Improvements in or connected with the Producing or Printing of Designs upon Waterproof Fabrics.
Year: 1893

page_text: Date of Application, 23rd June, 1893
Complete Specification Left, 22nd Mar., 1894-Accepted, 28th Apr., 1894
PROVISIONAL SPECIFICATION.
Improvements in or connected with the Producing or Printing of
Designs upon Waterproof Fabrics.
We, ISIDOR FRANKENBURG, of Greengate Rubber and Leather Works,
Salford, in the County of Lancaster, India-rubber Manufacturer, and CARL OTTO
WEBER, Ph.D., of Crumpsall, Manchester, in the County of Lancaster, Technical
Chemist, do hereby declare the nature of this invention to be as follows:-
This invention relates to an improved method of ornamenting or producing
designs upon waterproof fabrics during manufacture by means of the ordinary dyes
or colours such as are commonly employed in calico printing or wall paper
printing.
It consists essentially in the application to the proofed surface of a textile
fabric, of an alpha-oxycellulose or other of the cellulose derivatives to produce a
face capable of receiving or absorbing and fixing ordinary dyes such as used in
calico printing, then printing upon this prepared surface from engraved or surface
rollers and finally coating the printed surface with a thin coating of rubber or
rubber solution to fix the printed surface, the whole being subsequently vulcanized,
also in the preparation of an alpha-oxy cellulose for the purpose.
The special material which we prefer to employ is alpha-oxycellulose which
possesses the qualities of absorbing and fixing dyes to a very much greater degree
than calico or similar cotton fabrics.
We prepare this alpha-oxycellulose by taking perfectly clean cotton fibre-such
as what is known as cotton toppings-and thoroughly scouring it in a strong
solution of caustic soda or potash in water (about 2 p. c.). This scouring operation
may be carried on in an open kier or under pressure but we find that it is
advantageous to allow free access of air to the fibre under treatment the cotton
fibre is by this treatment chemically changed being partly converted into
oxy cellulose.
The scoured cotton is then repeatedly washed with water and subsequently
transferred to a tank containing a strong solution of bleaching powder of
about 6° Twd. It will be observed that this is a much stronger bleaching
solution than is employed in the ordinary process of bleaching cotton fabrics, and
although we might also employ bleach liquors of less strength we find the use of
strong solutions preferable, as they bring about in the shortest time the complete
conversion of the cotton fibre into alpha-oxycellulose. The product is allowed to
remain in this bleaching solution for about twelve hours, and is then removed,
carefully washed, first with water acidulated with hydrochloric acid and then with
clean water until every trace of lime is washed out. The cotton is thus converted
into a snow white but very tender mass, consisting almost entirely of alpha-
oxycellulose, but still showing the original structure of the cotton fibre.
This alpha-oxycellulose is now treated for about one hour in a strong boiling
solution of hydrochloric acid (about 20 p. c.) sulphuric or oxalic acid, or it is
impregnated with strong solutions of chloride of aluminium, magnesium or zinc and
heated with steam for about one hour. By either of these treatments the fibrous
structure of the alpha-oxycellulose is practically destroyed, the material being
completely disintegrated and reduced to the state of a white, impalpable powder of
almost pure alpha-oxycellulose.
The order in which the above processes are applied to the cotton fibre may be.
altered by following the scouring operation with the disintegrating operation by
acids and finishing with the bleaching or oxidizing operation. The latter may also

page_text: be carried out by means of other oxidizing agents than bleaching powder, such as
chromic acid, chromates, bichromates, chlorates, manganates and permanganates.
The product which is eventually obtained is however the same.
The great difference between this product and ordinary cotton is shown by the
behaviour of our alpha-oxy cellulose against boiling Fehling's solution. This
solution has no effect upon cotton, but is reduced by our alpha-oxycellulose, cuprous
oxide being precipitated upon it. The affinity of our compound for dyes is very
much greater than of ordinary cotton, the dyes being completely fixed without the
intervention of a mordant.
This alpha-oxycellulose we apply to the adhesive rubber surface of our water-
proof cloth, by passing the latter under a gauge, in front of which the dry powder
of alpha-oxycellulose is placed and we obtain in this manner upon the cloth an
even film, which owing to the great affinity of alpha-oxycellulose for dyes can be
printed upon like an ordinary calico.
We wish it however to be understood that although alpha-oxycellulose obtained
from cotton produces by far the best surface for printing upon, we may also employ
this and other derivatives of any other cellulose, such as amyloid, hydracellulose,
nitrocellulose, beta-oxycellulose, which may be obtained from wood pulp, jute, flax,
hemp, ramie or other of the numerous materials from which cellulose can be
isolated.
The surface prepared as above described is then printed upon with any of the
ordinary dyes used in the printing and dyeing of calicoes or wall papers by block or
machine printing, or stencilling, either according to the methods used in calico
printing, or those used in surface roller printing for wall paper, and the printing
may be done in one or more colours.
After the cloth has received the print a fine coat of rubber, rubber-solution or
cement is spread over it, which penetrates through the colour of the print and the
coating of alpha-oxy cellulose on to the underlying proofing. The whole is
subsequently vulcanized by either of the well known methods, such as the cold
cure, vapour, steam or dry heat process and by the process of vulcanization all
the various coatings are united and the printing rendered thoroughly fast.
We desire it to be understood that we are well aware that farina and other dust
have been applied to the proofing of waterproof fabrics to produce a surface for
ornamentation.
Dated this 21st day of June 1893.
WM. P. THOMPSON & Co.,
6, Bank Street, Manchester, Patent Agents.
COMPLETE SPECIFICATION.
Improvements in or connected with the Producing or Printing of
Designs upon Waterproof Fabrics.
We, ISIDOR FRANKENBURG, of Greengate Rubber and Leather Works,
Salford, in the County of Lancaster, India-rubber Manufacturer, and CARL
OTTO WEBER, Ph.D., of Crumpsall, Manchester, in the County of Lancaster,
Technical 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 :-
This invention relates to an improved method of ornamenting or producing
designs upon waterproof fabrics during manufacture by means of the ordinary dyes
or colours such as are commonly employed in calico printing or wall paper printing.
The thickenings employed may either be the ordinary starch or gum thickenings
as used in calico printing or the various resin thickenings employed in the
printing of sanitary wall paper, or india-rubber or other thickenings of a suitable
consistency.

page_text: In carrying out our process we apply to the proofed surface of a textile fabric a
coating of alpba-oxycellulose or any of the other cellulose derivatives hereinafter
named, and which are capable of receiving absorbing or fixing ordinary dyes, colours
and pigments such as are used in calico or wall paper printing. Upon the surface
prepared in this manner we print from engraved rollers and finally coat the printed
surface with a thin coating of rubber solution to protect the printed surface, the
whole being subsequently vulcanized by any of the well known methods.
We
e employ the alpha-oxy cellulose obtained from cotton fibre as herein described
in preference to the cellulose derivatives hereinafter mentioned, on account of its
special affinity for dyes particularly those known as basic dyes and its power of
receiving absorbing and fixing such dyes.
We prepare this alpha-oxycellulose by taking perfectly clean cottou-such us
that known as cotton toppings-and thoroughly scour it in a strong solution of
caustic soda or potash in water (about 24 %). This scouring operation may be
carried on in an open kier or under pressure but we find that it is advantageous to
allow free access of air to the fibre under treatment. The cotton fibre is by this
treatment chemically changed being partly converted into oxycellulose.
The scoured cotton is then repeatedly washed with water and subsequently trans-
ferred to a tank containing a strong solution of bleaching powder of about 6° Twd.
It will be observed that this is a much stronger bleaching solution than is employed
in the ordinary process of bleaching cotton fabrics, and although we might also
employ bleach liquors of less strength we find the use of strong solutions preferable
as they bring about in the shortest time the complete conversion of the cotton fibre
into alpha-oxy cellulose. The product is allowed to remain in this bleaching
solution for about twelve hours, and is then removed, carefully washed, first with
water acidulated with hydrochloric acid and then with clean water until every trace
of lime is washed out. The cotton is thus converted into a snow white but very
tender mass, consisting almost entirely of alpha-oxycellulose, but still showing the
original structure of the cotton fibre.
This alpha-oxycellulose is now treated for about one hour in a strong boiling
solution of hydrochloric acid (about 20 %) sulphuric or oxalic acid, or it is
impregnated with strong solutions of chloride of aluminium, magnesium or zinc and
heated with steam for about one hour. By either of these treatments the fibrous
structure of the alpha-oxy cellulose is practically destroyed, the material being
completely disintegrated and reduced to the state of a white, impalpable powder of
almost pure alpha-oxycellulose.
The order in which the above processes are applied to the cotton fibre may be
altered by following the scouring operation with the disintegrating operation by
acids and finishing with the bleaching or oxidizing operation. The latter may also
be carried out by means of other oxidizing agents than bleaching powder such as
chromic acid, chromates, bi-chromates, chlorates, manganates and permanganates.
The product which is eventually obtained is however the same.
A great difference between this product and ordinary cotton or cotton dust is
shown by the behaviour of our alpha-oxycellulose when treated with boiling
Fehling's solution. This solution has no effect upon cotton, but is reduced by our
alpha-oxy cellulose, cuprous oxide being precipitated upon it. The affinity of our
compound for dyes is very much greater than that of ordinary cotton, the dyes
being completely fixed without the intervention of a mordant.
This alpha-oxycellulose we apply to the adhesive rubber surface of our water-
proof cloth, by passing the latter under a gauge, in front of which the dry powder
of alpha-oxycellulose is placed and we obtain in this manner upon the cloth an even
film, which owing to the great affinity of alpha-oxycellulose for dyes can be printed
upon like an ordinary calico.
We wish it however to be understood that although we consider that alpha-
oxycellulose obtained from cotton in the manner described produces by far the best
surface for printing upon, we may also employ alpha-oxycellulose and any other

page_text: derivatives of cellulose, such as amyloid, hydracellulose, nitrocellulose, beta-
oxycellulose, which may be obtained by known processes from cotton, wood pulp,
jute, flax, hemp, ramie, cork or other of the numerous materials from which cellulose
can be isolated.
The surface prepared as above described is then printed upon with any of the
before mentioned dyes and thickenings, by block or machine printing or stencilling,
either according to the methods used in calico printing, or those used in surface
roller printing for wall paper, and the printing may be done in one or more
colours.
We also may subject our alpha-oxycellulose or any of the other above named
cellulose derivatives, to an ordinary dyeing process, before applying it to the india-
rubber surface. By thus treating the india-rubber surface with these dyed cellulose
derivatives coloured surfaces to be printed upon are obtained, which in the subse-
quent printing process, by the means and in the manner above described produce a
great variety of new effects.
After the cloth has received the print a fine coat of rubber solution is spread over
it, which penetrates through the colour of the print and the coating of alpha-
oxycellulose on to the underlying proofing. The whole is subsequently
vulcanized by any of the well known vulcanizing processes and by this process
of vulcanizing all the various coatings are united and the printing is rendered
thoroughly fast.
It is to be understood that as an equivalent to printing with dyes and colours and
coating same with a solution of rubber to protect them there may be mixed with
the dyes a rubber solution which will be printed on to the material therewith and
so render the printed colours fixed and permanent.
We desire it to be understood that we are well aware that farina and similar
materials have been applied to the proofing of waterproof fabrics to produce a
surface for ornamentation.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is :-
1. In the production of ornamental designs upon waterproof fabrics the applica-
tion to the proofed surface of a covering of alpha-oxycellulose or other cellulose
derivatives in a powdered form to receive the dye or printing and then printing
thereon substantially as described.
2. The process of preparing alpha-oxycellulose in a powdered condition substan-
tially as described.
3. The method or process of obtaining or producing ornamental designs upon
proofed fabrics substantially as described.
Dated this 21st day of March 1894.
WM. P. THOMPSON & Co.,
Manchester, Liverpool, and London, Patent Agents.