Improvements in and relating to the Manufacture of Dye Stuffs and Tanning Extraots.
Year: 1896

page_text: Date of Application, 23rd Apr., 1896
Complete Specification Left, 22nd Jan., 1897-Accepted, 13th Mar., 1897
[Communicated from abroad by the Firm of LEPETIT, DOLLFUS AND GANSSER,
of Milan and Susa (Piedimont), in the Kingdom of Italy, Chemical
Manufacturers.]
Improvements in and relating to the Manufacture of Dye Stuffs and
Tanning Extraots.
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:-
Several patents have of late years been taken out relating to the action of
bisulphite or of neutral sulphite of soda on compounds of the benzene or
naphthalene series in order to obtain new useful derivatives of the same.
The communicators have found that by treating vegetable colouring or tanning
extracts with bisulphites or sulphites of alkalis, they are changed into new bodies
with different characteristics from the extracts used in their preparation, and
having under many aspects valuable properties in dyeing and tanning.
In some cases the reaction gives products which are not easily soluble in water, such
are the new dyestuffs derived from old and young fustic extracts, in other cases
it gives products readily soluble in cold water such as the tanning substances
derived from quebracho, or hemlock or pine extract; both classes of compounds
have valuable properties as described in the following examples.
The following examples will show how the invention is carried out and what are
the characteristics of the new products obtained, which distinguish them from the
extracts used to prepare our new products.
300 kgs. of old fustic extract (of morus tinctoria) of 28° Bé. and 100 kgs. of
bisulphite of soda 35° Bé., are mixed, then heated for 8 hours at a temperature
between 110° and 115° C., in a closed vessel.
After the expiration of this time. the old fustic extract is changed into a con-
sistent mass of a pale yellow colour, consisting of a magma of microscopical
crystals of the new colouring matter, that is hereafter called for the sake of
brevity sulfomorine. The new product is very slightly soluble in cold or even in
hot water, it might be compared in many respects to the addition-products of
bisulphites with aldehydes and ketones, with the difference that though mineral
acids, added to it, put in liberty sulphurous anhydride, they do not regenerate the
primitive extracts, giring instead of it a pale yellow dyestuff not easily soluble in
water. The sulfomorine may be purified by washing it thoroughly with water.
It differs substantially from the old fustic extract from which it derives, as in
dyeing and printing on alum, chrome and tin mordants, it gives bright yellow shades
which would be scarcely obtainable with the usual fustic extract.

page_text: EXAMPLE II.
MANUFACTURE OF A YELLOW DYE FROM YOUNG FUSTIC EXTRACT (OF RHUS
COTINUS).
300 kgs. of young fustic extract of 25° Bé. are mixed with 100 kg. of bisulphite
of soda of 35° Bé. and then beated in a closed vessel at 140-150° C. for
8 hours.
The brown yellowish young fustic extract is changed into a thick mass of very
pale, almost white colour consisting of microscopical crystale of the new body. It
differs from the young fustic extract exactly as sulfomorine, described in
Example I, differs from young fustic extract and gives on wool and on cotton very
pure yellow shades of great intensity, whilst young fustic extract dyed in the
same way gives only dull shades lacking intensity.
MANUFACTURE OF A SOLUBLE QUERCITRON BARK EXTRACT FROM QUERCITRON
EXTRACT.
300 kgs. of quercitron hark extract of 28° Bé., are mixed with 100 kg. of
bisulphite of soda of 35° Bé. and then heated in a closed vessel at 140-145° C.
for 8 hours.
The product thus obtained differs from the quercitron bark extract, used in the
process, by its great solubility in cold water and by its property of giving on
mordanted, cotton shades twice as intense, and even more, than that obtained with
the quercitron extract before having been treated by this process. These
properties are very valuable for printers who require a quercitron bark extract as
soluble as possible.
In this example, the reaction has a marked analogy with the decomposition of
the glucoside of quercitron extracts by means of diluted acids, as generally used
in the manufacture of these extracts, but the result is a much better que, since
the product obtained by the bisulphite method as described in the present example
is much purer and does not contain the secondary reaction products and impurities
yielded by the action of acids.
MANUFACTURE OF A QUEBRACHO EXTRACT READILY SOLUBLE IN COLD
WATER FROM THE USUAL QUEBRACHO EXTRACT.
a. 300 kgs. of common or decolorized quebracho extract of 25° Bé. are mixed
with 80 kgs. of bisulphite of soda of 35° Bé. and heated in a closed vessel at
130-145° C. for 8 hours.
The product obtained differs from the usual quebracho extracts by its perfect
solubility even in cold water, and by its property of giving a soft, pale, nice pink
coloured leather very similar to hides tanned with mimosa bark. An important
property of our soluble extract is that it penetrates more rapidly into the pures
of hide, than usual less soluble quebracho extract.
b. 500 kgs. of quebracho extract 120 kgs. of bisulphite of soda at 30° Bé., or
180 kgs. of hydrosulphite of soda of 20° Bé. are stirred in an open copper vessel
with a double bottom heated by steam and provided with an agitator, for 8 hours
until a sample taken from the mass is easily soluble in cold water; this is generally
the case after 8 to 10 hours.
o. Soluble quebracho extracts may also be obtained by extracting the quebracho
wood in presence of bisulphite or sulphite of soda, for instance by boiling under
or without pressure 1000 kgs. of quebracho wood with water to which has

page_text: been added 110-130 kgs. of bisulphite of soda (35° Bé.) or crystallised neutral.
Bulphate of soda and evaporating the decoction until it tests 25-30° Bé.
In every caso, working as described under a, b, c, the extract is perfectly soluble.
in cold water and tans quicker than the quebracho extracts generally known, the
leather becomes softer and of a much paler colour of a pleasant pink shade. The
palest product is obtained as described under 2.
MANUFACTURE OF A HEMLOOK EXTRACT READILY SOLUBLE IN COLD WATER
FROM THE USUAL HEMLOCK EXTRACT.
Hemlock extracts (not soluble in cold water) are changed into soluble extracts
exactly by the same processes as used for quebracho extracts, that is to say working
as described under a and b in Example IV.
The hemlock extract thus heated dissolves readily in cold water and has as
compared with the usual hemlock extracts, the same advantages as soluble
quebracho compared with the usual quebracho.
The weights and temperatures inentioned may be altered of course to some
extent, and sulphites, bisulphites and hydrosulphites of potash and of ammonia
may be used instead of the sodium salts.
Dated this and dow of Ammil 1000
.
HASELTINE, LAKE & Co.,
45 Southampton Buildings, London, W.C., Agents for the Applicant.
Improvements in and relating to the Manufacture of Dye Stuffs and
Tanning Extracts.
1, 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 he
particularly described and ascertained in and by the following statement :-
Several patents have of late years been taken out relating to the action of
bisulphite or of neutral sulpbite of soda on compounds of the benzene or naphthalene
series in order to obtain new useful derivatives of the same.
The communicators have found that by treating vegetable colouring or tanning
extracts with bisulphites or sulphites of alkalis, they are changed into new bodies
with different characteristics from the extracts used in their preparation, and having
under many aspects valuable properties in dyeing and tanning.
In some cases the reaction gives products which are not easily soluble in water,
such are the new dyestuffs derived from old and young fustic extracts, in other
cases it gives products readily soluble in cold water such as the tanning substances
derived from quebracho, or hemlock or pine oxtract; both classes of compounds
have valuable properties as described in the following examples.
The following examples will show how the invention is carried out and what are
the characteristics of the new products obtained, which distinguish them from the
extracts used to prepare the now products.

page_text: bisulphite of soda 35° Bé., are mixed, the heated for 8 hours at a temperature
between 110° and 115° C., in a closed vessel.
After the expiration of this time, the old fustic extract is changed into a consistent
mass of a pale yellow colour, consisting of a magina of microscopical crystals of the
new colouring matter, which is hereafter called for the sake of brevity sulfomorine.
The new product is very slightly soluble in cold or even in hot water, it might be
compared in many respects to the addition-products of bisulphites with aldehydos
and ketones, with the difference that though mineral acids, added to it, liberate
sulphurous anhydride, they do not regenerate the primitive extracts, giving instead
of it a pale yellow dyestuff not easily soluble in water. The sulfomorine may be
purified by washing it thoroughly with water. It differs substantially from the old
fustic extract from which it derives, as in dyeing and printing on aluin, chrome and
tin mordants, it gives bright yellow shades which would be scarcely obtainable with
the usual fustic extract.
EXAMPLE II.
MANUFACTURE OF A YELLOW DYE FROM YOUNG FUSTIC EXTRACT (OF
RHUS COTINUS).
300 kgs. of young fustic extract of 25° Bé. are mixed with 100 kgs. of bisulphite
of soda of 35° Bé. aud then heated in a closed vessel at 140-150° C. for 8 hours.
The brown yellowish young fustic extract is changed into a thick mass of very
pale, almost white colour consisting of microscopical crystals of the new body. It
differs from the young fustic extract exactly as sulfomorine, described in Example I,
differs from young fustic extract and gives on wool and on cotton very pure yellow
sbades of great intensity, whilst young fustic extract dyed in the same way gives
only dull shades lacking intensity.
MANUFACTURE OF A SOLUBLE QUERCITRON BARK EXTRACT FROM
QUERCITRON EXTRAOT.
300 kgs. of quercitron bark extract of 28° Bé., are mixed with 100 kg. of bisul-
phite of soda of 35° Bé. and then heated in a closed vessel at 140-145° C.
for 8 hours.
The product thus obtained differs from the quercitron bark extract, used in the
process, by its great solubility in cold water and by its property of giving on
mordauted cotton shades twice as intense, and even more, than that obtained with
the quercitron extract before having been treated by this process. These properties
are very valuable for printers who require a quercitron bark extract as soluble as
possible.
In this example, the reaction has a marked analogy with the decomposition of
the glucoside of quercitron extracts by means of diluted acids, as generally used
in the manufacture of these extracts; but the result is a much better one, since the
product obtained by the bisulphite method as described in the present example is
much purer and does not contain the secondary reaction products and impurities
yielded by the action of acids.
MANUFACTURE OF QUEBRACHO EXTRACT READILY SOLUBLE IN COLD WATER 4
FROM THE USUAL QUEBRAOHO EXTRACT.
a. 300 kgs. of common or decolorized quebracho extract of 25° Bé. are mixed
with 80 kgs. of bisulphite of soda of 35° Bé. aud heated in a closed vessel
at 130-145° C. for 8 hours.
The product obtained differs from the usual quebracho extracts by its perfect 5

page_text: solubility even in cold water, and by its property of giving a soft, pale, nice pink.
coloured leather very similar to hides tanned with mimosa bark. An important
property of our soluble extract is that it penetrates more rapidly into the pores of
hide, than usual less soluble quebracho extract.
b. 500 kgs. of quebracho extract 120 kgs. of bisulphite of soda at 35° Bé., or of
a solution of sulphite of soda of 30° Be., or 180 kgs. of hydrosulphite of soda
of 20° B6. are stirred in an open copper vessel with a double bottom heated by
steam and provided with an agitator, for 8 hours until a sample taken from the mass
is easily soluble in cold water; this is generally the case after 8 to 10 hours.
c. Soluble quebracho extracts may also be obtained by extracting the quebracho
wood in presence of bisulphite or sulphite of soda, for instance by boiling under or-
without pressure 1000 kgs. of quebracho wood with water to which has been
added 110-130 kgs. of bisulphite of soda (35° Bé.) or crystallised neutral sulphate
of soda and evaporating the decoction until it tests 25-30° B6.
In every case, working as described under a, b, c, the extraut is perfectly soluble
in cold water and tans quicker than the quebracho extracts generally known, the
leather becomes softer and of a much paler colour of a pleasant pink shade. Tho
palest product is obtained as described under a.
MANUFACTURE OF A HEMLOOK EXTRACT READILY BOLUBLE IN COLD WATER
FROM THE USUAL HEMLOOK EXTRACT.
Hemlock extracta (not soluble in cold water) are changed into soluble extracts
exactly by the same processes as used for quebracho extracts, that is to say working-
as described under a aud b in Example IV.
The hemlock extract thus heated dissolves readily in cold water and has as
compared with the usual hemlock extracts, the same advantages as soluble quebracho
compared with the usual quebracho.
The weights and temperatures mentioned may be altered of course to some extent,
and sulphites, bisulpbites aud hydrosulphites of potash and of ammonia may be used
instead of the sodiuin salts.
Having now particularly described aud ascertained the nature of the said inven-
tion and in what manner the same is to be performed, as communicated to me
by my foreigu correspondents, 1 declare that what I claim is :-
1. The process berein described of producing new vegetable dyestuffs by the
action of bisulphite of soda on old and young fustic extracts and quercitron extracts
substantially as above described.
2. The process herein described of producing soluble tanning extracts by the
action of bisulphite, or sulphite, or hydrosulphite of soda on quebracho extracts in
order to obtain a product quite soluble in cold water substantially as above
described. The same for soluble hemlock extracts.
3. The new dyes consisting of yellow pastes or powders, very slightly soluble in
hot water, dyeing mordauted fibres in pure yellow shades on alumina, green yellow
on chrome, derived from old fustic and young fustic extracts. The brown yellowish
extract perfectly soluble in cold water, dyeing and printing on mordants yellow
shades, derived from quercitron bark extract.
4. The quebracho and hemlock extracts perfectly soluble in cold water which
give in tanning a pink colour to the hides, a very soft leather, and tan more rapidly.
than common quebracho or hemlock extract.
Din 2nd day of January 1897
HASELTINE, LAKE & Co.,
45 Southamptou Buildings, London, W.C., Agents for the Applicant.