The Manufacture or Production of Dye-stuffs for Cotton.
Year: 1898

page_text: Date of Application, 18th Nov., 1898
Complete Specification Left, 17th Aug. 1899-Accepted, 23rd Sept., 1899
[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, Breams Buildings,
Chancery Lane, E.C., in the County of London, Patent Agent, do hereby declare
the nature of this invention to be as follows:-
My foreign correspondents found some time since that blue dye-stuffs for cotton
are obtained by heating alpha' alpha amidonaphthol sulphonic acids, the azo colouring-
matters resulting from the combination of diazo compounds, and alpha¹ alpha*
amidonaphthol sulphonic acids, or the alpha' alpha dihydroxynaphthalenesulphonic
acids, alpha-alpha chloronaphtholsulphonic acids, alpha alpha amidonaphthol, or
alpha alpha dihydroxynaphthalene, with sulphur and alkaline sulphides, or with
alkaline polysulphides, or mixtures of sulphur and alkalies, or with substances acting
in the same or a similar manner, by subsequently treating the products thus obtained
with hot water, until the more readily soluble blue component part thereof has been
wholly dissolved out, filtering the so-formed solutions, and finally precipitating from
the joint filtrates the dye-stuffs with common salt, zinc chloride, or the like. These
colouring-matters produce on cotton, in boiling baths, with the addition of reducing
substances (such as grape sugar and sodium carbonate, alkaline sulphide, or the like),
and in cold baths containing alkaline sulphides, brown shades which turn to blue
when dyed wet goods are exposed to the action of the air and rinsed; whereas the less
readily soluble component part of the aforesaid products yields, in baths containing
alkaline sulphide, brown shades which are not altered by exposure to the air or by
rinsing..
My foreign correspondents have now found that new valuable blue colouring-
matters for cotton are obtained by heating the aforesaid alpha¹ alpha naphthalene
compounds, viz.:-alpha alpha amidonaphthol, alpha' alpha dihydroxynaphthalene,
sulphonic acids thereof, alpha¹ alpha chloronaphtholsulphonic acids, or the azo dye-
stuffs resulting from the combination of diazo compounds with alpha¹ alpha amido-
naphtholsulphonic acids, with sulphur and alkaline sulphides, or with alkaline
polysulphides, or mixtures of sulphur and alkalies, or with analogous substances
acting in the same or a similar manner, in the presence of zinc or zinc compounds.
This addition of zinc or zinc compounds to the mixtures to be melted, effects the
production of products which directly produce, on cotton, blue shades fast to the
action of light and alkalies. The advantage resulting therefrom consists in render-
ing unnecessary tedious and expensive operations, viz. :-extraction with hot water,
filtration of the extracts, and precipitation of the finished dye-stuffs from the joint
filtrates, because, according to the researches of my foreign correspondents, the
formation of the brown by-products is avoided by the said use of zinc or zinc
compounds.
In order to illustrate this new process more fully, the following example is given,
which is merely tvnical The parts are by weight.

page_text: EXAMPLE.
20 parts of dry powdered zinc chloride are stirred into a solution prepared from
132 parts of a 38 per cent. alpha¹ alpha amidonaphthol-alpha2 beta¹ disulphonic
acid paste, and 60 parts of soda-lye (containing 30 per cent. of NaOH). After the
addition of 87 parts of dry sodium sulphide, and 82 parts of flowers of sulphur, the
mixture is (while being stirred) slowly heated to 200 degrees Centigrade, and kept at
this temperature until the melt becomes solid, and can be easily reduced to a dry
powder. When this stage is reached, the iron vessel is closed, and the temperature
is raised to 240 degrees Centigrade, at which temperature the mass is kept for about
4 hours. The melt thus obtained forms a blueish-black powdery mass, and when
cool, it can be directly used for dyeing. It yields on cotton, in boiling baths con-
taining common salt, or common salt and sodium carbonate, pure blue indigo-like.
shades which are fast against the action of alkalies and light.
Other blue colouring-matters are obtained in an analagous manner, if the alpha]
alpha amidonaphthol alpha2 beta disulphonic acid used in the above example is
replaced by other alpha alpha amidonaphtholsulphonic acids, or by azo dye-stuffs
resulting from the combination of diazo or tetrazo compounds with alpha' alpha
amidonaphtholsulphonic acids, or by alpha¹ alpha amidonaphthol, alpha¹ alpha di-
hydroxynaphthalene, alpha¹ alpha dihydroxynaphthalene sulphonic acids, or alpha'.
alpha chloro-naphthol-sulphonic acids. In place of zinc chloride prescribed in the fore-
going example, other zinc compounds, such as zinc sulphate, zine carbonate, zinc oxide,
or the like, or metallic zinc, preferably in the form of zinc dust, can be used with the
same result.
My foreign correspondents wish it to be understood that they do not limit them-
selves to the particulars given in the above example, which is merely typical. Thus,
for instance, the soda-lye used therein can be replaced by sodium carbonate, ammonia,
or the like. In place of sulphur and sodium sulphide, sulphur and potassium sulphide,
or alkaline polysulphides, or mixtures of sulphur and alkalies, or the like substances,
acting in the same or a similar manner, can be likewise used. The proportions and
temperatures mentioned in the above example may also vary within certain limits.
Such or the like modifications or alterations do not alter the nature of the present
invention, which relates to the production of blue dye-stuffs for cotton by subjecting
the above defined alpha alpha, naphthalene compounds, or derivatives, to the action
of alkaline sulphide-carrying compounds, in the presence of zinc or zinc compounds,
and at high temperatures.
Dated this 18th day of November 1898.
NEWTON & SON,
Agents for the Applicant.
CUMI LEIE DIEUITICATIVA.
The Manufacture or Production of Dye-stuffs for Cotton.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Breams 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 found some time since that blue dye-stuffs for cotton are
obtained by heating alpha, alpha, amido naphtolsulphonic acids, the azo colouring
matters resulting from the combination of diazo-compounds and alpha, alpha,
amidónaphtholsulphonic acids, or the alpha, alpha, dihydroxynaphthalenesulphonic
acids, alpha, alpha, chloronaphtholsulphonic acids, alpha, alpha amidonaphthol,

page_text: or alpha, alpha, dihydroxynaphthalene with sulphur and alkaline sulphides
or. with alkaline polysulphides, or mixtures of sulphur and alkalies, or with
substances acting in the same or a similar manner by subsequently. treating
the products thus obtained with hot water until the more readily soluble blue
5 component part thereof has been wholly dissolved out, filtering the so formed solutions.
and finally precipitating from the joint filtrates the dye-stuffs with common salt,
zinc chloride or the like. These colouring-matters produce on cotton in boiling baths
with the addition of reducing substances (such as grape sugar and sodium carbonate
alkaline sulphide or the like) and in cold baths, containing alkaline sulphides, brown
shades which turn into blue when the dyed wet goods are exposed to the action of
the air and rinsed, whereas the less readily soluble component part of the aforesaid
products yields in baths containing alkaline sulphide, brown shades which are not
altered by exposure to the air or by rinsing.
My foreign correspondents have now found that new valuable blue colouring
matters for cotton are obtained by heating the aforesaid alpha, alpha, naphthalene
compounds or derivatives viz alpha, alpha, amidonaphthol, alpha, alpha, dihydroxy-
naphthalene, sulphonic acids thereof, alpha, alpha, chloronaphtholsulphonic acids, or
the azo dye-stuffs resulting from the combination of diazo-compounds with alpha,.
alpha, amidonaphtholsulphonic acids, with sulphur and alkaline sulphides or with:
alkaline polysulphides, or mixtures of sulphur and alkalies or with analogous
substances acting in the same or a similar manner, in the presence of zinc or. zinc
compounds. This addition of zinc or zinc compounds to the mixtures to be melted.
effects the production of products which directly produce on cotton blue shades fast to'
the action of light and alkalies. The advantage resulting therefrom consists in.
rendering unnecessary tedious and expensive operations viz. extraction with hot water,
filtration of the extracts and precipitation of the finished dye-stuffs from the joint
filtrates, because according to the researches of my foreign correspondents the
formation of the brown by-products is practically avoided by the said use of zinc or
zine compounds.
.
In order to illustrate this new process more fully the following example is given
which is merely typical. The parts are by weight.
EXAMPLE.
20 parts of dry powdered zinc chloride are stirred into a solution prepared from
132 parts of a 38 per cent. alpha, alpha, amidonaphthol-alpha, beta, disulphonic acid
paste and 60 parts of soda-lye (containing 30 per cent. of NaOH.) After the addition
of 87 parts of dry sodium sulphide and 82 parts of flowers of sulphur the mixture is
(while being stirred) slowly heated in an iron vessel by means of a metallic bath to
200 degrees Centigrade (temperature of the bath) and kept at this temperature until
the melt becomes solid and can be easily reduced to a dry powder. When this stage
is reached, the iron vessel is closed and the temperature of the bath is raised to
240 degrees Centigrade at which temperature the mass is kept for about 4 hours.
The melt thus obtained forms a blueish black powdery mass and when cool it can be
directly used for dyeing. It yields on cotton in boiling baths containing common
salt or common salt and sodium carbonate pure blue indigo like shades which are fast
against the action of alkalies and light.
Other blue colouring-matters are obtained in an analogous manner if the alpha,
alpha, amidonaphthol alpha, beta, disulphonic acid used in the above example is
replaced by other alpha, alpha, amidonaphtholsulphonic acids, or by azo dye-stuffs
resulting from the combination of diazo or tetrazo compounds with alpha, alpha
amidonaphthol sulphonic acids, or by alpha, alpha, amidonaphthol alpha, alpha
dihydroxynaphthalene alpha, alpha, dihydroxynaphthalene sulphonic acids or
alpha, alpha, chloronaphtholsulphonic acids. In place of zinc chloride prescribed in the
foregoing examples other zinc compounds such as zinc sulphate, zinc carbonate, zinc
oxide or the like, or metallic zinc preferably in the form of zinc dust can be used
with the same result.

page_text: My foreign correspondents wish it to be understood that they do not limit them-
selves to the particulars given in the above example which is merely typical. Thus
for instance the soda lye used therein can be replaced by sodium carbonate ammonia
of the like. In place of sulphur and sodium sulphide sulphur and potassium sulphide
or alkaline polysulphides or mixtures of sulphur and alkalies or the like substances
acting in the same. or a similar manner can be likewise used. The proportions and
*temperatures mentioned in the above example may also vary within certain limits.
Such or the like modifications or alterations do not alter the nature of the present
invention which relates to the production of blue dye stuffs for cotton by subjecting
the above defined alpha, alpha, naphthalene compounds or derivatives to the action
of alkaline sulphide carrying compounds in the presence of zinc or zinc compounds
and at high temperatures.
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 blue dyestuffs for cotton from the following alpha, alpha
naphthalene compounds or derivatives viz. alpha, alpha, amidonaphthol, alpha, alpha,
amidonaphtholsulphonic acids, alpha, alpha, dihydroxynaphthalene alpha, alpha, di-
hydroxynaphthalenesulphonic acids alpha, alpha, chloronaphtholsulphonic acids the
azo colouring matters obtainable by coupling alpha, alpha amidonaphtholsulphonic
acids with diazo or tetrazo products which process consists in heating at elevated
temperatures the aforesaid alpha, alpha, naphthalene compounds or derivatives with
sulphur and alkaline sulphide or the like alkaline sulphide carrying substances in the
presence of zine or zinc compounds.
4
2. As products of manufacture the new blue dye-stuffs for cotton obtainable by the
process hereinbefore claimed.
Duted this Oth dow of Aust 1800