; a colouring
matter is obtained, which produces from blackish-blue to bluish-black shades.
My foreign correspondents do not limit themselves to the particulars given in
the above examples, which are merely typical, as the directions contained therein
can be varied within certain limits. Thus, for instance, the isolation of the blue,
blackish-blue, or bluish-black dyestuffs from their watery solutions, may be
effected in any other manner known and in use for similar purposes. Such or
the like modifications do not alter the nature of this invention, which relates to the
production of blue, blackish-blue, or bluish-black cotton dyes from the products
obtained by melting, with sulphur and alkaline sulphides or the like, the said
alpha, alpha, naphthalene derivatives.
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 manufacture of blue, blackish-blue or bluish-black cotton dye-stuffs
from the products resulting from the melting of alpha, alpha, amidonaphthol
alpha, alpha-dihydroxynaphthalene, alpha, alpha, amidonaphthol sulphonic acids,
alpha alpha dihydroxynaphthalenesulphonic acids, or salts thereof,
with sulphur and alkaline sulphides, or with sulphur and alkalies,
with alkaline polysulphides, or with the like mixtures or substances acting in
the same or a similar manner, as set forth.
or
2. For the production of blue, blackish-blue or bluish-black cotton dyestuffs,
the separation into two distinct parts of the products obtainable, by melting with
sulphur and alkaline sulphides, with sulphur and alkalies, or the like alkaline
sulphide-carrying compounds, the hereinbefore defined alpha, alpha, naphthalene
compounds, which action of separation is based on the different degree of solubility
of the two component parts contained in the products obtainable by the said
melting process, as set forth.
3. The process of producing blue, blackish-blue, and bluish-black cotton dye-

page_text: stuffs, which process consists in repeatedly treating with hot water those products
which result from the action of sulphur and alkaline sulphides, sulphur and alkalies,
or the like alkaline sulphide-carrying substances, on the said alpha, alpha
naphthalene compounds, until the more readily soluble component part thereof
has been wholly dissolved out, filtering off the solutions thus obtained, and isolating
from the joint filtrates, in any suitable manner, the blue, blackish-blue, or bluish-
black cotton dye-stuffs.
.
4. As new articles of manufacture, the new blue, blackish-blue, or bluish-black
cotton dye-stuffs obtainable as hereinbefore described.
Dated this 14th day of Anvil 1808
NEWTON & SON,
Agents for the Applicants.