Improvements in the Manufacture of Colouring Matters Containing Sulphur.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Colouring Matters Containing
Sulphur.
We, READ HOLLIDAY & SONS, LIMITED, Manufacturing Chemists, of Turnbridge,
Huddersfield, in the County of York, JOSEPH TURNER, Director of the said Com-
pany, of the same place, and HARRY DEAN, Chemist, of Greenhead Road, Hudders-
field, aforesaid, and JAMES TURNER, Chemist, of Spink Field Road, Birkby,
Huddersfield, aforesaid, both in the employment of the said Company, do hereby
declare the nature of this invention to be as follows:-
In the course of our experiments in developing an invention made by us
relating to the manufacture of certain amido-sulpho acids of the phenolic and
carbo oxylic series by heating with bi-sulphite of soda, the following bodies:-
I. Para nitro phenol. II. Ortho nitro phenol. III. Ortho nitro salicylic acid.
IV. Para nitro salicylic acid. V. Meta nitro benzoic acid, we discovered that the
said sulpho acids may be made to yield useful shades by heating in a suitable
manner with sodium sulphide and sulphur or with caustic alkalies and sulphur.
The shades obtained vary considerably according to the proportions used and
the temperature employed. In general the temperature may vary between 160° C.
and 260° C. the most beneficial results usually being obtained at a temperature
intermediate between the two. The products obtained dye vegetable fibre shades
ranging from drab and brown to violet and greenish blacks. The following
example illustrates the manner in which our invention is carried into effect.
We take say 30 parts crystallized sulphide of soda and after melting add 5 parts
sulphur, and continue heating till the sulphur dissolves, we then add 10 parts
para amido phenol sulphonic acid and gradually raise the temperature to about
250° C. and maintain at this temperature for 2 or 3 hours. The melt is then
allowed to cool and may be used directly for dyeing. Further we may take with
advantage mixtures of any of the above mentioned sulpho acids with nitro or
nitroso phenols or naphtols or their sulpho acids amido oxy benzene or naphtalene
or their sulpho acids in molecular proportions, and heat with sodium sulphide
and sulphur or caustic alkalies and sulphur, as above described.

page_text: Improvements in the Manufacture of Colouring Matters Containing
Sulpbur.
We, READ HOLLIDAY & SONS, LIMITED, Manufacturing Chemists, of Turnbridge,
Huddersfield, in the County of York, JOSEPH TURNER, Director of the said Com-
pany, of the same place, and HARRY DEAN, Chemist, of Greenhead Road, Hudders-
field. aforesaid, and JAMES TURNER, Chemist, of Spink Field Road, Birkby,
Huddersfield, aforesaid, both in the employment of the said Company, do hereby
declare the nature of this invention and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement:
In the course of our experiments in developing an invention made by us
relating to the manufacture of certain amido sulpho acids of the phenolic and
carboxylic series by heating with bisulphite of soda the following nitro bodies.
1. Para nitro phenol.
2. Ortho nitro phenol.
3. Ortho nitro salicylic acid.
4. Para nitro salicylic acid.
5. Meta nitro benzoic acid.
We discovered that the said sulpho acids may be made to yield useful shades
by heating in a suitable manner with sodium sulphide and sulphur or with caustic
alkalies and sulphur. The shades obtained vary considerably according to the
temperature employed and the proportions used. "In general the temperature may
vary between 160° C. and 260° C. the most beneficial results usually being
obtained at a temperature intermediate between the two. The products obtained
dye vegetable fibre shades ranging from drab and brown to violet and greenish
blacks.
The following example illustrates the manner in which our invention is carried
into effect.
We take say 30 parts crystallized sulphide of soda and after melting add 5 parts
of sulphur, and continue heating until the sulphur dissolves, we then add ten parts
of para amido phenol sulphonic acid and gradually raise the temperature to
about 250° C. and maintain it at this temperature for 2 to 3 hours. The melt
is then allowed to cool and may be used directly for dyeing. Further we may
take with advantage mixtures of any of the above mentioned sulpho acids with
nitro or nitroso phenols or naphtols or their sulpho acids, amido oxy benzene or
naphtalene or their sulpho acids in molecular proportions and heat with sodium
sulphide and sulphur or caustic alkalies and sulphur as above described, and a
as illustrated by the following. examples.
II.
120 parts of caustic soda 40° Be. are heated in a suitable vessel and 20 parts
of sulphur added, the heating is continued until the sulphur is completely
dissolved, we then add a mixture consisting of 20 parts ortho amido phenol
sulphonic acid and 20 parts para amido phenol sulphonic acid, and raise the
temperature to 200° C. for a few hours. The product of the reaction dyes vege-
table fibres black.
ITT

page_text: added a mixture consisting of 23 parts amido sulpho salicylic acid and 20 parts
para amido phenol sulphonic acid. The temperature is then raised to about
200° C. and maintained at this temperature until no further increase of colouring
matter is noticed. The product dyes vegetable fibres black.
IV.
90 parts of caustic soda 40° Be. are heated along with 15 parts of sulphur
until the sulphur is dissolved. We then add a mixture consisting of 109 parts
para amido oxy benzene and 19 parts para amido oxy benzene sulphonic acid
and raise the temperature to 200° C. and maintain at this temperature for 2
to 3 hours. The product may be used directly for dyeing and dyes vegetable
fibres bluish blacks.
The colouring matters obtained according to the preceding examples may be
with advantage treated with oxidising agents on the fibre, such as a solution of
chromic acid.
Having now particularly described and ascertained the nature of our said
invention, and in what manner the same is to be performed, we declare that what
we claim is:
1. The production of dyestuffs by heating the amido sulpho acids prepared as
hereinbefore described with sodium sulphide and sulphur or caustic alkalies and
sulphur at temperatures varying from 160° to 260° C.
2. The production of colouring matters by heating mixtures of the sulpho
acids, herein before referred to, with nitro or nitroso phenols or naphtols or their
sulpho acids in molecular proportions, together with sodium sulphide and sulphur,
or caustic alkalies and sulphur to about 220° C. for about 2 to 3 hours.
3. The production of dye stuffs by heating mixtures of the said sulpho acids
with amido phenols or naphtols in molecular proportions, together with sodium
sulphide and sulphur or caustic alkalies and sulphur to about 220° C. for about
2 to 3 hours.
4. As a new article of manufacture colouring matters produced substantially
according to the method herein before described and claimed in the foregoing
claims.
WM. BROOKES & SON,
55 and 56, Chancery Lane, London, Agents for the Applicants.