Improvements relating to the Manufacture of Colouring Matters.
Year: 1890

page_text: Date of Application, 8th July, 1890
Complete Specification Left, 26th Mar., 1891-Accepted, 2nd May, 1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by the firm of K. OEHLER, of Offenbach-on-the-Main,
in the Empire of Germany.]
Improvements relating to the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co. Patent Agents,
45 Southampton Buildings, in the County of Middlesex do hereby declare the
nature of this invention to be as follows::
Phenyl hydrazine and other aromatic hydrazines combined with aldehydes,
ketones and chinones form condensation products, suitable for dyeing. This
property has been very largely used for the manufacture of colouring matters, and
several patents have been taken out for the same for instance.
Germ. Pat. No. 34294 (Tartrazine of the Badische Anilin und Soda-Fabrik.
دو
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No. 40745
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No. 40746
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No. 46321
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No. 45272
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No. 46746
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of the Actien Gesellschaft für Anilin Fabrication,
Berlin.
of Prof. Meyer.
of the Actien Gesellschaft für Chemische Industrie,
Basel.
Use has been made, in the processes described in these patents of dioxytartaric
acid, benzaldehydes, benzylidenacetone, cinnamic-aldehyde phenanthrene-chinone,
isatine methyl- isatine benzyl and retinechinone on one side, phenyl-tolyl xyly!
a and ẞ naphthyl-hydrazine and their sulpho acids, diphenyl-hydrazine sulpho acid
and dihydrazinestilben disulpho-acid on the other side.
But the nitrated aromatic hydrazines and their sulpho acids have not yet been
used for the production of hydrazone dye stuffs (so called by Schultz: Chemie des
Steinkohlentheers, II Edition 2d. vol. page 353). The reason of this may be that
most of these dye stuffs prepared of nitrohydrazines and ketones are not fast against
the influence of light.
.
An exception to this is made by the combination of the nitroxylylhydrazine
sulpho-acid with dioxyltartaric acid which has hitherto not yet been described; the
greenish yellow dyed with it on the fibre turns only after a long exposure to light
into a slight reddish yellow; besides it is faster to milling than for instance
tartrazine.
I use nitroxyly-dine-sulpho acid which has been described by Sertig (Annalen
der Chemic Pharmacie, tome 230; page 338.)
METHOD OF PRODUCING THE DYE STUFF.
a. Preparation of the nitroxylyl-hydrazine-sulpho-acid.
THE An alumint form the nitroxxlidinosulnha-roid by transforming it in the
a. Preparation of the nitroxylyl-hydrazine-sulpho-acid.
This acid is obtained from the nitroxyl
lidinosulpha-acid by transforming it in the
well known manner into its diazo-compound and reducing this preferably with sodium
bisulphide.
100 lbs. of nitroxylidinesulpho-acid are dissolved in 300 lbs. of water with the aid
of 22 lbs. of soda, and mixed with a solution of 30 lbs. of sodium nitrite in 150 lbs. of
water. This liquor is gradually introduced whilst stirring into a cooled mixture
of 50 lbs. of sulphuric acid 66° Baumé and 200 lbs. of water, the stirring is
continued for some hours. I then add 400 lbs. of a solution of sodium-bisulphide of
40 Baumé heated to 60° Centigrade until the precipitated diazo-nitroxylidine-
sulpho-acid is perfectly dissolved; after the addition of 250 lbs. of sulphuric acid
of 66° Baume, I heat until the hydrazinesulpho acid is completely precipitated;
then filter it off, wash press and dry it.

page_text: The nitroxylylhydrazine-sulpho acid thus obtained forms a crystalline light
brownish powder which dissolves with difficulty in cold and somewhat easier in hot
water; it crystallizes in thick, often bushy arranged needles or in short prisms.
The sodium salt of this acid is readily soluble in water and crystallizes in bright
silky lustred long needles.
The hydrazine sulpho acid can also be obtained by treating the diazotated
nitroxylidine sulpho-acid with chloride of tin.
b. Condensation of the nitroxylylhydrazine-sulpho-acid with dioxytartaric acid.
I dissolve 100 lbs. of nitroxylylhydrazine sulpho acid and 21 lbs. of soda in
500 lbs. of water and add this liquor to a solution of 50 lbs. of dioxy-tartarate of
sodium in 1200 lbs. of water and 150 lbs. of hydrochloric acid of 20° Baumé and stir
for some hours.
The compound at first produced consists of 1 molecule of dioxy-tartaric acid and
I molecule hydrazine sulpho-acid and forms a fine yellow precipitate which com-
bines by slowly heating to 80° Centigrade with a second molecule of hydrazine-
sulpho acid, forming the dyestuff. After filtering, the latter is precipitated with
salt, filtered off, pressed and dried.
It forms a yellow crystalline powder, soluble in water with a pure yellow colour.
Chloride of barium precipitates it from its cold aqueous solution nearly completely
in form of a crystalline barium salt, which is soluble only in a large quantity of hot
water concentrated sulphuric acid dissolve the dye-stuff with a yellow colour.
Dated this 8th day of July 1890.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements relating to the Manufacture of Colouring Matters.
I, HENRY HARRIS LAKE, of the firm of Haseltine Lake & Co., Patent Agents,
45 Southampton Buildings, in the County of Middlesex, 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 :-
Phenyl hydrazine and other aromatic hydrazines combined with aldehydes ketones
and chinones form condensation products, suitable for dyeing. This property has
been very largely used for the manufacture of colouring matters, and several
patents have been taken out for the same for instance
•
German Patent No. 34294 (Tartrazine) of the Badische Anilin and Soda Fabrik.
وو
No. 40745
"
"
No. 40746
"
No. 46321
"
"
No. 45272
No. 46746
2
59
وو
وو
of the Actien Gesellschaft für Anilin Fabrication,
Berlin.
of Prof. Meyer
of the Actien Gesellschaft für Chemische Industrie,
Basel.
Use has been made in the processes described in these Patents of dioxytartaric-
acid, benzaldehydes, benzyliden-acetone cinnamic-aldehyde, phenanthrene-chinone,
isatine, methyl isatine, benzyl and retinechinone on one side, phenyl-tolyl-xylyl
a and naphthyl-hydrazine and their sulpho acids, diphenyl-hydrazine sulpho-acid
and dihydrazine stilben disulpho-acid on the other side.
But the nitrated aromatic hydrazines and their sulpho-acids have not yet been
used for the production of hydrazone dye stuffs (so called by Schultz: Chemie des
Stein Kohlentheers, II Edition 2d vol. page 353). The reason of this may be that
most of these dye stuffs prepared of nitrohydrazines and ketones are not fast against
the influence of light.
An exception to this is made by the combination of, the nitroxylyl hydrazine
sulpho-acid with dioxyltartaric acid which has hitherto not yet been described; the

page_text: into a slight reddish yellow, besides it is faster to milling than, for instance
tartrazine.
I use nitroxylydine-sulpho acid which has been described by Sertig (Annalen
der Chemie & Pharmacie, tome 230; page 338.)
METHOD OF PRODUCING THE DYE STUFF.
a. Preparation of the Nitroxylylhydrazine-sulpho-acid.
This acid is obtained from the nitroxylidine sulpho-acid by transforming it in
the well known manner into its diazo-compound and reducing this preferably with
sodium bisulphide.
100 lbs. of nitro-xylidinesulpho-acid are dissolved in 300 lbs. of water with the
aid of 22 lbs. of soda, and mixed with a solution of 30 lbs. of sodium nitrite in
150 lbs. of water. This liquor is gradually introduced whilst stirring into a cooled
mixture of 50 lbs. of sulphuric acid 66° Baumé and 200 lbs. of water, the stirring
is continued for some hours. I then add 400 lbs. of a solution of sodium bisulphide
of 40 Baumé heated to 60° Centigrade until the precipitated diazonitroxylidine-
sulpho-acid is perfectly dissolved; after the addition of 250 lbs. of sulphuric acid
of 66° Baumé. I heat until the hydrazinesulpho-acid is completely precipitated;
then filter it off, wash press and dry it.
The nitroxylylhydrazine-sulpho acid thus obtained, forms a crystalline light
brownish powder which dissolves with difficulty in cold and somewhat easier in hot
water it crystallizes in thick, often bushy arranged needles or in short prisms.
The sodium salt of this acid is readily soluble in water and crystallizes in bright
silky lustred long needles.
The hydrazine sulpho acid can also be obtained by treating the diazotated
nitroxylidinesulpho-acid with chloride of tin.
b. Condensation of the nitro-xylyl-hydrazine-sulpho-acid with dioxytartaric
acid.
I dissolve 100 lbs. of nitroxylyl hydrazine sulpho acid and 21 lbs. of soda in
500 lbs. of water and add this liquor to a solution of 50 lbs. of dioxy-tartarate of
sodium in 1200 lbs. of water, and 150 lbs. of hydrochloric acid of 20° Baumé and
stir for some hours.
The compound at first produced consists of 1 molecule of dioxy-tartaric acid and
1 molecule of hydrazine sulpho-acid and forms a fine yellow precipitate which
combines by slowly heating to 80° Centigrade with a second molecule of hydrazine-
sulpho acid, forming the dye stuff. After filtering, the latter is precipitated with
salt, filtered off pressed and dried.
It forms a yellow crystalline powder, soluble in water with a pure yellow colour.
Chloride of barium precipitates it from its cold aqueous solution nearly in the form
of a crystalline barium salt, which is soluble only in a large quantity of hot water,
concentrated sulphuric acid dissolves the dye-stuff with a yellow colour.
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
by my foreign correspondent, I declare that what I claim is :-
First. The method of producing nitroxylylhydrazine sulpho-acid by treating
nitroxyly-dine-sulpho-acid with bisulphides of alkalies or with chloride of tin.
Second. The method of producing a yellow dye stuff, by the condensation of
nitroxylylhydrazine-sulpho-acid with dioxy tartaric acid.
Third. The new yellow hydrazon dye stuff produced according to Claims 1 and 2
and having the properties above described.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.

page_text: COMPLETE SPECIFICATION.
Improvement in Swaging Machines.
1, JEROME CARLTON TAFT, of No. 10, West Clifford Street, Providence, Rhode
Island, United States of America, Mechanic, do hereby declare the nature of my
invention for IMPROVEMENT IN SWAGING MACHINES, and in what manner the same is
to be performed, to be particularly described and ascertained in and by the following
statement :-
Heretofore in swaging-machines it has been customary to employ a single set of
oppositely reciprocated dies thus materially restricting the range of work to which
the said machines were applicable, and it is the object of my invention to provide for
the employment of another set of oppositely reciprocated dies at right angles to the
former set, whereby the efficiency of the machine can be greatly extended; and my
invention consists in the improved construction and arrangement of the sets of
swaging-dies, as hereinafter fully set forth.
Fig. 1, represents a front view of the machine showing the arrangement of the dies,
the front covering-plates which serve to hold the dies in position being removed.
Fig. 2, represents a vertical axial section of the machine.
Fig. 3, represents an enlarged longitudinal section of one of the forcers by means
of which the dies are operated.
Fig. 4, represents an end view of the same.
Fig. 5, represents an enlarged end view of the sets of dies separate from the
machine.
Fig. 6, represents an enlarged front view of the die-holding head.
In the accompanying drawings, A represents the frame of a rotary swaging-machine,
of ordinary construction; B the die-holding head which is provided with a hollow
shaft or shank C; upon which is placed the driving pulley D. The rotary die-holding
head B is provided with the cross grooves a, a, arranged at right angles to each other,
and within the said grooves are placed the sliding forcers which are provided at
their outer ends with the bearing rollers b, the said rollers being adapted to engage
with the adjustable beaters F held in suitable grooves made in the annular flange c:
the forcers E and beaters F, being retained in proper position within their holding
grooves, by means of the retaining plates d and e, respectively, which are fastened to
the die-holding head B and frame A, by means of suitable screws.
The dies ffff, are arranged loosely within the inner portion of the grooves a a,
in advance of the sliding forcers E, the dies ff, which form one oppositely recipro-
cated set, serving to form a lateral guide for the dies ff, of the other set, one set
being arranged at right angles to the other, and both sets being adapted for simul-
taneous operation by the beaters. The loose blocks g g may also be placed in the
groove a at opposite sides of the thinner dies f¹ f¹, to serve as a directing guide for
the same, and the outer end of the thinner dies can also be guided by resting within a
guiding groove h, made in face of the forcers E, by means of which the loose
dies are operated.
Instead of employing the forcers and detached dies as hereinbefore described, the
dies and forcers can be made in one piece; but in most cases I prefer to use the
separate forcers and dies.
The dies shown in the drawings are especially adapted for swaging the clearing-
grooves of drill-blanks, the dies ff, being provided with a longitudinal groove i
adapted to swage the edge of the drill, while the dies f¹ fare provided with a
rounded edge j, which is adapted to swage the grooves, and by changing the dies in
the machine for others of varying size or shape, the grooves of the drill-blank can be
carried to the required depth.
In swaging the drill-blank G shown in section in Fig. 6, the grooved guiding

page_text: dies ff, which operate upon the edge of the blank are arranged to have a very slight
movement, while the rounded dies f,, which form the groove have a much greater
movement, the engagement of the beaters F with the former set of dies being made
less than that of the latter, and by reason of the inequality of movement of the two
sets of dies, I am enabled to practically employ the dies of one set as a guide for
the dies of the other set, and this guiding arrangement of the dies and the unequal
movement, is especially adapted for the manufacture of grooved drill-blanks.
As shown in the drawings, the die holding head B is made to revolve while the
beaters are held stationary, but the die-head B may be held stationary while the
beaters are made to revolve, if preferred.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :
1. In a swaging-machine, the combination with the die-holding head, of the sets
of dies arranged at right angles to each other, the inner faces of the dies of one set,
being adapted to form a guide for the dies of the other set, substantially as described.
2. In a swaging machine, the combination with the die-holding head, of the sets
of combined forcers and swaging-dies, arranged at right angles to each other, sub-
stantially as described.
3.-In a swaging-machine, the combination with the die-holding head, of the sets
of swaging-dies arranged at right angles to each other, the dies of one set being pro-
vided with a longitudinal groove, and the dies of the opposite set with a rounded edge,
substantially as described.
4. In a swaging-machine, the combination with the die-holding head, of the sets
of combined forcers and swaging-dies arranged at right angles to each other, and the
guiding-blocks at the opposite sides of the die, substantially as described.
5. In a swaging-machine, the combination with the die-holding head, of the sets
of swaging-dies arranged at right angles to each other, the inner faces of the dies of
one set, being adapted to form a guide for the dies of the other set, the said guided
dies having a greater movement, substantially as described.
6. In a swaging-machine, the combination with the dio-holding head, of the sets
of swaging-dies arranged at right angles to each other, the dies of one set being made
to have a greater movement than the dies of the other set, substantially as described.
Dated this 17th day of June 1890
JEROME CARLTON TAFT.
Haseltine, Lake & Co.,
45, Southampton Buildings, I.ondon, Agents for the Applicant.