The Manufacture and Production of New Colouring Matters for Animal Fibre.
Year: 1897

page_text: Date of Application, 12th July, 1897
Complete Specification Left, 7th Apr., 1898-Accepted, 18th June, 1898
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Colouring Matters for
Animal Fibre.
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
communicated to me by the Badische Anilin & Soda Fabrik of Ludwigshafen-on-
Rhine, in the Empire of Germany) to be as follows:-
-
My foreign correspondents have acquired patent rights for the manufacture of
mordant dyeing colouring matters from nitro-anthraquinones some of which are
well known in commerce under the name of anthracene blues (seo Letters Patents
Nos. 19588, 195891, 1314793, 130292, 15246, 15325.)
In the manufacture of anthracene blues a nitro-anthraquinone, or reduction
product therefrom, is treated with fuming sulphuric acid with or without, the
presence of a reducing agent, such as sulphur, and in this way intermediate
colouring matters are obtained which are soluble in water, and possess the chemical
character of sulphuric acid esters. On treatment with water under suitable con-
ditions they yield mixed colouring-matters containing poly-oxy-anthraquinone
sulpho-acids. My foreign correspondents have now discovered that such sulphuric
acid esters can be combined with phenolic bodies including the hydroxy-carboxylic
acids and that the new products thus obtained constitute soluble colouring
matters which dye wool from the acid bath very efficiently giving bright violet,
to blue, shades; the initial materials before condensation with a phenolic body
under similar conditions giving only brown-red to bordeaux-red shades. If the
goods dyed with the new colouring matters, without a mordant, be subsequently
treated with chrome greenish-blue to bluish-green shades are obtained.
The condensation with the phenols can be effected in various ways. It succeeds
best if the water-soluble colouring-matters are applied in the form of their esters
with sulphuric, or boracic, acids. It is therefore advantageous to add the phenolic
body chosen to the reaction mixture obtained by the treatment of the dinitro-
anthraquinone with fuming sulphuric acid in the presence of a reducing agent, or
of this and of boracic acid. This mixture with the phenolic body is then heated,
to say about sixty, to eighty, degrees Centigrade, for several hours, or as long us
it may be necessary in each case.
The following example will serve to further illustrate the nature of the inven-
tion but the details can in all cases be varied. The parts are by weight.
Mix about ten parts of 1.41 dinitro-anthraquinone with fifty, to one hundred
parts of fuming sulphuric acid and one and a half parts of finely divided sulphur.
The fuming sulphuric acid may contain for instance twelve to forty per cent. free
anhydride. Heat the mixture moderately for several hours but not higher than
about one hundred and thirty degrees Centigrade. When the colouring-matter is
practically completely soluble in water allow the melt to cool and add, at the
ordinary temperature, about eight parts of gallic acid. Stir the mixture all the
time and heat gradually to about fifty, to sixty, degrees Centigrade. The melt
assumes a brown colour and after about five, or six, hours the reaction is complete.
Allow the melt to cool, pour it into ice water, precipitate with common salt and
collect in the usual way. In the dry state the new colouring-matter is a black
powder readily soluble in water. Instead of gallic acids other phenols, or carboxy-
phenols, or their derivatives, can be used.

page_text: The method of production is essentially the same for all these colouring matters
but the temperatures, the proportions of the phenolic bodies used, the strength of
fuming acid and other details can be varied considerably.
Instead of pure 1.4' dinitro-anthraquinone orude dinitro-anthraquinone, such
as is obtained by nitrating anthraquinone, can be used.
Dated this 12th dow of Tulu 1907
JOHNSONS & WILCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Colouring Matters for
Animal Fibre.
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
communicated to me from abroad by the Badische Anilin & Soda Fabrik of Ludwig-
shafen-on-Rhine, in the Empire of Germany) 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 acquired patent rights for the manufacture of
mordant dyeing colouring matters from nitro-anthraquinones some of which are
well known in commerce under the name of anthracene blues (see Letters Patents
Nos. 19588 of 1891, 19589 of 1891, 13147 of 1892, 13029 of 1892, 15246 of 1892,
15325 of 1892).
In the manufacture of anthracene blues a nitro-anthraquinone, or reduction-
product therefrom, is treated with fuming sulphuric acid, with, or without, the
presence of a reducing agent, such as sulphur, and in this way intermediate
colouring-matters are obtained which are soluble in water, and possess the chemical
character of sulphuric acid esters. On treatment with water under suitable con-
ditions they yield mixed colouring-matters containing poly-oxy-anthraquinone
sulpho acids. My foreign correspondents have now discovered that such sulphuric
acid esters can be combined with phenolic bodies including the hydroxy-carboxylic
acids, and that the new products thus obtained constitute soluble colouring-
matters which dye wool from the acid bath very efficiently giving bright violet,
to blue, shades; the initial materials before condensation with a phenolic body
under similar conditions giving only brown-red to bordeaux-red shades. If the
goods dyed with the new colouring matters, without a mordant, be subsequently
treated with chrome, greenish-blue to bluish-green shades are obtained.
The condensation with the phenols can be effected in various ways. It succeeds
best if the water-soluble colouring-matters are applied in the form of their esters
with sulphuric or boracic acid, which latter result for instance when boracic acid
is used in the sulphuric acid melt. It is therefore advantageous to add the phenolic
body chosen to the reaction mixture obtained by the treatment of the dinitro-
anthraquinone with fuming sulphuric acid in the presence of a reducing agent, or
of this and of boracic acid. The mixture with the phenolic body is then heated
to say about sixty, to eighty, degrees Centigrade, for several hours, or as long as
it may be necessary in each case.

page_text: The following example will serve to further illustrate the manner in which the
invention is carried into practical effect but the details can in all cases be varied.
The parts are by weight.
Mix about ten parts of 1.41 dinitro-anthraquinone with fifty to one hundred
parts of fuming sulphuric acid and one and a half parts of finely divided sulphur.
The fuming sulphuric acid may contain for instance twelve to forty per cent. free
anhydride. Heat the mixture moderately for several hours but not higher than
about one hundred and thirty degrees Centigrade. When the colouring-matter is
practically completely soluble in water allow the melt to cool and add, at the
ordinary temperature, about eight parts of gallic acid. Stir the mixture all the
time and heat gradually to about fifty, to sixty, degrees Centigrade. The melt
assumes a brown colour and after about five, or six, hours the reaction is complete.
Allow the melt to cool, pour it into ice water, precipitate with common salt and
collect in the usual way. In the dry state the new colouring-matter is a black
powder readily soluble in water. Instead of gallic acid other phenols or carboxy-
phenols or their derivatives can be used.

page_text: The method of production is essentially the same for all these colouring-matters;.
but the temperatures, the proportions of the phenolic bodies used, the strength of
the fuming acid and other details can be varied considerably.
It is not essential that the 1.4' dinitro-anthraquinone used in carrying out this
invention be pure, as crude dinitro-anthraquinone such as is obtained by nitrating
anthraquinone, can be economically employed.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, I declare that what I claim is:-
1. The process for the manufacture of new colouring-matters by condensing the
sulphuric or horacic acid esters hereinbefore defined, with phenolic bodies includ-
ing the hydroxycarboxylic acids all substantially as herein before described.
2. The manufacture of new colouring-matters for animal fibre in the manners
herein before described in the example.
3. As new products of manufacture the new colouring-matters for animal fibre
such as result from the processes herein before described.
Dated 171
L A 1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.