Improvements in Dyeing or Printing Fibres Black, or Shades approaching thereto, with Aniline, its Homologues, or Derivatives.
Year: 1892

page_text: Date of Application, 11th June, 1892
Complete Specification Left, 13th Mar., 1893-Accepted, 13th May, 1893
UATION.
Improvements in Dyeing or Printing Fibres Black, or Shades
approaching thereto, with Aniline, its Homologues, or
Derivatives.
I, WILLIAM JULES SAMUEL Grawitz, of 62, Boulevard Gambetta, Nogent-
sur-Marne, (Seine) France, Civil Engineer, do hereby declare the nature of this
invention to be as follows :-
;—
Fibres which are dyed by means of a mineral salt of aniline (or of one of its
homologues or derivatives) under the oxidising action of a chlorate (the color
being developed by weathering after drying) are liable to become weakened.
The object of the present invention is to overcome this defect by the employment
of a ferrocyanide or a ferricyanide concurrently with a salt of vanadium or other
agent capable of bringing about the decomposition of the chlorate and its reaction
on the salt of the alkaloid employed.
I may use any of the prussiates for the purposes of this invention, that is to say
not only the double cyanides of iron and of the alkalies which are the best known
but also the double cyanides in which the iron is replaced by manganese, chromium,
nickel, or cobalt. I would also have it understood that two or more prussiates
may be used together, for instance red prussiate of potash and red prussiate of
ammonia. Similarly that two or more salts of aniline may be employed together,
for instance hydrochlorate of aniline and nitrate of aniline. Likewise that vanadate
of ammonia may be used conjointly with another soluble vanadate. In the same
way chlorate of potash may be substituted for chlorate of soda or both may be
used together.
I do not confine myself to the use of pure aniline that yields black as this process
is applicable to its homologues such as toluidines, xylidines, or derivatives such as
paraphenylendiamine and in general to all artificial amines, known to yield colors
approaching black with the decomposition products of the chlorates, whether for
printing or for dyeing purposes, and whether the matters to be treated are
unbleached or dyed, in the raw state, spun or woven, or in course of manufacture.
I will here indicate, merely by way of example the preparation of a bath
containing
CRUVIDIONAL MULTIVATION.
Improvements in Dyeing or Printing Fibres Black, or Shades
approaching thereto, with Aniline, its Homologues, or
Derivatives.
I, WILLIAM JULES SAMUEL GRAWITZ, of 62, Boulevard Gambetta, Nogent-
sur-Marne, (Seine) France, Civil Engineer, do hereby declare the nature of this
invention to be as follows:-
Fibres which are dyed by means of a mineral salt of aniline (or of one of its
homologues or derivatives) under the oxidising action of a chlorate (the color
being developed by weathering after drying) are liable to become weakened.
The object of the present invention is to overcome this defect by the employment
of a ferrocyanide or a ferricyanide concurrently with a salt of vanadium or other
agent capable of bringing about the decomposition of the chlorate and its reaction
on the salt of the alkaloid employed.
I may use any of the prussiates for the purposes of this invention, that is to say
not only the double cyanides of iron and of the alkalies which are the best known
but also the double cyanides in which the iron is replaced by manganese, chromium,
nickel, or cobalt. I would also have it understood that two or more prussiates
may be used together, for instance red prussiate of potash and red prussiate of
ammonia. Similarly that two or more salts of aniline may be employed together,
for instance hydrochlorate of aniline and nitrate of aniline. Likewise that vanadate
of ammonia may be used conjointly with another soluble vanadate. In the same
way chlorate of potash may be substituted for chlorate of soda or both may be
used together.
I do not confine myself to the use of pure aniline that yields black as this process
is applicable to its homologues such as toluidines, xylidines, or derivatives such as
paraphenylendiamine and in general to all artificial amines, known to yield colors
approaching black with the decomposition products of the chlorates, whether for
printing or for dyeing purposes, and whether the matters to be treated are
unbleached or dyed, in the raw state, spun or woven, or in course of manufacture.
I will here indicate, merely by way of example the preparation of a bath
containing
Aniline salt (hydrochlorate)
(or 1 equivalent)
Yellow prussiate of potash
-
1295 grammes
795
"
(or of an equivalent containing
of an equivalent of potash)
Chlorate of soda
(or
of an equivalent containing
2 equivalents of oxygen)
the total volume of the bath being 13 litres.
335
"
The fibrous materials impregnated with this mixture do not dye black but by
adding two to five grammes of vanadate of ammonia a magnificent black is produced
either by weathering or by steaming after drying and the fibre is entirely preserved.
The solution of the chlorate and especially that of the vanadium salt should be
11

page_text: to be dyed. Or the textile materials may first be impregnated with the salt
of vanadium and (the surplus liquid having been expelled) then with the other
matters.
By progressively increasing the proportion of the chlorate, as much as four
equivalents of oxygen may be supplied. The proportion of prussiate above
indicated is that which best preserves the fibre but I would have it understood that
the same may be varied. It may be greatly diminished, for instance to one-tenth,
as the prussiates appear to have a specific preservative action. For the yellow
prussiate an equivalent quantity of the red prussiate may be substituted, which
represents almost the same weight.
r
Instead of mixing a soluble prussiate with the dye bath, an insoluble prussiate
(or prussiates) may be fixed upon the fibre in a preliminary operation.
Dated this 11th day of June 1892.
J. S. GRA WITZ,
By A. M. & Wm. Clark,
53, Chancery Lane, London, Chartered Patent Agents.
COMPLETE SPECIFICATION.
Improvements in Dyeing or Printing Fibres Black, or Shades
approaching thereto, with Aniline, its Homologues, or
Derivatives.
I, WILLIAM JULES SAMUEL GRAWITZ of 62, Boulevard Gambetta, Nogent-
sur-Marne (Seine) France, Civil Engineer, 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 :-
This invention relates to dyeing or printing vegetable textile fibres or silk,
black or shades approaching thereto with aniline its homologues or derivatives.
Fibres which are dyed by means of a mineral salt of aniline (or of one of its
homologues or derivatives) under the oxidizing action of a chlorate (the color being
developed by weathering-i.e. exposing to air in ageing rooms or in ageing machines
- after drying) are liable to become weakened. The object of the present invention
is to overcome this defect by the employment of a ferrocyanide or a ferricyanide
concurrently with a salt of vanadium or other agent capable of bringing about the
decomposition of the chlorate and its reaction on the salt employed. I may use
any of the prussiates for the purposes of this invention, that is to say not only the
double cyanides of iron and of the alkalies which are the best known but also
the double cyanides in which the iron is replaced by manganese, chromium, nickel,
or cobalt. I would also have it understood that two or more prussiates may be
used together, for instance red prussiate of potash and red prussiate of ammonia.
Similarly that two or more salts of aniline may be employed together, for instance
hydrochlorate of aniline and nitrate of aniline. Likewise that vanadate of
ammonia may be used conjointly with another soluble vanadate.
In the same
way chlorate of potash may be substituted for chlorate of soda, or both may be
used together.
I do not confine myself to the use of pure aniline that yields black as this process
is applicable to its homologues such as toluidines, xylidines, or derivatives such as
paraphenylendiamine, and in general to all artificial amines, and all the alkaloids
known to yield colors approaching black with the decomposition products of the
chlorates whether for printing or for dyeing purposes and whether the matters to
be treated are unbleached or dyed, in the raw state, spun or woven, or in course of
manufacture.
I will here indicate, merely by way of example, the preparation of a bath
containing

page_text: Yellow prussiate or potasn
(or of an equivalent containing
of an equivalent of potash)
Chlorate of soda
(or
-
of an equivalent containing
2 equivalents of oxygen)
the total volume of the bath being 13 litres.
The grammes
335
"
The fibrous materials impregnated with this mixture do not dye black, but by
adding two to five grammes of vanadate of ammonia a magnificent black is produced
by weathering-i.e. exposing to air in ageing rooms or in ageing machines-after
drying and the fibre is entirely preserved. By steaming, a good black is obtained
but the fibre is a little weakened. The solution of the chlorate and especially that
of the vanadium salt should be added cold to the mixture of aniline salt and
prussiate. It is preferable in practice to add the vanadium salt to the bath just
before impregnating the fibrous material, in the proportion of about one-tenth
of a gramme of vanadate per kilo. of material to be dyed. Or the textile materials
may first be impregnated with the salt of vanadium and (the surplus liquid having
been expelled) then with the other matters, one or other of these last-mentioned
modes of operating being preferred because the vanadium is liable to form an
insoluble compound with the prussiate in the bath, so that the mixture speedily
becomes inactive.
By progressively increasing the proportion of the chlorate as much as four
equivalents of oxygen may be supplied. The proportion of prussiate above
indicated is that which best preserves the fibre, but I would have it understood
that the same may be varied. It may be greatly diminished, for instance to
one-tenth, as the prussiates appear to have a specific preservative action. For the
yellow prussiate an equivalent quantity of the red prussiate may be substituted,
which represents almost the same weight. Instead of mixing a soluble prussiate
with the dye bath, an insoluble prussiate (or prussiates) may be fixed upon the
fibre in a preliminary operation.
In conclusion, I would remark that in order to obtain a good color on silk, it is
preferable to repeat the dyeing operation two or more times.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what
I claim is―
In dyeing or printing vegetable textile fibres or silk by means of a mineral
salt or salts of aniline or of one of its homologues or derivatives under the oxidizing
action of one or more chlorates, the color being developed by weathering after
drying, the conjoint use of one or more prussiates (ferrocyanides ferricyanides or
other double cyanide specified) and of one or more salts of vanadium or other
agent capable of bringing about the decomposition of the chlorate in the presence
of a salt of aniline or of one of its homologues or derivatives whereby the complete
preservation of the fibre is ensured.
100
W. J. S. GRAWITZ,
By A. M. & Wm. Clark,
53, Chancery Lane, London, Chartered Patent Agents.