Patented Jan.

28, 1936 2,028,776

UNITED STATES 2,028,776

PATENT OFFICE
CELLULOSC ARTICLES AND METEOD OF
PREPARNG THE SAME
Harold Hibbert, Montreal, Quebec, Canaia, as
signor to Celanese Corporation of America, a
corporation of Delaware
No Drawing. Application April 23, 1932,
Serial No. 60229
10 Claims, (C. 91-0)
This invention relates to the preparation of ization, whereby a layer of relatively impervious
foils, films and other articles made of cellulose polymerization product is formed.
or its derivatives, and relates more particularly . Articles to be treated in accordance with this
to rendering the same more impervious to mois invention may be of any suitable form. This in
tre. vention is particularly applicable to the treat
ment of foils Or transparent paper having a thick
An object of my invention is to render articles
and particularly sheet-like articles made of Cel neSS of the Order of 0.001' to 0.003' to be used
ulosic material more impermeable by condensing for Wrapping articles Or for any other suitable
thereon a liquid capable of polymerization to form purpose. The articles to be treated by this in
solid or semi-solid resinous material and then Sub vention on the other hand may be in the form of 10
jecting the same to polymerization, whereby a films to be used for photographic, cinemato
layer of resinous material is formed on the Sur graphic or other purposes, or other sheet-like ma
faces of said articles to render the Sane more in terials, which may be made by casting or fiawing
pervious or waterproof. A further object of my a Solution of the cellulose or cellulose derivative
s invention is to employ a volatile vinyl compound on to smooth metallic or glass surfaces, such as 15
as the polymerizable liquid in Such process. Oth film. Wheels, drums, bands, tables, etc. as is well
er objects of this invention will appear from the known in the art.
folloying detailed description. Other articles such as yarns, fabrics or articles
Articles made of, or containing on the Surface made of plastic compositions containing deriva
thereof, cellulose, regenerated cellulose or ceilu tives of cellulose may be treated by this invention. 20
lose derivatives are not as impervious to Water, In its broad a Spects this invention includes the
either in liquid or vapor state, as is often de treatment of paper, cardboard, cotton fabrics and
sired. For instance, it has been found that thin other articles made of cellulose ibres.
foils made of regenerated cellulose or cellulose The articles to be treated by this invention may
25 acetate plastics to be used in the Wrapping of be made of or contain on at least the surface 25
tobacco products or foodstuffs are more or eSS thereof any Suitable cellulosic material, such as
permeable so that moisture in the form of vapors cellulose itself, regenerated cellulose, or deriva
may pass through the same, whereby the original tives of cellulose. The derivatives of cellulose in
humidity of the wrapped articles in tine becomes clude besides nitrocellulose, organic derivatives of
3. altered. cellulose such as organic esters of cellulose and 30
I have found that if Such articles are Subjected cellulose ethers. Examples of organic esters of
to the vapors of yolatile liquids capable of be cellulose are cellulose acetate, cellulose formate,
coming polymerized to a solid or semi-solid con cellulose butyrate and cellulose propionate while
sistency under such conditions as to cause at examples of cellulose ethers are ethyl cellulose,
35 least part of the vapors to become condensed or methyl cellulose and benzyl cellulose. Generally 35
absorbed on the surfaces of Such articles, and the if the articles are made of cellulose derivatives,
same are then subjected to a process causing there will be present plasticizers such as triacetin,
polymerization, the resulting layer of polymerized diethyl phthalate, dibutyl phthaliate, diethyl tar
compound renders the articles more impervious trate, dibutyl tartrate and any other desired ma
40 to moisture, air or other gases. The condensing terials. Such as pigments and effect materials, as is 40
or absorbing of the Vapors is of great advantage well known in the cellulose derivative plastic art.
over the application of the material as a liquid, This invention is of general application to the
since much more uniform thin layers may be de treatment of the articles with the vapors of a
posited in this manner, and the use of a diluent polymerizable liquid. Such liquid may be a sub
45 or solvent to make the necessary dilute solution stantially unpolymerized vinyl compound, such 45
of the liquid, if it is to be applied as a liquid, is as the unpolymerized divinyl ether, vinyl acetate,
avoided. styrene, which is the vinyl benzene, vinyl ethyl
In accordance with my invention I render ar ether, vinyl ethyl carbonol, etc. Polymerizable
ticles made of, or containing cellulosic materials liquids other than vinyl compounds may be
50 at least on the surface thereof, more impervious used, examples of which are glycide or glycidol 50
or waterproof by subjecting the same to the va C2H3O.CH2.OH, or other glycides, which poly
pors of a liquid capable of polymerization under merize at elevated temperatures in the presence
such conditions that part of the same becomes of catalysts such as alkalies or zinc chloride.
condensed or is absorbed on the surface of the Conveniently in order to deposit the vinyl com
55 article and then subjecting the same to polymer pound onto the Surface to be treated, the surface 55
 2 2,028,776
is exposed to the vapors of the vinyl compound. duce a rubber-like, water-resistant surface, thus
In the case when the foil or surface of the arti imparting greatly increased impermeability and
cle to be treated is made of derivatives of cellu . Waterproofness to the foil.
lose, some of the vinyl compounds are mutually It is to be understood that the foregoing de
soluble with the derivative of cellulose and there tailed description is given merely by way of illus
fore are absorbed on the Surface of the Same. tration and that many variations may be made
In order to promote the condensation of the therein, without departing from the spirit of my
vinyl compound on to the surfaces of the article invention.
to be treated, such surfaces are preferably kept Having described my invention, what I claim.
10 at a low temperature. and desire to Secure by Letters Patent is: O
The polymerization of the polymerizable con 1. Method of rendering surfaces of non-metal
pound after it has been applied to the surface lic articles more impermeable, which comprises
may be conducted in any suitable manner. Thus
in the case of vinyl compounds, the polymeriza exposing surfaces of articles to vapors of a vola
tile polymerizable material selected from the
15 tion may be accomplished by heating to tempera group consisting of Substantially unpolymerized 5
tures of 70 to 100° C. or more, by exposure to light vinyl compounds and glycides to deposit the poly
rays, particularly sunlight or light rich in ultra merizable material on said surfaces, and then
violet rays, such as emitted from a mercury vapor polymerizing said polymerizable material to form
lamp. If desired, catalysts such as benzoyl per a surface coating.
20 oxide or other organic peroxides, uranium salts 2. Method of rendering surfaces of cellulosic
and the like, promoting the polymerization of material more impermeable, which comprises ex
the vinyl compound may be employed, and Small posing surfaces of cellulosic material to vapors
quantities of these catalysts may be incorporated of a volatile polymerizable material selected from
in or coated on the cellulosic films, foils Or other the group consisting of substantially unpoly
25 articles, either during their manufacture or after merized vinyl compounds and glycides, to deposit 25
their formation. the polymerizable material on said surfaces, and
If desired, a thin layer of paraffin wax, teresin then polymerizing said polymerizable material to
wax, beeswax or other wax may be incorporated form a surface coating.
in or applied to the surface of the foils or other
30 articles, either before or after application and of3.cellulose
Method of rendering surfaces of derivative
material more impermeable, which 30
polymerization of the vinyl compound. If the comprises exposing surfaces of derivatives of cel
foil is made of regenerated cellulose, a thin So lulose to vapors of a volatile polymerizable ma
lution containing the wax, nitroCellulose and a terial Selected from the group consisting of sub
plasticizer such as triphenyl phosphate, dissolved stantially unpolymerized vinyl compounds and
35 in a suitable solvent may be applied to the foil glycides, to deposit the polymerizable material 35
to coat the same with verythin coatings of these On Said Surfaces, and then polymerizing said
materials, in order to increase their impermeabil polymerizable material to form a surface coating.
ity either before or after the application and 4. Method of rendering surfaces of cellulose
polymerization of the vinyl compound. acetate material more impermeable, which com
40 Thin foils, films, sheets or other articles made prises exposing surfaces of cellulose acetate to 40
or treated in accordance with this invention have vapors of a volatile polymerizable material se
greatly increased impermeability to moisture or
other liquids. Thin foils prepared in accordance lected from the group consisting of substantially
unpolymerized vinyl compounds and glycides, to
with this invention are eminently suitable for deposit the polymerizable material on said sur
45 the wrapping of cigars, cigarettes Or other t0 faces, and then polymerizing said polymerizable 45
bacco articles and confectionary, cakes and other material to form a surface coating.
foodstuffs.
By way of an example of a method of carrying to 5.foilsMethod of imparting greater impermeability
or films containing cellulosic material,
out my invention the following is given. Thin which comprises exposing the same at low tem
50 foils of a thickness of 0.00' to 0.003' made of a peratures to the vapors of a volatile polymeriz 50
plastic composition containing cellulose acetate
and plasticizer, is passed around a drum within ableof
material selected from the group consisting
substantially unpolymerized vinyl compounds
a closed chamber. Cold brine is circulated with and glycides, whereby the polymerizable material
in the drum to maintain its temperature be
55 low 10, say 0° C. Wapors of divinyl ether, is deposited on the surface of said foils or films,
(CH2:CH)2O, are passed into the chamber and and then polymerizing Said polymerizable mate 55
a portion of the vinyl ether is condensed on or rial to form a coating on the surface of said foils
absorbed in the Surface of the cool foil. If it or films.
is so desired to cause the divinyl ether to be de 6. Method of imparting greater impermeability
60 posited on both sides of the foil, two cooled to foils or films containing cellulose acetate, 60
drums may be provided either in one chamber or which comprises exposing the same at low tem
peratures to the vapors of a volatile polymeriz
in separate chambers, the drums being so ar able material selected from the group consisting
ranged that on One of the drums, one side of the
foil is exposed to the vapors, while the other of substantially unpolymerized vinyl compounds
65 side of the foil is exposed to the vapors while and glycides, whereby, the polymerizable material 65
on the other drum. 1. is deposited on the surface of said foils or films,
The foil with the vinyl ether condensed on the and then polymerizing said polymerizable mate
surface thereof is then passed into another rial to form a coating on the surface of said foils
chamber to cause the polymerization thereof. Or films. . . . . ,w

70 This chamber may be heated to 80 to 100° C. to 7. Method of imparting greater impermeability 70

cause polymerization of the vinyl compound, or
the chamber may be flooded with ultra-violet
light and be maintained at ordinary temperatures
or elevated temperatures up to 100° C. In this
75 manner, the divinyl ether polymerizes to pro
to foils or films containing cellulosic material
comprising exposing the same to the vapors of a
substantially unpolymerized vinyl compound to
deposit a layer of the vinyl compound on at least
one surface of the foil or film and then poly- is
 2,028,776 3
inerizing the vinyl compound to form a solid to compound to deposit a layer of the divinyl ether
semi-solid resin material. compound on at least one surface of the foll or
8. Method of imparting greater impermeability film and then polymerizing the divinyl ether com
pound to form a solid to semi-Solid resin material.
to foils or films containing cellulose acetate Com
prising exposing the same to the vapors of a Sub 10. Method of imparting greater imperime
stantially unpolymerized vinyl compound to de ability to foils or films containing cellulose ace
posit a layer of the vinyl compound on at least tate comprising exposing the same to the Vapors
One surface of the foil or film and then polymer of a substantially unpolymerized divinyl ether
izing the vinyl compound to form a solid to semi compound to deposit a layer of the divinyl ether
0 Solid resin material. compound on at least one surface of the film or 10
9. Method of imparting greater impermeabil foil and then polymerizing the divinyl ether to
ity to foils Or films containing cellulosic mate form a Solid to Semi-Solid resin material.
rial comprising exposing the same to the vapors
of a SubStantially unpolymerized divinyl ether HAROLD HIBBERT.