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Патент USA US2136544

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2,156,544
Patented Nov. 15, 1938
UNITED STATES PATENT OFFICE
TRANSPARENT COATED SHEET MATERIAL
Erich Gebauer-Fuelnegg, deceased, late of Evans
ton, 111., by Marie Gebauer—Fuelnegg', Evans
ton, Ill., administratrix, and Eugene W. Moffett,
Pittsburgh, Pa., and Edouard M. Kratz, Chi
cago, Ill., ‘assignors to Marbon Corporation,
Gary, 1nd,, a corporation of Delaware
No Drawing. Original application April 26, 1534, 0
Serial No. 722,510. Divided and this applica
tion January 14, 1938, Serial No. 184,956
4 Claims. (Cl. 91-68)
This invention relates to transparent coated
sheet or ?lm material and to a method of prepar
ing the same. More particularly, this inven
tion relates to the manufacture of thin, trans
the penetration of water vapor, gases and greases,
by coating the same with a ?rmly adhering
pellicle, or thin layer of- substances obtained from
a polymerized butadiene, such as may be prepared
requisite degree of ?exibility and pliability to
by the reaction between rubber and rubber-like
compounds with metal halides, hydrogen halides,
render it suitable for use as a wrapping.
or free halogens.
5 rparent, ‘composite, sheet material having the
.
We have also found, conversely, that if the
has heretofore been made from a large number (base film is prepared from a polymerized buta
of di?erent materials, including colloidal proteins, diene compound, such as one of,those just referred 10
such as gelatin, or glue and casein; from cellulosic to, or other rubber derivatives, the transparency
and clarity of such base-?lms in some instances
derivatives, such as cellulose nitrate, cellulose ace
tate, regenerated cellulose and cellulose ethers; may be greatly improved by applying thereto a
and from many other types of substances. In the coating of various ?lm forming materials, such as
copending application of Erich Gebauer-Fuelnegg - the colloidal proteins, gelatin, casein, zein and 15
and Eugene W. Mo?ett, Serial No. 708,429, ?led the like, or cellulose derivatives, such as the esters
.
January 26, 1934, there is'also described a thin and ethers of cellulose.
A method of increasing the transparency and
transparent sheet material made from the hydro
clarity of rubber hydrochloride sheet and ?lm ma
chloride derivatives of natural,’ or synthetic rub
ber, or rubber-like compounds, including the terial is disclosed in our copending application 20
Serial No. ‘704,050, ?led December 26, 1933. Our
polymerized butadiene compounds.
copending application Serial No. 722,510, ?led
In general, however, .some of the more com
monly known transparent sheets or ?lms when April 26, 1934, of which this application is a
formed as a single ply ?lm, lack certain desirable division, is a continuation in part of applicationv
,
properties, such as imperviousness toward the ‘Serial No. 704,050.
This invention therefore relates to transparent
transmission of water vapor, gases, or grease, or‘
lack the desired degree of clarity, transparency, sheet material of a composite or multi-ply char- '
or ?exibility under various temperature and acter, the plies, or layers of which, however, are
?rmly bonded together. In its preferred ‘form,
humidity conditions.
It is well known, for instance, that protein one of the constituent plies comprises a ?lm of
base ?lms, such as ?lms prepared from gelatin or rubber hydrochloride. Composite ?lms embody
casein, and cellulosic ?lms, such as regenerated ing our present invention possess certain dis
cellulose ?lms, are relatively sensitive to extremes tinctive advantages over the single layer type of
?lm either with respect to the imperviousness of
of climatic conditions of temperature and humid
ity, and, further, that such ?lms are not by the sheet material toward the transmission of 35
water vapor, gases, grease, or the like, or with‘
themselves sufficiently resistant to the trans
mission of ‘water vapor, gases, or grease to make respect to the degree of transparency, clarity or
them entirely satisfactory for particularwrapping brilliance of the sheet material.
As is well known, transparent sheet material
10
15
20
25
30
35
-
purposes. It is ‘for this reason that such base
40 ?lms are sometimes provided withv a coating of a
, moistureproo'f character, such as a nitrocellulose
It is therefore an important object of our in
vention to provide a transparent sheet material‘
of a comp site or multiply character, wherein
coating containing small quantities of waxy sub
the plies are ?rmly bonded together and possess
stances, gums, resins, or the like, or mixtures
different properties and characteristics which
supplement each other to produce a sheet ma
thereof.
'
.
_
_
terial particularly adapted for wrapping pur 45
The copending application of Erich Gebauer
.
Fuelnegg, Louis K. Eilers and Eugene W. Moffett, poses.
It is a further important object of this inven
entitled “Transparent sheet material and coating
therefor”, Serial No. 666,222, ?led April 14, 1933,‘ ' tion to provide a thin, transparent, ?exible ?lm ‘
discloses, a coating composition for transparent or sheet material prepared by uniting two or
more ?lms of different composition, one of the
,50 ?lms prepared from the reaction product of rub
ber and a metal halide. Our invention includes constituent ?lms or plies comprising the reac
tion or end product of a polymerized butadiene
the use of such a coating composition in the manu
compound, such as natural or synthetic rubber, '
facture of transparent coated sheet material.
45
We have now found that various base ?lms may
55 be improved with respect to their resistance to
or rubber-like compounds, with a halogen or a -
halogen containing compound.
'
2
2,136,544
Other and further important objects of this
invention will become apparent from the follow
ing description and appended claims.
In general, our invention contemplates the
formation of transparent, composite sheet ma
terial by ?rst forming a relatively transparent
?lm or sheet, for convenience referred to as the
base ?lm or sheet, and then coating such ?lm or
sheet with a pellicle or layer of material that is
10 likewise transparent.
15
As will later be explained
in more detail, however, the same composition.
that may in one instance be employed in forming
the base ?lm, may likewise be employed as a
coatingfor a base ?lm of different composition.
The base ?lm is preferably made in a single
continuous operation by casting a solution of the
?lm forming material onto a smooth, highly pol
ished surface from which the base ?lm, formed
upon the evaporation of the solvent, or as ‘other
20 wise formed, may be readily stripped. Suitable
types of base ?lms may be prepared from col
loidal proteins, such as gelatin or casein, and the
like, by methods already known to the art or
as described in the following patents and pend
25 ing applications:
Hoskins Patent No. 1,764,839; , Kratz Patent
No 1,847,656; Kratz Patent No. 1,893,172; Kratz
et al. application, Serial No. 630,406, ?led August
25, 1932; and Kratz et al. application, Serial No.
30 668,808, ?led May 1, 1932.
A suitable base ?lm may also be prepared from
cellulose derivatives, such as the esters or ethers
of cellulose, regenerated cellulose, cellulose ace
probably due not so much to the chlorine con
tent as to the altered structure of the rubber
molecule itself.
In order to further illustrate our invention,
if the base ?lm is characteristically a protein
?lm, such as gelatin, casein or zein, such a base
?lm may be coated with the end product, pre
pared as above described from the reaction of
rubber and a metal halide, dissolved in benzene
to a solids content between 11/2 and 5%, and 10
preferably about 3%. Other solvents than ben
zene, such as naphtha may be employed for dis
solving the coating material. Preferably a low
boiling solvent is used that is not capable of dis
solving the material of the base ?lm.
15
If the base ?lm is largely composed of a cel
lulosic derivative,’ such as regenerated cellulose,
the coating composition may suitably comprise
a solution of the end product just described in
naphtha. The concentration of the coating solu 20
tion should be between 11/2 and 15% of solids by
weight of the mixture, and preferably about 3%.
If the base ?lm is to be a rubber hydrochloride
?lm, we prefer to use the method of applica
tion Serial No. 708,429 above referred to._ Ac 25
cording to that application, rubber hydrochlo
ride, prepared by the reaction between rubber
and liquid hydrogen chloride or hydrogen chlo
ride gas under pressure and in the absence of a
solvent, is dissolved in a suitable solvent, such 30
as benzene or ethylene dichloride, to a desired
concentration.
This solution is then cast on a
smooth endless surface and the solvent evapo
rated to leave a thin, transparent ?lm of rub
tate, cellulose nitrate, ethyl cellulose, and the
like. The art of making cellulosic derivative
?lms is well known and requires no detailed de
ing resisters or anti-oxidants may be added to
We also contemplate the use of base ?lms pre
the ?lm composition.
However, when other methods of preparing
scription.
pared from polymerized butadiene compounds by
40 the reaction of such compounds with a halogen
or compounds containing halogen. More speci?
ber hydrochloride.
Plasticizers, ?llers and age— ,
rubber hydrochloride are used, unless the rub
ber or rubber hydrochloride is carefully puri?ed
to remove foreign substances, such as proteins,
cally, our invention contemplates the use of a
resins or the like, the sheet or ?lm material
rubber hydrogen halide, such as rubber hydro
chloride. Themethod of forming rubber hydro
45 chloride is described more fully in the copend
ing application of Erich Gebauer-Fuelnegg and
Eugene W. Moffett, Serial No. 708,429, ?led Jan
‘formed from the rubber hydrochloride will fre
quently exhibit a slightly milky or cloudy effect,
uary 26, 1934, or may be found in the literature.
A suitable type of coating for any of these
50 base ?lms is described in the copending appli
cation of Erich Gebauer-Fuelnegg, Louis K. Eilers
and Eugene W. Moifett, entitled “Transparent
sheet material and coating therefore”, SerialNo.
666,222; ?led April 14,1933. The coating com
55 positions therein referred to under the trade
sometimes referred to as a haze or fog, and will 45
not be so clearly transparent and brilliant as is
desirable when the sheet material is to be used
for wrapping purposes. Such clouds, hazes or
fogs are encountered, for example, if the rubber
hydrochloride is unsatisfactorily puri?ed, or the 50
sheet material cast and dried at relatively high
humidities or too low temperatures to obtain
high clarity and transparency.
According to ‘our present invention, we have
found that the clarity and transparency of rub 55
names of Pliolite and Plioform are prepared from ‘
ber hydrochloride sheet or ?lm material may be
the reaction products of rubber, or rubber-like
compounds of the polymerized butadiene type,
greatly increased by applying a relatively thin
coating or pellicle of a transparent ?lm forming
and a metal halide, such as tin tetrachloride. In . material of different composition to one or both ,
60 the preparation of such reaction products and surfaces of the rubber hydrochloride sheet.
60
similar products, crude rubber, either milled or
More particularly, we have found that where
unmilled, is dissolved in a suitable solvent, such
as benzene, to 'give a rubber cement. This rub
ber cement is then treated with a metal halide,
65 such as tin tetrachloride or the like, and the re
action allowed to proceed until the mass has
been reduced in viscosity to a suitable point. An
end product may then be precipitated by the ad
dition of alcohol or acetone, but preferably‘ it is
70 steam distilled from the reaction mass and the
rubber hydrochloride sheet or ?lm material is
product thus obtained is dried. The composi
tion of the end product depends upon the point
at which the reaction has been interrupted, but
in general the end product contains only a minor
proportion of chlorine and its properties are
formed by casting a solution of the rubber hydro
chloride onto a smooth surface, the sheet fre
quently has irregularities on the surface oppo 65
site that in contact with the casting surface and
these irregularities impair the transparency and
clarity of the sheet. The transparency and clar
ity of the sheets may, however, in accordance
with our present invention, be greatly improved 70
by coating only the surface having these irreg
ularities with a solution of transparent ?lm form
ing‘ material dissolved in a solvent that is not a
solvent for the rubber hydrochloride base sheet
or film.
3
2,136,544
The following types of ?lm forming materials
may be employed in coating the base ?lm of rub
ber hydrochloride, for example:
Protein
Gelatin, casein, and zein.
Cellulosié derivatives-
be used as the base ?lm and as the coating ?lm or
pellicle:
'
Chlorinated diphenyls.
'
10 Hydrogenated rubber.
Base ?lm
_
Rubber chloride
Rubber hydrochloride
Zein
< End product from the reaction
between rubber and a metal
h
.
Cellulosic derivatives
Natural and synthetic gums, waxes and resins
and combinations thereof. '
End product from the reaction between rubber
Chlorinated rubber.
As speci?c examples of the composition of gel
atin and casein ?lms that may successfully be
20 employed for coating a rubber hydrochloride base
?lm, reference is made to the issued patents and
Rubber chloride
Rubber hydrochloride
End product from the reaction be
'
Rubber derivatives
Rubber hydrochloride
.15
Regenerated cellulose
Ethyl cellulose
Diphenyls (chlor
20
tween rubber and a metal halide
25 isfactorily employed for coating a rubber hydro- '
Rubber chloride
_
Protein
Zein
The following example il
lustrates a preferred formula for the nitrocellu
25
' Gliadin
Starch derivatives
Starch esters
Starch ethers
Solids
Hordein
Cellulosic derivatives
Cellulose ethers
Cellulose esters
Rubber derivatives
Rubber chloride
30
Rubber hydrochloride 4
ill/2% chlorinated diphenyl.
21/2% nitrocellulose (regular ‘1A; sec. soluble
cotton).
End product from the reactiorrbe
tween rubber and a metal halide.
,
35 Solvents—
95% mixed solvents.
It will be understood that in using any partic
ular coating ingredient for application to a spe
'
40% solvent naphtha‘ (by vol.).
60% ethyl acetate (by vol.).
lected that gives the desired properties to the
40 formula serves as a plasticizing and anchoring
In place of
,agent for the nitrocellulose ?lm.
using chlorinated diphenyls alone, the following
mixture may be employed:
45. 5% para?‘in wax.
45% dammar gum.
.
35
' ci?c base ?lm, a coating ingredient will be se
The chlorinated diphenyl used in the foregoing
.
tween rubber and a metal halide
Protein
Hydrogenated rubber, or hydro
rubber
Cyclo'rubber, or polyeloruhber
End product from the reaction be
Of the various cellulosic derivatives, we have
found that cellulose nitrate may be 'most sat
solvents);
,
Gelatine
Casein
Zein
Cellulosic
Cellulose nitrate
Cellulose acetate
pending applications listed previously.
lose coating solution (percentages being by
weight of the'mixtureexcept in the case of the
Ru )ber derivatives
Cellulose nitrate
Alkyl or aryl celluioses
10
halide
Cellulose acetate
Regenerated cellulose
and a metal halide. "
'
Coating ?lm
Rubber derivatives
‘
Protein layer
Gelatine
Casein
.
chloride base ?lm.
'
.
Cellulose nitrate, cellulose acetate, regen
erated cellulose, ethyl cellulose.
Cyclo rubbers.
ing the types of film’ forming materials that may
I
50% chlorinated diphenyl (technically known as
.“hard arochlor 4465").
It will also be understood that other solutions
of nitrocellulose in various solvents, employing
various plasticizing and anchoring agents known
coated article and a solvent for the coating in
gredient will be selected that is not a good solvent 40
for the ingredients of the base ?lm.
'
As will be apparent from a consideration of the
foregoing chart, in eachof the combinations of
base ?lms and coating pellicles embodying our
invention, at least one of the constituent sheets, 45
?lms or plies of the composite sheet is composed
largely of a rubber derivative, such as a halide,
hydrogen halide, or an end product prepared from
the reaction of a 'metal halide with rubber or a
rubber-like compound. In general ?lms prepared 50
from these various rubber derivatives all have the
stances, either in admixture with gums and res
very desirable property of being resistant to the
penetration of water, water vapor, gases and
ins or by themselves, may be used for coating
greases.
to the art .and various waxes and wax-like sub
Some of the rubber hydrochloride ?lms when 55
prepared as a single integral and uncoated ?lm,
however, have a tendency, previously referred to,
of exhibiting a slight cloudiness or foggy appear
coating solution may be prepared by dissolving ance. For this reason we prefer to coat the rub
60 the end product in naphtha up to a concentra- _ ber hydrochloride ?lms with a relatively thin 60
tion of about 10% by weight of the solution. pellicle of one of the other ?lm, forming mate
Various natural and synthetic gums and resins, rials. In this way, the cloudiness of the base ?lm
waxy‘ substances and the like may be added to of the rubber hydrochloride is cleared up and a
beautifully transparent, clear and sparkling sheet
the coating solution, if desired.
65
_
The coating operations may be carried out in is obtained.
Where the base ?lm or sheet of rubber hydro
any of the usual ways, such as by dipping, in a
tower coater, or by doctoring or “wicking” vthe chloride‘is coated' on both sides, ageing of the
coating solution onto one of both sides of the rubber hydrochloride base ?lm‘ is largely pre
vented. Suitable coating ‘solutions for this pur
base ?lm. The solvent used in the coating com
pose may be prepared from natural and arti?cial 70
position is preferably one that is easily vola
tilized at a relatively low temperature and one gums and resins and waxy substances. For in
that is not a good solvent for the base ?lm or stance, a coating, of chlorinated diphenyl applied
to bothsides of the rubber hydrochloride base
sheet.v
.
In order to illustrate the further scope of our ?lm is effective in retarding aging of the base ?lm.
The coating of the rubber hydrochloride base’ 75
75 invention, the following table is given as show
purposes.
.
When the end product isolated from the reac
tion mass of rubber and tin tetrachloride is ap
plied to a base ?lm of rubber hydrochloride, the
2,186,544
ilim with any of the film forming materials above
enumerated also serves to eliminate static and ,
thus aids in the handling or the rubber hydro
chloride ?lm or sheet material when used on 8.11
tomatic wrapping and bag forming machines.
Although this invention has been described as
applied to rubber hydrochloride sheet or ?lm ma
terial specifically, it will be understood that the
method herein described is applicable to other
hydrohalides of rubber and rubber-like com
pounds of natural or synthetic origin. The term
“rubber” as used herein, and in the claims is in
tended to cover generically rubber itself and the
We claim:
1. Transparent composite sheet material com
prising a ?exible casein sheet enveloped in a thin
coating of rubber hydrochloride.
2. Transparent composite sheet material comi
prising a ?lm layer of casein having ?rmly an
chored thereto a second layer of a rubber hydro
chloride.
3. Transparent composite sheet material com
prising a base ply of casein and a coating there
on of a rubber hydrohalide.
chief rubber-like constituents of natural or syn
4. A thin transparent and ?exible wrapping
sheet comprising a base ply of casein having an
chored thereon a thin pellicle of rubber hydro
thetic rubber, balata, gutta percha and the like.
chloride.
We are aware that numerous details of the
process may be varied through a wide range with
out departing from the principles of this inven
tion, and we therefore, do not purpose limiting
the patent granted hereon otherwise than neces
sitated by the prior art.
MARIE GEBAUER-FUELNEGG,
Administratria: of the Estate of Erich GebauerFuelnegg, Deceased.
EUGENE W. MOFFETI'.
EDOUARD M. KRATZ.
10
_
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