Improvements in or relating to Sulphuretted Solutions and Compounds used for the Production of Films or Coatings.
Year: 1891

page_text: Date of Application, 24th Feb., 1891
Complete Specification Left, 19th Nov., 1891-Accepted, 19th Dec. 1891
PROVISIONAL SPECIFICATION.
[Communicated from abroad by FREDERICK CRANE, 41, Barclay Street, New
York, United States of America, Manufacturing Chemist.]
Improvements in or relating to Sulphuretted Solutions and
Compounds used for the Production of Films or Coatings.
I, JOSEPH SINCLAIR FAIRFAX, of 433 Strand, in the County of London,
Consulting Engineer and Patent Agent, do hereby declare the nature of this
invention to be as follows :--
The object of this invention-as communicated to me by my foreign corre-
spondent is to produce a substance or compound which is not injuriously affected
by exposure to the atmosphere, and is waterproof. Such a substance has many
applications in the arts, such as flexible films, as a coating for paper, leather, textile
fabrics, or as a substitute for india rubber in some of its applications, and for many
other useful purposes.
It has long been suggested that compounds of dissolved pyroxyline, or soluble
nitro-cellulose with various fixed and essential oils, and also oleo resins, would
produce a substance or compound suitable for the above purposes; and many
patents have been issued, in this and other countries, for the saine. Such compounds,
however, have been found useless in practice, owing to the tendency of the fatty
oils to decompose under atmospheric influences, to become soft and offensive in
odour, and to cause disintegration of the compound; while the tendency of the oleo
resins and drying oils to oxydize, and of the essential oils to evaporate, left the
resultant compound hard and brittle; and even when combined with pyroxyline to
the extent of three or four times its weight, they did not give the compound
sufficient body.
After long and careful experimenting, it has been discovered that by combining
with soluble pyroxyline or nitro-cellulose bodies known as sulphur balsams-
which also include the general class of substances known as sulphuretted oils-a
stable compound could be produced, not liable to decompose, oxydize, or evaporate;
practically unaffected by the atmosphere; waterproof, of great body, and very
flexible; and which can be used for the purposes above mentioned.
But
The pyroxyline or nitro-cellulose used in the manufacture of these compounds
is of that grade or kind known in the arts as soluble pyroxyline or nitro-
cellulose, and is obtained by subjecting vegetable fibre or cellulose to the action
of nitric acid, or of nitric and sulphuric acids, in the well known manner.
before combining this nitro-cellulose with sulphuretted oil, it is preferred to
dissolve the nitro-cellulose in some solvent which is also a solvent of the
sulphuretted oil, and then to combine the said substances as hereinafter described.
The sulphur balsams above mentioned are prepared by the addition of sulphur to
certain fixed oils.
Cotton seed oil, and olive oil, have been frequently used and are found to be well
adapted for the purpose in view; but rape, castor, sesame, palm, cod liver, sperm,
and some other fatty oils-both animal and vegetable-and oleic acid, may be used.
It should be added that these different oils produce compounds of different shades
of colour, and where a light colour is desired, olive oil is found to be the best; but
for a dark, opaque substance, cotton seed oil is the best.
The sulphur may be combined with the oil, in the manner following. The oil to
be treated is first heated in a suitable vessel to about 125° C., at which temperature
an amount of sulphur-depending on the oil used-is slowly added and stirred into
the oil, and the temperature of the mixture is then raised to 210° C., at which

page_text: .
point it is maintained for two or more hours. During the process of combining the
oil and sulphur, large quantities of sulphuretted hydrogen are evolved, showing that
the sulphur has entered into chemical combination with the oil. But I do not
confine myself to this exact method of producing the said sulphur balsam, as any
other practical method having the same result, may be used.
It is found that in preparing this sulphur balsam or sulphuretted oil, sulphur
to the amount of from one ninth to one fifth of the weight of the oil could be
advantageously used; but the best proportion of sulphur will be found to vary, as
it depends on the oil used, and on the degree of fluidity desired in the resultant
compound. The proportions above named have been found to produce good
results when used with a temperature of about 210° C., for a compound of syrupy
consistency when cold.
This sulphuretted oil is a neutral body, insoluble in ethyl and methyl alcohol and
water, but soluble in chloroform, ether, benzole, benzoline, amyl acetate, propyl
acetate, butyl acetate, fusel oil, and others; of a syrupy consistency when cold, and
fluid when hot.
To the sulphuretted oil, when cold, pyroxyline is added, preferably, however,
first dissolved in some solvent which is also a solvent of the sulphuretted oil, and
will act harmoniously when introduced into the compound. The amount of
pyroxyline to be added is regulated by the degree of flexibility desired in the
resultant compound; it appearing that the lesser proportion of pyroxyline gives
greater flexibility to the compound, while a greater proportion gives less flexibility.
In addition to the pyroxyline, there may be ground into the compound as much
pigment as is necessary to give colour or greater body to the compound. After
the addition of the pyroxyline and pigment, and their thorough incorporation with
the sulphuretted oil, the compound is ready for use, and may be used by any method
mentioned herein.
The following formula has been found to give good results as a coating for textile
fabrics, paper and leather.
7 gallons of butyl acetate.
3 gallons petroleum naphtha.
15 pounds of pyroxyline.
30 to 40 pounds of sulphuretted oil.
1 to 2 pounds of such pigment as may be required.
The same formula is found to be well adapted for films if thinned down sufficiently
Lo spread slightly before setting by the addition of more of the pyroxyline solvent.
The same formula has also been used for producing a compound for floor cloth or
linoleum, with the addition, however, of more pigment, or of ground wood, ground
cork, flock, or other like material to give substance.
In the place of butyl acetate in the above formula, there may be used mixtures
of propyl and butyl acetate, and also amyl acetate.
To this compound of prepared oil and pyroxyline, or to the prepared oil before
combination with the pyroxyline, camphor, or other latent solvent of pyroxyline
may be added, and the resultant compound can then be applied to fabrics in the
same manner as rubber is now applied.
Dated this 22.1 2
.1.
1001

page_text: COMPLETE SPECIFICATION.
Improvements in or relating to Sulphuretted Solutions and
Compounds used for the Production of Films or Coatings.
I, JOSEPHI SINCLAIR FAIRFAX, of 433, Strand, in the County of London,
Consulting Engineer and Patent Agent, 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 :-
The object of this invention-as communicated to me by my foreign corre-
spondent is to produce a substance or compound which is not injuriously affected
by exposure to the atmosphere, and is waterproof. Such a substance has many
useful applications in the arts, as for example, flexible films, as a coating for paper,
leather, textile fabrics, or as a substitute for india-rubber in some cases, and for
many other purposes.
Such
It has long been suggested that compounds of dissolved pyroxyline-or soluble
nitro-cellulose with various fixed and essential oils, and also oleo resins, would
produce a substance or compound suitable for the above purposes; and many
patents have been obtained-in this and other countries-for the same.
compounds, however, have been found useless in practice, owing to the tendency
of the fatty oils to decompose under atmospheric influences, to become soft and
offensive in odour, and to cause disintegration of the compound; while the tendency
of the oleo resins and drying oils to oxydize, and of the essential oils to evaporate,
left the resultant compound hard and brittle. Even when combined with pyroxyline
to the extent of three or four times its weight, they did not give sufficient body to
the compound.
After long and careful experimenting, it has been discovered that by combining
with soluble pyroxyline or nitro cellulose bodies known as sulphur balsams (which
also include the general class of substances known as sulphuretted oils) a stable
compound could be produced, not liable to decompose, oxydize, or evaporate,
practically unaffected by the atmosphere; waterproof, of great body, and very
Hexible; and which can be used for the purposes indicated above.
The pyroxyline or nitro-cellulose used in the manufacture of these compounds
is of that grade or kind known in the arts as soluble pyroxyline or nitro-cellulose,
and is obtained by subjecting vegetable fibre or cellulose to the action of nitric
acid or of nitric and sulphuric acids-in the well known manner. But before
combining this nitro cellulose with sulphuretted oil, it is preferred to dissolve the
nitro-cellulose in some solvent which is also a solvent of the sulphuretted oil, and
then to combine the said substance as hereinafter described. The sulphur balsams,
above mentioned, are prepared by the addition of sulphur to certain fixed oils.
Cotton seed oil, and olive oil, have been frequently used, and are found to be
well adapted for the purpose in view; but rape, castor, sesame, palm, cod liver,
sperm, and some other fatty oils, (both animal and vegetable), and oleic acid, may
be used. It should be added that these different oils produce compounds of
different shades of colour; and where a light colour is desired, olive oil is found
to be the best; but for a dark, opaque substance, cotton seed oil is the best.
The sulphur may be combined with the oil in the manner following. The oil to
be treated is first heated in a suitable vessel to about 125° C. at which temperature
an amount of sulphur (depending on the oil used) is slowly added, and stirred into
the oil; and the temperature of the mixture is then raised to 210° C. at which
point it is maintained for two or more hours. During the process of combining
the oil and sulphur, large quantities of sulphuretted hydrogen are evolved, showing
that the sulphur has entered into chemical combination with the oil. But I do not
confine myself to this exact method of producing the said sulphur balsam, as any
other practical method--having the same result-may be used.
It is found in preparing this sulphur balsam-or sulphuretted oil-that sulphur to

page_text: the amount of from one ninth to one fifth of the weight of the oil could be
advantageously used. But the best proportion of sulphur will be found to vary, as
it depends on the oil used, and on the degree of fluidity desired in the resultant
compound. The proportions above named have been found to produce good results
when used with a temperature of about 210° C., for a compound of syrupy con-
sistency when cold.
This sulphuretted oil is a neutral body, insoluble in ethyl and methyl alcohol and
water, but soluble in chloroform, ether, benzole, benzoline, amyl acetate, propyl
acetate, butyl acetate, fusel oil and others; and is of a syrupy consistency when
cold, and fluid when hot.
In the sulphuretted oil-when cold-pyroxyline is added; preferably, however,
first dissolved in some solvent of the sulphuretted oil which will act harmoniously
when introduced into the compound. Such solvents are amyl acetate, propyl
acetate and butyl acetate, and mixtures thereof with petroleum naphtha. The
amount of pyroxyline to be added is regulated by the degree of flexibility desired
in the resultant compound; as it appears that a small proportion of pyroxyline_
gives a good amount of flexibility to the compound, while a greater proportion
gives less flexibility.
In addition to the pyroxyline, there may be ground into the compound as much
pigment as is necessary to give colour or greater body to the compound. After
the addition of the pyroxyline and pigment, and their thorough incorporation with
the sulphuretted oil, the compound is ready for use, and may be used by any method
mentioned herein.
The following formula has been found to give good results as a coating for
textile fabrics, paper and leather.
7 gallons of butyl acetate.
3 gallons petroleum naphtha.
15 pounds of pyroxyline.
30 to 40 pounds of sulphuretted oil.
1 to 2 pounds of such pigment as may be required.
The same formula is found to be well adapted for films if thinned down sufficiently
to spread slightly before setting by the addition of more of the pyroxyline solvent.
The same formula has also been used for producing a compound for floor cloth or
linoleum, with the addition, however, of more pigment, or of ground wood, ground
cork, flock, or other like material to give substance.
In the place of butyl acetate in the above formula, there may be used mixtures
of propyl and butyl acetate, and also amyl acetate.
'
To this compound of prepared oil and pyroxyline, or to the prepared oil before
combining with the pyroxyline, camphor, or other latent solvent of pyroxyline may
be added, and the resultant compound can then be applied to fabrics in the same
manner as rubber is now applied.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, I declare that what I
claim is :
1. A neutral sulphuretted oil compound, prepared by heating oil to a temperature
of about 125º C., adding thereto sulphur, and increasing the temperature of the
mixture to about 210° C., substantially as and for the purpose herein described.
2. A neutral sulphuretted oil compound, insoluble in ethyl, and methyl alcohol
and water, but soluble in chloroform, ether, benzole, benzoline, amyl, propyl or
butyl acetates, or fusel oil, substantially as and for the purpose herein described.
3. The combination of a neutral sulphuretted oil compound with pyroxyline or
nitro-cellulose, and a mutual solvent, substantially as and for the purpose herein
described.
4. A film or coating for fabrics, paper, leather or other suitable substances,
composed of a compound of sulphuretted oil with pyroxyline or nitro-cellulose, and

page_text: a mutual solvent such as butyl acetate, or petroleum naphtha or both, substantially
as and for the purpose herein described.
5. A flexible and waterproof film or coating, stable under atmospheric
influences, composed of ingredients prepared substantially in the manner, and in
the proportions herein described.
.Dated this 19th day of November 1891.
FAIRFAX & WETTER,
433, Strand, London, Agents for the Applicant.