Improvements in the Manufacture or Production of Resin Soap.
Year: 1898

page_text: PROVISIONAL SPECIFICATION.
Improvements in the Manufacture or Production of Resin Soap.
I, CARL, DREHER, of 7, Jacob Strasse, Freiburg, Baden, in the German Empire,
Ph.D., and Chemist, do hereby declare the nature of this invention to be as
follows:-
-
This invention relates to the manufacture or production of resin soap, for
washing textile fabrics, and for like purposes.
At the present time a soap very rich in free unsaponified resin is a great
desideratum, and numerous attempts have been made to produce such a soap
containing the free resin distributed uniformly throughout it in a very fine state
of division, so as to be suitable, for instance, for use in the manufacture of paper.
So far, however, it has not been possible to obtain a soap containing more than
from 25 to 30 per cent. of unsaponified resin, and even this can only be done with
difficulty.
Now, I have discovered that all resins can be dissolved with great facility in
phenol, and its homologues, and creṣol, that is to say, when mixed with crude
carbolic acid, a partial saponification with a small amount of alkali will directly
yield resin soaps containing a very high percentage of resin, without acquiring
the use of any special apparatus.
Soaps so prepared will produce perfectly uniform emulsions in water and con-
tain in an unsaponified form, say 50 per cent. of the resin employed.
It is thus possible to produce resin soaps with only, say 9.5, parts, of carbonate
of sodium, whereas the neutral soda-salt of resin requires 19 parts.
Solid ammonia soaps can also be produced in like manner, which soaps up to
the present have not been obtainable.
In carrying out the invention, the resin may be first dissolved in the phenols,
and the alkali may be added in solution, or vice versa.
Or a resin soap may first be produced, as heretofore, and to this may be added
a carbolic solution of resin so as to enrich it.
Soaps thus prepared are very suitable for sizing paper pulp, and the phenols
neither affect the colouring matter, nor do they produce risk of fire, being them-
selves completely incombustible. Furthermore, they are entirely volatilized
when the paper is passed, in the ordinary way, through the hot drying rolls,
and thus the finished paper is absolutely inodorous..
Dated this 18th day of November 1898.

page_text: improvements in the Manufacture or Production of Resin Soap.
I, CARL DREHER, of 7, Jacob Strasse, Freiburg, Baden, in the German Empire,
Ph.D., and Chemist, 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, that is to say:-
This invention relates to the manufacture or production of resin soap, suitable
for use in the manufacture of paper and for other purposes.
It is well known that resins, especially the cheaper kinds at present on the
market, such as colophony, besides being used for the manufacture of lacquers
and. varnishes, are extensively employed in the manufacture of resin soap.
Such soap is however only used in small quantities as a substitute for fat or
oil soaps for washing textile fabrics, but is very largely used for sizing paper pulp
in the manufacture of paper. When used for this latter purpose, fir-resin or
colophony is dissolved by boiling with alkalies or alkaline carbonates, and the
disintegrated paper pulp is soaked in the solution in the cylinder engine, where-
upon the resin is precipitated upon the paper fibre by the addition of acids or
salts of aluminium, such as alum, or aluminium sulphate.
Now, experience has shewn that the sizing of paper pulp becomes the more
intimate and effective, and also the use of resin soap for this purpose the more
economical, in proportion as it contains a larger amount of free unsaponified
resin, that is to say, the less alkali or alkaline carbonate is employed for the
unsaponification of a given amount of resin.
For many years endeavours have been made to reduce the quantity of alkali,
saponification being now effected by 14 to 16 parts of soda to 100 parts of
colophony, whereas formerly as much as 20 to 25 parts of soda were generally
employed.
Resin soap is not intended to yield in water a clear solution, but a milky white
emulsion.
Now the manufacture of such a resin soap, (containing free resin evenly and
very finely distributed) becomes more difficult and uncertain in proportion as
free resin in a purer state is desired to be produced. since large quantities of
resin, retained in the resinous glue or size are instantly set free in the presence
of water, as a mucous mass, which renders the soap useless for the sizing process.
It is therefore necessary that an extremely intimate mixture of the resin with
the alkali be effected, and for this purpose special distributing and mixing devices,
stirring apparatus, digesters, and the like, are used.
However, in spite of employing the most efficient apparatus, the manufacture
of a suitable résin soap remains at present one of the most difficult operations
in connection with the manufacture of paper, so that a general want is felt for a
thoroughly reliable method of producing a soap rich in resin. Even with the
most suitable apparatus (such as Ahrledter's digester with stirring apparatus) and
with every care and experience applied, it is only possible to obtain a
containing from 25 to 30% of unsaponified resin.
resin soap
Now, I have discovered that all resins can be dissolved with great facility in
phenol and its homologues, and cresols, that is to say by mixing them with crude
carbolic acid, and by partial saponification of the solutions by means of a small
quantity of alkali, resin soaps containing an extremely high percentage of resin
can be obtained direct and without any special apparatus, said soaps producing
perfectly uniform emulsions in water, and containing 50 % of the used resin in
an unsaponified form. It is thus possible to produce resin soaps with the

page_text: theoretical minimum of alkali, that is to say, for instance, with 9.5 parts of
carbonate of sodium, whereas it is known that for obtaining total saponification,
as for producing the neutral soda-salt of resin, 19 parts of carbonate of sodium
are required.
A proof as to how smoothly and evenly the saponification of the resins in phenol
solutions takes place is, that solid ammonia soaps can be produced by this method,
which, under other circumstances, are not obtainable at all.
For carrying out my invention the resin may be first dissolved in the phenols,
the alkali or alkaline carbonate solution being added subsequently. A neutral
soap, or one poor in free resin, may however be first produced (this being an easy
operation) and to this whilst in a liquid state may be added the carbolic solution
of resin, or the phenol or carbolic solution may be added to the alkali solution.
The first method is the simplest, whilst the second may be employed for sub-
sequently enriching soaps poor in resin.
-
The following is one example of the mode of carrying out the invention:-
100 parts of disintegrated colophony, while being heated to about 100° C., are
dissolved in 20 parts of raw carbolic acid, the boiling point of which is between
190 and 200° C., and. while stirring, a solution of 9.5 of calcined carbonate of
soda in 20 parts of water is added.
The reaction ceases after heating for a short time, the operation being then
complete.
The product treated with water at 60 to 70° C., immediately yields
tory uniform emulsion.
a satisfac-
As further examples, instead of the above proportion of soda, 12.5 parts of a
soda lye of 43° B. may be employed; or 37 parts of concentrated ammonia of a
sp. gr. 0.885 may be employed.
Furthermore, a resin soap containing 100 parts of resin and 15 parts of soda,
may be enriched by bringing into it a hot solution of 25 parts of resin in 5 parts
of carbolic acid, whilst the whole is kept stirred. Such a soap melts at about
100° C. and contains, before enrichment, about 25% of free resin, in fact it is
a soap for use in the manufacture of paper which may be made in the ordinary
way if an efficient saponifying process be employed.
The mixture yields direct with water at from 60° to 70° C., a uniform milky
emulsion.
Heretofore, even by using the best known apparatus, several hours boiling was
required for obtaining a uniform saponification, whereas if the resin has been
previously dissolved in carbolic acid saponification takes place smoothly and in a
few minutes at a temperature of from 80° to 100° C. It is owing to the solution,
by means of carbolic acid, that the product is most finely distributed and is con-
sequently attacked by the alkali. in such a uniform and rapid manner.
For the manufacture of paper in the cylinder engine with this resin soap, from
3 to 6 grammes of resin are used on an average to 1 litre of water, this percen-
tage corresponding at most to .6 to 1.2 grammes of carbolic acid per litre of
water. As the latter is soluble in water, the paper pulp only absorbs or retains
the resin, whilst the carbolic acid passes away with the waste water.
The paper pulp after being drained, contains only traces of carbolic acid which
in contact with the hot drying rollers volatilize completely together with the
moisture, so that the finished paper is entirely free from phenol, and is there-
fore odourless.
As the phenols and their homologues have a perfectly neutral action upon
colouring matters, the paper is not in the least discoloured by their presence.
As, moreover, phenols are incombustible, the danger of fire is not in the least
increased, as would be the case were other organic solvents employed for the
resins, such for example as various hydro-carbons (benzol, petroleum, or the like)
as have already been suggested for the same purpose, but which, owing to their
combustibility, were found unsuitable. Furthermore, as the latter are not

page_text: soluble in water, they remain in the paper and cause the same to become stained
and to assume a disagreeable odour.
Having now particularly described and ascertained the nature of my said
invention, and in what manner the same is to be performed, I declare that what
I claim is:
1. In the manufacture or production of resin soaps, the employment of phenol
and its homologues as solvents for the resin, substantially as and for the purposes
set forth.
2. The employment of resin soaps, produced in the manner hereinbefore
described for use in the manufacture of paper.
3. A resin soap manufactured substantially as described with reference-to one
or other of the examples hereinbefore set forth.
4. My improvements in the manufacture or production of resin soap, substan-
tially as herein before described.
.1
1000
ERNEST DE PASS,
Chartered Patent Agent,
78, Fleet Street, London, & 5A, Market Street, Nottingham,
Agent for the Applicant.