The Manufacture and Production of New Colouring-matters of the Anthracene Series.
Year: 1899

page_text: Date of Application, 8th July, 1899
Complete Specification Left, 4th Apr., 1900-Accepted, 5th May, 1900
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Colouring-matters of the
Anthracene Series.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin and Soda Fabrik, of Lud-
wigshafen-on-Rhine, in the German Empire) to be as follows:
In the Specifications of Letters Patent 19588 and 19589; of the year 1891, and
13029, of the year 1892, all granted to me on communications from my present
foreign correspondents, the production of blue mordant-dyeing colouring-
matters from nitro-anthraquinone is described. Certain of the colouring-matters
there described are well known in commerce under the name of anthracene blues.
The present invention relates to the production, from certain of these dyes, viz.,
those of a more greenish shade of blue, of new colouring-matters of similar dye-
ing properties but which are distinguished from the colouring-matters from which
they are obtained, mainly in that they possess extraordinary fastness to fulling.
The colouring-matters which are used as initial material for the purposes of
the present invention are, for instance, those which can be obtained in accord-
ance with the processes of the Letters Patent hereinbefore referred to, when using
fuming sulphuric acid containing about 12 per cent. free anhydride, for the
treatment of dinitro-anthraquinone, (see, for instance, in the aforesaid Specifica-
tions, Example 1 of 19588/91, and Example 2 of 13029/92.) Moreover, the
colouring-matter obtained according to the process of Letters Patent 16495, of
1897, (also granted to me upon a communication from my foreign correspon-
dents), by the treatment of dinitro-anthraquinone simultaneously with. fuming
sulphuric acid, boracic acid and sulphur can be used. Such colouring-matters
prepared as aforesaid, and suitable for use for the purposes of this invention are
known on the market as anthracene blue WG; anthracene blue WG extra; and
anthracene blue WGG. Further the colouring-matter known in commerce as
brilliant alizarine cyanine can also be treated according to the present invention.
The new process for the production of the colouring-matters fast to fulling
consists essentially in treating the initial materials referred to, at a high tempera-
ture, with either ammonia and a fixed alkali, such as caustic soda, or with a
fixed alkali alone. On treating with caustic alkali and ammonia the reaction
must be effected under pressure. When working with fixed caustic alkali the
treatment may either be effected under pressure, or at ordinary pressure.
The products obtained when ammonia and fixed alkali are used are different
from those obtained when fixed alkali alone is used. In the first case the product
obtained dyes chrome mordanted wool giving a shade which is practically the same
as that yielded by the initial colouring-matter, but the colouration obtained with
the new colouringmatter satisfies the highest requirements as regards fastness to
fulling. If the treatment hereinafter more particularly described, with fixed
alkali alone, be adopted; the colouring-matter obtained not merely possesses this

page_text: increased degree of fastness, but dyes chrome mordanted wool yielding shades
which are redder than those of the initial product.
The following examples will serve to further illustrate the nature of the inven-
tion. The parts are by weight:
EXAMPLE I.
Mix together about 100 parts of the colouring-matter paste known in commerce
as anthracene blue G, equal to 10 parts dry colouring-matter, and 20 parts of
solid caustic soda, and stir this mixture into about 100 parts of ammonia water
containing about 20 per cent. NH3. Heat the mixture in an autoclave for about
seven hours at 150° Centigrade. Allow the melt to cool, dilute with water, and
precipitate the colouring-matter by means of an acid. Filter and wash. -
The product thus obtained can at once be used as a paste for dyeing. When
dry it constitutes a powder possessing a bronze-like lustre. It is almost insoluble.
in hot water. but is soluble in caustic soda and carbonate of soila, the solution
being a pure blue, and in sodium acetate the solution being violet-blue.
alcohol the solution is violet, and in concentrated sulphuric acid it is yellow-red.
The colour obtained on wool mordanted with chrome is of a greenish-blue shade.
EXAMPLE II.
In
Mix together 100 parts of the product obtained according to Example I of the
Specification of Letters Patent 16495, of 1897, in the form of a paste corre-
sponding to ten parts dry colouring-matter, and 20 parts of solid caustic soda
and 100 parts of ammonia water, containing 20 per cent. NH3. Heat the mixture
in an autoclave for about seven hours at a temperature of 150° Centigrade..
Work up in the manner described in Example I. The colouring-matter obtained
closely resembles that obtained according to Example I.
EXAMPLE, DII.
Mix together about 100 parts of the colouring-matter known in commerce as
anthracene blue G, in the form of a 10 per cent. paste corresponding to ten
parts dry colouring matter, and 38 parts of caustic soda lye, containing aliout 24
per cent. Na OH. Heat this mixture in an autoclave for about 3 hours at a tem-
perature of 160-1650 Centigrade. Allow to cool, pour the melt into water, boil
up, precipitate the colouring-matter by means of acid, and filter. The colouring-
niatter so obtained, when dry, is a powder possessing a metallic lustre, which is
almost insoluble in hot water, but which dissolves in alcohol and aniline giving
red-violet solutions, in concentrated sulphuric acid the solution is bordeaux-red,
the solution in sodium acetate is violet, in carbonate of soda, violet-blue, and in
caustic soda, blue.
EXAMPLE IV.
Mix about 100 parts of the anthracene blue G paste and 50 parts of solid caustic
soda, and heat the mixture to boiling for about three hours.
with water and precipitate the colouring-matter. with acid.
obtained has similar properties to that obtained according to Example II.
EXAMPLE V.
Dilute the melt
The product so
Mix together, about 100 parts of 10 per cent. paste of the colouring matter”
altained naudin

page_text: In the foregoing examples the proportions of the agents used, the degree of
temperature and the pressure employed can be varied considerably without
departure from the invention.
noted thin Q4h J
1000
The Manufacture and Production of New Colouring-matters of the
Anthracene Series.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by the Badische Anilin and Soda Fabrik, of Lud-
wigshafen-on-Rhine, in the German Empire) and in what manner the same is
to be performed to be particularly described and ascertained in and by the fol-
lowing statement:
:
In the Specifications of Letters Patent 19588 and 19589 of the year 1891, and
13029 of the year 1892 all granted to me on communications from my present
foreign correspondents, the production of blue mordant-dyeing colouring
matters from nitro-anthraquinone is described. Certain of the colouring-matters
there described are well known in commerce under the name of anthracene blues.
The present invention relates to the production from certain of these dyes, viz.
those of a more greenish shade of blue, of new colouring-matters of similar dye-
ing properties but which are distinguished from the colouring-matters from which
are obtained, mainly in that they possess extraordinary fastness to fulling.
The colouring matters which are used as initial materials for the purposes of
the present invention are, for instance, those which can be obtained in accord-
ance with the processes of the Letters Patent hereinbefore referred to, when using
fuming sulphuric acid containing about twelve per cent. free anhydride, for the
treatment of dinitro-anthraquinone, (see for instance in the aforesaid Specifica-
tions Example 1 of 19588/91, and Example 2 of 13029/92.) Moreover, the
colouring matter obtained according to the process of Letters Patent 16495 of
1897 (also granted to me upon a communication from my foreign correspon-
dents) by the treatment of dinitro-anthraquinone simultaneously with fuming
sulphuric acid boracic acid and sulphur can be used. Such colouring matters
prepared as aforesaid, and suitable for use for the purposes of this invention are
known on the market as anthracene blue WG; anthracene blue WG extra; and
anthracene blue WGG. Further the colouring-matter known in commerce as
brilliant alizarine cyanine can also be treated according to the present invention.
The new process for the production of the colouring matters fast to fulling
consists essentially in treating the initial materials referred to, at a high tempera-
ture, with either ammonia and a fixed alkali, such as caustic soda, or with a
fixed alkali alone. On treating with caustic alkali and ammonia the reaction
must be effected under pressure. When working with fixed caustic alkali the
treatment may either be effected under pressure or not, that is at, or above ordi-
nary pressure.
The products obtained when ammonia and fixed alkali are used are different
from those obtained when fixed alkali alone is used. In the first case the product
obtained dyes chrome mordanted wool,, a shade which is practically the same

page_text: as that vielded by the initial colouring-matter, but the colouration obtained with
the new colouring matter satisfies the highest requirements as regards fastness to
fulling. If the treatment hereinafter more particularly described, with fixed
alkali alone, be adopted, the colouring matter obtained not merely possesses this
increased degree of fastness, but dyes chrome mordanted wool, shades which
are redder than those of the initial product.
The following examples will serve to further illustrate the nature of the. inven-
tion and the manner in which it may be carried into practical effect, but the inven-
tion is not confined to the said examples. The parts are by weight.
EXAMPLE I.
Mix together about one hundred parts of the colouring matter paste, known
in commerce as anthracene blue WG, equal to ten parts dry colouring matter, and
twenty parts of solid caustic soda, and stir this mixture into about one hundred
parts of ammonia water containing about twenty per cent. NH. Heat the mix-
ture in an autoclave for about seven hours at one hundred and fifty degrees Cen-
tigrade. Allow the melt to cool, dilute with water, and precipitate the colouring-
matter by means of an acid: Filter and wash:
In
The product thus obtained can at once be used as a paste for dyeing. When
dry it constitutes a powder possessing a bronze-like lustre. It is almost insoluble
in hot water, but is solubile in caustic soda and carbonate of soda, the solution
being a pure blue, and in sodium acetate the solution being violet-blue.
alcohol the solution is violet, and in concentrated sulphuric acid it is yellow-red.
The colour obtained on wool mordanted with chrome is of a greenish blue shade.
EXAMPLE 2.
Mix together one hundred parts of the product obtained according Example 1
of the Specification of Letters Patent No. 16495 of 1897, (in the form of a paste
corresponding to ten parts dry colouring-matter) and twenty parts of solid caustic
soda and one hundred parts of ammonia water, containing twenty per cent. NH.
Heat the mixture in an autoclave for about seven hours at a temperature of one
hundred and fifty degrees Centigrade. Work up in the manner described in
Example 1. The colouring matter obtained closely resembles that obtained
according to Example 1 of this specification:
EXAMPLE 3.
Mix together about one hundred parts of the colouring matter known in com-
merce as anthracene blue WG in the form of a ten per cent, paste corresponding
to ten parts dry colouring matter and thirty eight parts of caustic soda lve, con-
taining about twenty four per cent. Na OH. Heat this mixture in an autoclave
for about three hours at a temperature of one hundred and sixty, to one hun-
dred and sixty five degrees Centigrade. Allow the melt to cool and pour it into
water, boil up, precipitate the colouring matter by means of an acid, and filter.
The colouring matter so obtained, when dry, is a powder possessing a metallic
lustre, which is almost insoluble in hot water, but which dissolves in alcohol and
aniline, the solutions being red-violet, in concentrated sulphuric acid the solu-
tion is bordeaux red, the solution in sodium acetate is violet, in carbonate of
soda, violet blue, and in- caustic soda, blue.
EXAMPLE 4.
Mix about one hundred parts of the anthracene blue W G paste, and fifty parts
of solid caustic soda, and heat the mixture to boiling for about three hours.
Dilute the melt with water and precipitate the colouring matter with acid: The
product so obtained has similar properties to that obtained according to Example 3.
EXAMPLE 5.
Viv together about one hundred parts of ten per cent. paste of the colouring

page_text: 16495 of 1897, and forty parts caustic soda lye (containing about twenty four
per cent: NaOH) and heat the mixture in an autoclave for about ten hours at a
temperature of one hundred and sixty degrees Centigrade. Allow the melt to
cool and work it up in the manner described in the foregoing Example 3. The
product so obtained when dry, is a powder of a bronze like lustre, which is almost
insoluble in hot water and difficultly soluble in sodium acetate, the solution being
red-violet; it is soluble in carbonate of soda, the solution being violet-blue, and
in caustic soda, the solution being blue. The solution in alcohol and' aniline is
cherry-red, and in concentrated sulphuric acid, violet.
In the foregoing examples the proportions of the agents used, the degree of
temperature, and the pressure, employed, can be varied considerably without
departure from the nature of the invention.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I.
claim is:-
-
.
1. The manufacture of new colouring matters of the anthracene series by heat-
ing the colouring matters horeinbefore defined, with ammonia and fixed caustic
alkali simultaneously.
2. The manufacture of new colouring matter of the authracene series by heat-
ing the colouring matters herein before defined, with fixed caustic alkali.
3. The manufacture of new colouring matters of the anthracene series, sulj-
stantially as hereinbefore described in the several foregoing examples.
4. As products of manufacture the new colouring matters of the anthracene
series such as can be obtained substantially as hereinbefore described.
Dated this 30th day of March 1900.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.