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Патент USA US2137168

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Patented Nov. 15, 1938 -
2,137,168
fiJNlTED STATES‘ PATENT OFFICE‘ ,
2,137,168
'
’
PRODUCTION
I .
,
or SELF-SUSTAINING l '
TRANSPARENT mus
Harold Alvin Lovey, New Orleans, La.
~ No Drawing. Application May 20,1986,
Serial No. 80,919
K is Claims. v(c1. 91-368)
will assist in bursting the granules of starch to
The present invention relates to a composite
self-sustaining ?lm of a high degree ofv trans-I
parency made from a water-soluble carbohy
drate, and, preferably, carrying on one or both
5. sides of the ?lm a waterproo?ng coating. In
one form of the invention, only one side of the
?lm carries a waterproo?ng coating‘and the other
side is inherently adhesive and is adapted to
easily' bond itself to most surfaces, except those
10 which are waxy, greasy or oily.
produce a gelatinous mass. Anyv alkali may be
used as a treating agent, but it is preferred to
use caustic soda. The amount of caustic soda
used will vary in accordance with the desired
adhesiveness of the ?nal starch hydrate ?lm, and
it generally may be stated that the caustic soda
may be added in an amount equal to one-half
(l/z) of one per cent (1%) to four per cent (4%),
based on the weight of the dry starch.
Any of the‘ water-soluble carbohydrates from
the starches down through most of the sugars
may be used, such “amylin”, dextrines, and starch
gums, the saccharides, water-soluble carbohy
, ,
10
Broadly, in accordance with the present inven
tion, the starch, such as cassava starch, is treated
so as to cause the granules of starch to swell
and disintegrate, and produce a gelatinous mass,
15 \ drate gums, such as acacia or the like, pentoses, ' which clari?es into a more or less transparent
ethers and esters thereof, and many polyhydric - stringy mass. Therefore, any agent may be used
alcohols of relatively high molecular weight.
In the more speci?c aspect of the invention, the
self-sustaining ?lm is a starch derivative, or
20 stated differently, a starch .base,'as for example,
starch hydrate, hydrolyzed starch, dextrinized
,25
which performs the above function. Instead of
using caustic soda, potassium hydroxide, am
monium hydroxide, lithium hydroxide and simi
lar compounds may be used.
20
Instead of using alkalies, the amines, such as
starch, water-soluble. starch esters and water
soluble starch ethers. Starch acetate,'starch ni
rate and starch xanthate, are examples of wate
di-methyl amine and related homologs of this
series may be used. Instead of using caustic
alkalies, other alkalies may be used, such as
oluble starch esters.
'
sodium carbonate. Basic salts and readily
It has heretofore been proposed to make self- Y hydrolyzable salts of weak acids may also be
ustaining starch ?lms, as pointed out in my. used. Generally stated, the starch solution or
prior Patent No. 2,012,344, granted ‘August 27,
any_water-soluble carbohydrate may be mixed
1935. Broadly, the methods therein set forth
30 may be utilized for the preparation of the pres
with water, or any material which will perform
the same function as water, and a small amount
ent ?lms.v
,
-
of acid, base, salt, catalyst, enzymatic substance,
.
In accordance with the present invention, the .or any material which will break down the
transparency and/or clarity and/ ?exibility of starch or water-soluble carbohydrate material
the water soluble carbohydrate, and especially into a more or less transparent mass. .
35 starch ?lms, is greatly improved, and its tend
The amount of alkali or equivalent agents used
ency to disintegrate and/or decay .is greatly in—. will determine the adhesiveness of the starch ,
hibited and reduced to a minimum.
hydrate ?lm. Using alkalies other‘ than caustic
The present invention will be illustrated by the soda, or other treatment agents, so much thereof
preparation of a starch ?lm, but it is to
un
‘will be added which will produce a pH‘ or alkalin-'
40 derstood that the procedure herein-set forth is
applicable to thetreatment of all solublecarbo
hydrates which will form self-sustaining fairly
ity in the cooking operation equivalent to that I
produced by the caustic soda in the amount
speci?ed.
‘
transparent ?lms from a solution,‘ preferably an
aqueous solution.
Any of the available starches may be used for
the alkali is heated, preferably, in a water jacket
with continued stirring to about 160° F; This is
preparing the ?lm, although preference is given
the preferred temperature in the case of cassava
to the root starches rather than to the cereal
starches. Examples of suitable starches are
will be different.
those derived from corn, potato, arrow-root, rice,
0 cassava, or the like, The use’ of cassava starch
is highly desirable, as this produces the toughest
and strongest self-sustaining ?lms.v
.
'
Utilizing cassava starch, the latter is mixed
with about six (6) to ten (10) times its weight
55 of water, to which may be added an alkali which
The starch mass which has been treated with
starch.
For other starches, the temperatures
.
The time that the starch is treated with the ‘
disintegrating agent ‘will, of course, vary with
the character of the starch and the character of
the disintegrating agent. An additional factor
in?uencing the time of treatment is the size and
shape of the treatment container. In the above
speci?c example, the cooking of the cassava ‘
2
2,137,168
starch is carried out in a one gallon cylindrical
(15%) of the protein adhesive increasing agents
vessel, whose diameter and height are preferably
the same. The time of cooking is about twenty
(20) minutes to one-half hour, after the starch
reaches the temperature of about 165° F. This
temperature, is, preferably, although not neces
sarily, maintained approximately constant dur
may be introduced into the mass.
To the plastic solution either with or without
the adhesive-increasing agent, there is added a
ing the cooking operation.
suitable plasticizing agent in amounts equivalent
to ?fteen per cent (15%) to forty per cent (40%)
of the weight of the dry starch. The plasticizing
agent may be a glycerol or a glycol, as for exam
The excess alkali present in the starch solution
10 is preferably neutralized with any suitable neu
ple, ethylene glycol, propylene glycol, di-ethylene
tralizing agent, but preferably with phosphoric
glycol and similar polyhydric alcohols, as well as 10
the various sugars including the mono-, di- and
acid, using phenol phthalein as an indicator.
tri-sacchroses, the pentoses and pentosan gums.
Nearly all of the inorganic acids and organic
Practically all of the carbohydrates have a
If
the carbohydrate is substantially hygroscopic, its 15
acids are the chemical equivalents of phosphoric , de?nite plasticizing value for the starch ?lm.
16 acid as a neutralizing agent. except those acids
which have an oxidizing effect, such as nitric
effectiveness as a. plasticizing agent is correspond
acid, chloric acid, per chloric acid, chromic acid,
ingly greater than those carbohydrates which
and similar compounds. Phosphoric acid is pre
ferred, since it appears to produce a plastic with
the fact that only a few per cent of the neu
are less hygroscopic.
As illustrative of the mono-sacchroses, refer
ence is made to glucose and fructose.
v20
As representatives of the di-sacchroses, refer
tralizing agent is necessary, sulphuric, hydro
ence is made to sucrose and maltose.
better ?owing properties. However, in view of
chloric, acetic and oxalic acids may well be used.
A ?lm produced from the above mass is in
herently adhesive because the starch has been
cooked- under alkaline conditions. In other
words, an alkaline cook produces an adhesive
?lm, the adhesive qualities of which vary with
in limits in accordance with the amount of al
kali produced.
.
.
Under some conditions, it may be desirable to
produce a ?lm which does not possess an ad
hesive surface to produce a starch hydrate ?lm
or a water soluble carbohydrate ?lm which does
not have an adhesive surface, and in order to do
so it is merely necessary to cook the starch under
neutral or non-alkaline_condition, that is, main
tain a pH as near 7 as possible. In all events,
it is important to avoid an alkali cook when it
is desired to produce a ?lm with a non-adhesive
surface.
.
Those ?lms which have little or no adhesive
properties may have the adhesive properties in
tensi?ed by incorporating in the ?lm an adhesive
45 agent. Any agent which will mix well with a
starch hydrate solution and become an integral
soluble part thereof may be incorporated in any
suitable manner in the starch mass. Similarly,
any water-soluble carbohydrate‘ which is not in
50 herently‘adhesive, may have its adhesive quali
ties increased by adding thereto an adhesive in
creasing agent. Examples of‘ suitable adhesives
are dextrine carbohydrate gums, such as arable,
tragacanth, karaya, gum ghatti, irish moss,
05 quince seed, and locust bean, as well as glue, gel
atin, casein, alginic compounds, including al
‘ ginates, and blood and egg albumen;
Where it is desirable to increase the adhesive
As representatives of the tri-sacchroses, refer
ence is made to mellitose and railinose.
Zylose and arabonose are representatives of
the pentoses, and mannan and araben are repre
sentative of the pentosan gums.
In addition, various natural gums above re
ferred to, and which contain substantial amounts
of the’ pentosan gums are very well suited for
this work. These natural gums are gum traga
canth, arabic, karaya, and- the like.
In the preferred form of the invention, it is
desirable to add to the plastic solution a pre
servative medium to inhibit organic disintegra
tion and decay of the starch ?lm. Any material
may be used, either organic or inorganic, which
will so function. Examples thereof are borax,
sodium benzoate, sodium salicylate, sodium or
thophenyl-phenate, beta-naphthol and the like. 40
These compounds are set forth by way of exam
ple, and not limitation. The amount of pre
servative added will depend on a number of fac
tors including the character of the starch and the
kind of preservative agent used. However, when 45
using borax in an amount equal to four per cent
(4%) of the weight of the dry starch gives sat
isfactory results. When using sodium-ortho
phenyl-phenate, it is desirable to add one-thirti
eth (1/30) of one percent (1%) based on the 60
weight of the dry starch.
Any preservative which will inhibit the decay
of organic matter, retard the growth of mold,
fungi, bacteria and protozoa will maintain the
utility and value of the starch ?lm. Most all ‘of
the inorganic salts possess varying degrees of
e?ectivenessin this role, and most of the aro
matic organic compounds may be introduced into
the starch‘ hydrate mass as a water solution, or
if
these or any other compounds are not soluble
ingredient may be added in various amounts, gen- '
qualities of the starch hydrate ?lm, the adhesive
so
in water, soluble'derivatives may be formed and
erally in amounts around ten per cent (10%). -these introduced into the mass. For example,
Broadly, however, it may be stated that the ad
the' aromatic hydrocarbons and their derivatives
hesive increasing agent may be introduced into may be sulphonated, or some other treatment ef
the plastic mass in amounts varying from ten per fected to bring the insoluble compound into the
65
cent (10%) to ninety per cent (90%) of the ul
soluble form. Further, the insoluble compounds
timate weight of the ?lm. When the protein may be introduced in the form of an emulsion.
products, such as gelatin, casein, albumen and Additional examples of the preservatives are the
the like are introduced into the starch hydrate water soluble inorganic salts. of such metals as
copper, arsenic, mercury, thalium, antimony, and 70
70 ?lm, the amount should not exceed approxi
mately about ?fteen per cent (15%) based on the like. Other effective organic agents inhibit
the dry weight of the starch, since around this ing decay arev substantially all of the aromatic
percentage the transparency of the resulting ?lm alcohols and all of the turpene alcohols, of which
is substantially reduced, and borders on trans
cresol, resorcinol, thymol, are representative, and
76 lucency. Any amount below ?fteen per cent are mentioned merely as representative of the 75
3
2,187,168
aromatic alcohols; and pineol and borneol, which
equal to about ten per cent (10%), based on th
are representative of the turpene alcohols and
are mentioned merely as representative of the
weight of the dry starch.
_.
Y
‘The starch ?lm may be produced as above set
turpene alcohols.
,
‘forth and preferably includes an adhesive in-‘
In general, it may be stated that the amount creasing agent, a plasticizing agent, a preserva
vof preservative agent will vary in accordance tive agent and a clarifying agent. In some cases,
with the toxicity of the preservative agent, and any or all of these various agents may be omitted, somewhat in accordance with the character of but in order to produce a high class commercial
the material treated, that is, whether the basic article, it is preferred to proceed to improve the
material is starch, a starch nitrate, a starch ace-‘ quality of the ?lm by the treatment above set 10
tate or some other water soluble carbohydrate.
In the case of highly toxic materials, amounts ,
forth.
'
’
will be necessary, and as much as up to four‘ per
The starch plastic, including ‘any or all of the i
above additive agents, is spread into ?lm form.
This may be done by providing a clean polished
surface of metal, such as nickel, stainless steels, 16
aluminum and the like or non-metallic surfaces,
such as polished Bakelite, glass, rubber and equiv
cent (4%) may be desirable to inhibit decay in
alent surfaces.
varying from about one-thirtieth (1,450) to one
?fth (1A,) of one per cent (1%) based on the
15 weight of the dry ?lm, will inhibit decay, while
for the less active agents, such as borax,jmore
-
-
Any smooth polished surfaces‘ of the character
It has been discovered that transparency and above set forth may be coated with a thin ?lm 20
clarity of the ?lm, and particularly starch ?lms, . of wax, such as carnauba wax, candeiim-paramn,
may be substantially improved by the. addition and the like, or instead of using wax, oils mayv
of a clarifying'agent to the plastic mass. Suit
be used, such as cotton seed oil, corn oil, oleo
able clarifying agents are the amino compounds. stearene, etc. The starch plastlc'is extruded or
In general, it may be stated that the substituted poured on this surface and gauged down to the 25'
ammonias, and their addition products, are suit
desired thickness by a doctor blade or scraper
able. Included in this generic term are the which moves over strips ofv vsuch thickness as
a warm humid atmosphere. ,
,
amines, amides, imides, anilines, anilides, the
will produce an ultimately dried ?lm of the de-_
cyclic nitrogen compounds, such " as pyridine,
sired dimensions. The dried ?lm may'range in
quinoline, acridine and the-like, as. well as the‘ thickness fromabout 0.0005 to 0,008 depending
hydrazines, hydroxyl amines and the oximes.
on whether’it is used as a wrapping ‘or packag
It may be stated that the more alkaline the ing sheet, or whether it ‘is used as an adhesive
amine, the less the amount required. However, material, as hereinafter more fully pointed out.
there appears to be other aspects to' the clarify
The carrier surface and the thin ?lm starch"
ing of the plastic than the alkalinity alone. Ex
is dried in an'oven at about 160° to 185° for
periments indicate that the amines have the about ten (10) minutes. If lower-temperatures
capacity of digesting and dispersing the shells are used for drying, the~~drying~ period is corre
spondingly longer.
_ of the starch granules which appear to be a form
may vary greatly, so The
longtemperature
as the temperature
of drying‘
is,
of hemi-cellulose, and thereby eliminate the
not su?icient‘to burn or damage the ?lm. 1
40 ‘slight cloudiness which results from their pres
ence. Alkalinity alone does not produce this‘
It may be stated that the time of drying varies
result.
with the thickness of the ?lm, the temperature
The amount of clarifying agent added de- _ and the relative humidity of the drying air,_tli'e
velocity with which the air passes .over the dry
particular amino compound used. Using the ing sheet, the amount of water evaporated from
amines, satisfactory results are obtained by add
the sheet, ‘and the tendency of the starch hydrate
pends on the character of the starch and the
ing from one per cent (1%) to ten per cent
?lm to oxide or skin over.
The time of drying .
‘(10%) of the weight of the dry starch. When -may vary from two and three-fourths (23/4) min-g '
using tetra substitutedamines (such as tetrone utes to more than an hour. The'optimum' cori-~
B) and treating‘ cassava starch, one percent ditions for a ?lm .of one-thousandth (M000) ofv
(1%) of this quaternary substituted amine, based an inch thick are a moisture content of eighty
on the weight of the dry starch, is used.
'
per cent (80%), axtemperature of about 185° F.
When using tri-ethanol amine and treating‘ dry bulb, and 135° F. wet bulb, and an air veloc
cassava starch, ten per cent (10%) of this amine, ity of about 300 linear feet ‘per minute. These
based on the weight of the starch is used.
Amino ‘derivatives, such as the acct-amines, as
4 conditions will prevent skinning over of a nor‘mal starch cook. _
for example, acet-amide, acet-anilide, and the
' The?lm, after drying, is stripped from the
like, as well as the alcohol amines, such as mono-,
spreading surface when the moisture content has
been reduced su?lciently to produce a fairly dry
?lm. As an example, it has been found that the
di- and-tri-ethanol-amine. ' The ethanol amines
have the dual function of both clarifying and
plasticizing the dried ?lm and may replace some
?lm is satisfactorily dried when it has had its
moisture-content reduced so that the moisture
content varies from twelve (12) to twenty (20)
per cent of, the weight of the‘= dried starch com
of the glycerol aboverefer'red to as a suitable
plasticizer for the starch ?lm.
Tetrone B marketed by
_
~
‘and Haas of
Philadelphia is a quaternary or tetra substituted
, .
'
-
position ?lm.
-
‘
ammonium with alkyl groups and with a molec
The removal of the film from the carrier sur
ular weight of-approximately 1'70. This product face is effected by picking the ?lm from the
is so active in its solvent power that it dissolves ' spreading carrier surface, and then winding the >
70 cellulose present in the starch, and as a result v ?lm upon a roll of from about one-quarter ('A) 70
it is only necessary to add about one per cent of an inch to several inches in diameter, de
(1%) to obtain the desired result. On the other pending upon the type of device used and the
hand, less‘ active amino compounds must be rate of removal.
added in greater quantities, for example, if suc
The ?lm should be promptly unwound‘where
cinamide is used, it should be added in an amount short spreading is made, and if the operation
4
2,187,168
is continuous, the ?lm should pass only partly
around the roll onto the other equipment for
the subsequent operations.
The ?lm produced as above set forth may have ‘
one or both of its surfaces coated to render
either both surfaces of the ?lm waterproof, or
only one surface waterproof, leaving the other
surface uncoated so as to take advantage-of the
adhesive character of the surface and adapt the
10 ?lm to such uses as hereinafter set forth.
It is within the province of the present in
vention to coat the ?lm in any manner, includ
ing the method set forth in my prior Patent No.
2,012,344.
,
When coating only one face of the ?lm, the
coated composition may be applied prior to re
moval of the starch ?lm from its carrier surface,
and the application may be by means of a spray
gun, by a brush, or the composition may be ?owed
20 on or printed on the surface by means of a suit
able printing roll.
_
.The waterproofed coating composition may be
applied to the carrier surface and the composi
tion dried to remove the volatile solvents. The
starch plastic is then spread over this surface,
drying the starch ?lm as above described.
Thereafter, the starch ?lm carrying the water
proo?ng coating which is in effect a lamination
sheet comprising the starch ?lm and the water
30 proo?ng ?lm thereon may be lifted from the
carrier surface. The material may then. be
wound upon rolls, which are trimmed to the de
sired width by means of suitable cutting knives
already in use for this general type of produc
35 ‘tion._ These rolls may then be cut into smaller
widths while coiled or the rolls may be unwound
and passed between slitting wheels or slitting
knives and subsequently wound in coils to pro
vide an adhesive tape of the desired width and
diameter. The ?lm may be supplied in large
stock-size sheets of standard dimensions, or in
suitable smaller cut-to-size dimensions. In
stacking these sheets, which have only one side
coated or waterproofed and the other side of an
adhesive character, it is obviously necessary to
avoid two starch surfaces coming in contact with
each other, as the adhesive nature of this ma .
terial will prevent subsequent separation with
out destruction of the composite ?lm.
60
The waterproo?ng composition itself may be
any of the materials set forth in my prior patent.
However, in general the waterproo?ng lamina
tion may consist of a coating resulting from ap
plying to the starch ?lm solutions of the cellu
lose esters, of which the cellulose acetates, the
nitrates and benzoates are typical examples; cel
lulose ethers in general, of which cellulose
.
Per cent
Carbon
15
Hydrogen
2.5
‘Sulphur _________________ -1 ___________ --
82
One surface of the starch ?lm may be rendered
waterproof and non-adhesive by coating the
same with a thin, ?lm derived from natural and
synthetic waxes which may be applied from 10
either a solution of the same, or by application in
the molten state of the wax. - These coating
compositions are plastlcized with suitable soften
ing agents to make the resulting waterproo?ng
?lm on the starch su?iciently ?exible and plastic
15
so that the ?nal starch ?lm carrying the water
proo?ng composition may be used for any of
the herein described purposes.
It is desired to point out that one of the fea
tures of the present invention is the provision of
a self-sustaining starch ?lm made of a starch
'or a starch derivative, one surface of the ?lm
having a waterproofed protective coating. and
the other surface being characterized by ad
hesive qualities enabling the ?lm to be used for
any purpose where this adhesive charactermay
be taken advantage of.
.
-
The following are representatives of suitable
waterproo?ng compositions:
.
1. Cellulose
Ethyl
Per cent
nitrate _____________________ __ 15
acetate ________ _.'. _____________ _~__
Butyl
5
acetate ____________ -.' ______ __'____
20 -
Benzol ______________________________ __
12
Methanol ____________________________ __
8
those speci?cally hereinbefore mentioned.
Per cent 40
3. Natural resins ________________________ __
Butyl acetate ________________________ __
25
40
Acetone _____________________________ __
15
Benzol _____________ __‘ _______________ __
12
Methanol ________________________ __'____
8 .45
The solvent mixture of the above set forth com
position may be modi?ed to meet the requirey '
ments of the various types of natural resins in
order to produce a clear transparent ?lm. It
will also serve for most of the synthetic resins.
~
Per cent
4. Rubber solutions (solids) _____________ __
10
Ethylene dichloride ___________________ __
90
Other solvents such as carbon bi-sulphide, 55
solutions of natural resins such as dammars,
coating composition.
chlorinated rubbers, rubber hydrochloride, syn
thetic rubber solutions, such as thiokol.
Thiokol is prepared by the polymerization of
chlorinated ole?ns with polysul?des. In the pre
70 ferred form ethylene di-chloride is heated at
around its boiling point with sodium polysul?de
(Na2s4), in which it is used in the proportion of
about two and one-half (21/2) times the amount
of ethylene di-chloride. The reaction is com
pleted in about six (6) hours.
35
2. In the above composition, the cellulose nitrate
may be substituted by a cellulose ether, including
methyl ethyl, and benzyl ethers are- examples;
65 may be derived from rubber solutions made from
30
40
Dibutyl phthalate _____________________ __
acetone, solvent naphtha, etc. may be used in
place of the above depending upon the _par
ticular form of rubber used in formulating the
kauris, copals and the like; synthetic resins in
general of which the phenol aldehydes, the glyc
eryl phthalates, the cumars, the vinyl esters and
the like are examples. The waterproo?ng coating
13
The combusion analysis of thiokol is
-
Per cent
5.. Waxes ________ __,___________________ __
6-10
Solvents ___________________________ __ 94-90
The solvents or solvent mixtures will depend
upon the particular wax used. For para?in, 65
solvent naphtha may be used; for halowaxes or
chlorinated naphthalenes, ethylene dichloride
may be used; for true waxes such as spermacetl,
carnauba and the like varying mixtures of ace
tone, ethyl acetate and the like may be used.
70
It may be stated, in general, that the pre
ferred waterproo?ng composition consists of
those compositions containing nitrocelluloses
such as cellulose nitrate.
Of course, the com
position is dissolved in'a suitable solvent and a 75
15'
2,187,16Q
nominal amount of plasticizer is added. It may leave no free adhesive surface then the material be desirable, in some cases, to add a small amount may also be used ingeneral for wrapping or for
of wax-like substances to improve the .water . any purpose for which it is desirable to provide
proofness of the dried coating. For example, the
a' transparent substantially waterproof ?exible
base of the waterproo?ng composition may be composite sheet.
.
cellulose nitrate together with a small proportion
One of the important products of the present
of wax or natural resins together with a small invention is a clear transparent non-decayable
proportion of wax or rubber solution, together vstarch ?lm which carries a waterproo?ng coat
with a small proportion of wax. The use of the ing on one face and is relatively dry on the
waxes while quite desirable in the nitro-cellulose
other face, said dry face becoming adhesive only 10
containing compositions is not quite so desirable when moistened. Such a sheet may be used as
in other waterproo?ng compositions. It is de-* a mending tape and may be sold in the usual
sired to point out that in one form of the present ‘ spool form. It may also be used as a protective
invention, it is desirable to use. the ‘same plasti
covering for books, maps, drawings and prints,
15 cizer for the starch ?lm as is used for the water
the adhesive aids of the ?lm being, of course, 15
proo?ng composition. .For example, di-ethylene
applied to the objects.
glycol may be used to plasticize the starch ?lm
and the ultra-cellulose coating composition. It
The ?lm ‘may also be applied to colored litho
graphed and printing matter, and it may be
may be stated that when both the starch ?lm
stated that it has been impossible to put a water
proof lacquer coating on such materials because 20
and the coating composition contain the same
plasticizing agent, that this plasticizing agent
which is common to each lamination of the ?lm
tends to improve the bond between the two dis
similar‘ laminations. Instead of using di-ethyl
25 ene glycol as a plasticizerpfor, both the starch
?lm and the coating composition, ethylene-gly
'
col-mono-methyl-ether may be used.
'
While it has been stated that a ‘common plas
ticizer may be used in a starch ?lm lamina
'
such a material causes the inks to‘ run.
This
disadvantage is entirely eliminated in accordance
with ‘the use of .the product herein disclosed.
a The hereindescribed laminated sheet is also
suitable as a-decalcomania or a transfer, as well 25
as for ornamental decorations for, glass. It may
be used in connection with transparent signs.
Advertising‘. novelties, oil and water paintings
and photographs may be protected and covered
a 80
tion and in the waterproo?ng lamination, it is by this type of sheet.
within the province of the present inventionto
The herein-disclosed self-sustaining starch,
use di?erent plasticizers in these two laminations ?lm is adapted for use in the pharmaceutical
and use a' separate bonding agent between the . ?eld. The material may be used'as an adhesive
starch ?lm lamination and the waterproo?ng tape for bandage closures and wound coverings,
lamination and di-ethylene glycol and ethylene; and also as a medicated tape and as a surgical 35
glycol-mono-methyl-ether may be used as bond
ing agents. '
>
"
' If plasticizers are already present in the starch
?lm composition and in the waterproo?ng com
position, then about 10% of the above com-.
pounds, based on the weight of the starch ?lm,
,may be used to improve the, bonding of the two
laminations.
‘
On the other hand, if the above substances
or their substantial equivalents are to be used
in the starch ?lm as a plasticizer and a bonding
age'nt,.then it is preferred to have present in
the starch ?lm an amount equal _to about thirty
per cent (30%) of the weight of the starch.
As previously pointed out, the present inven
tion contemplates the provision of a self-sus
taining starch ?lm which has been impregnated
with or coated with a waterproo?ng material so
as to coat'one or both sides of the starch ?lm.
If both sides of the starch ?lm are coated, then,
of course, it is not necessary to prepare the
starch ?lm so that it, has adhesive qualities.
However, if only one face of the starch ?lm is
coated, then it is necessary to proceed-as here- '
dressing tissue, said subject matter being claimed
in applicant's co-pending application Serial
Number 84,563, ?led June 10, 1936.
In general, it may be stated that when the self
sustaining starch ?lm carrying a waterproofing
coating is used as a wrapping material and is not
provided with an adhesive surface, that it should
vary in thickness between 0.001 and 0.0001.
When the ?lm is provided with an adhesive sur
face, the thickness, in general, should range from we
about 0.001 to 0.003, as the case may require.
This is the preferred thickness when the material
is used for mending purposes.
'
It may be pointed out that the ?lm of the
adhesive surface may be used for bonding and 50
sealing purposes by moistening the potentially
adhesive surface or the surface need not be
‘moistened.
In this case, the ?lm will act as a
bonded and adhesive medium. by the simple
expedient of applying heat'or heat and pressure. 55
In certain cases, when the adhesive surface is
moistened, the seal maybe made more e?ective
by applying heat and pressure.
'
,
It may be stated that in the broad aspect of
the present invention, all water soluble carbo co
hydrates may be formed into self-sustaining
in set forth to digest the starch with su?lcient
alkali to produce a starch ?lm, which has in
herent adhesive properties. Of course, if the transparent ?lms, the water-soluble cellulose
?lm is to be coated on both sides. then it is -esters and cellulose ethers may also be used to
not necessary to incorporate any adhesive-in
prepare self-sustaining transparent ?lms and the
creasing agent.
65
water-soluble
esters andcarbohydrates,
ethers, may be
includingthece'llur;
treated as herein "j
If the starch ?lm is not inherently adhesive, .lose
it may still bevcoated on only one side and used set forth to produce composite waterproof ?lms.
for many Purposes.
'
'
In- general,‘ it may be stated thatthe water
In general, it may be stated that the starch soluble carbohydrates are dissolved in a sum
cient amount of water to obtain a viscose plastic 70v
70 ?lm if made from a non-adhesive starch com
.position and ‘coated on one or both sides, but solution or colloid and extrude the same through .
preferably on both sides, may be used as a trans
alslot or other known type of ?lm-forming device
" parent waterproof wrapping for many products. ' onto a carrier surface upon which it is dried
If the ?lm is made from an adhesive starch
75 ?lm and is waterproofed on both sides so as to
and subsequently removed. In the case of starch,
only, it is necessary to cook the same to render 75
6
2,187,168
the starch water soluble and thereby produce a
common non-volatile solvent present in both ?lms
- workable plastic mass from which the ?lms are
and acting as a plasticizer for both ?lms.
9. A new article of manufacture comprising a
formed.
.
It is within the province of the present inven
transparent ?exible self-sustaining inherently
tion to use mixtures of different starch bases to
adhesive carbohydrate ?lm formed. of a member
of the group consisting of starch derivatives, sac
charides, starch gums, carbohydrate gums, pen
toses, ethers and esters thereof, the ?lm having
present an agentinhibiting organic disintegra
provide the self-sustaining starch base ?lm. For
example, the starch hydrate base may be mixed
with starch nitrate to provide a ?lm which has
inherent adhesive properties or which does not
Similarly, dex
tion of the ?lm, said agent being compatible with 10
trinized starch may be mixed with starch acetate the carbohydrate ?lm and incapable of substan
or starch nitrate. Any of these mixtures may be , tially reducing the transparency of the ?lm, one
treated in accordance with the present invention face of said ?lm having adhesive properties, and
as herein disclosed. .
the other face carrying a waterproo?ng ?lm, said
What is claimed is:
?lms being bonded together by a common non 15
1. A new article of manufacture consisting of volatile solvent present in both ?lms and acting
ll) have any adhesive properties.
a transparent ?exible self-sustaining‘ inherently
adhesive starch base ?lm, adapted as a protective
covering for a book and the .like, one face of said
20 ?lm having adhesive properties, said face being
capable of being moistened, and the other face
of which carries a waterproo?ng ?lm.
2. A new article of manufacture consisting of
a transparent ?exible self-sustaining starch base
?lm possessing substantially no inherent adhesive
properties but made adhesive by having incorpo
rated there'in an adhesive material.
,3. A new article of manufacture consisting of
a transparent ?exible self-sustaining starch base
30 ?lm possessing substantially no inherent ad
hesive properties but made adhesive by having
incorporated therein an adhesive material, one
face only of said ?lm carrying a waterproo?ng
agent, and the other face being adhesive in
35
character.
-
4. A new article of manufacture consisting of
a transparent ?exible self-sustaining inherently
adhesive starch base ?lm, having present an agent
inhibiting organic disintegration said agent be
40 ing compatible with the starch base ?lm and
incapable of substantially reducing the trans
parency thereof, one face of said ?lm having
adhesive properties and the other face carrying
a waterproo?ng ?lm, the latter being bonded to
45 the starch ?lm by a common-non-volatile solvent
present in both ?lms and acting as a plasticizer
for both ?lms.
5. A new article of manufacture consisting of
as a plasticizer for both ?lms.
10. A new article-of manufacture comprising
a transparent ?exible self-sustaining inherently
adhesive starch base ?lm having present an 20
agent inhibiting organic disintegration of the
?lm, said agent being compatible with and in
capable of substantially reducing the trans
parency of the starch base ?lm, one face of said
?lm having adhesive properties, and .the other
face carrying a water-proo?ng. ?lm, said ?lms
being bonded together by a common non-volatile
solvent present in‘ both ?lms and acting as a
plasticizer for both ?lms.
_
‘ 11. A new article of manufacture comprising
a transparent ?exible self-sustaining inherently
adhesive starch base ?lm clari?ed by the pres
ence of the reaction product of the starch and
a clarifying agent of the substituted ammonia
type capable of digesting and dispersing the shells
of the starch base, one face of said ?hn having
adhesive properties and the other face carrying
a waterproof ?lm, said ?lms being bonded to
gether by a common non-volatile solvent present
in both ?lms and acting as a plasticizer for both
?lms.
12. A new article of manufacture comprising
- a transparent ?exible‘ self-sustaining inherently
adhesive starchvbase ?lm clari?ed by the pres- ,
ence of the reaction product of ‘the starch and
a. clarifying agent selected from the group con
sisting of amines, amides, imides, anilines, ani
lides, the- cyclic nitrogen compounds including
a transparent ?exible self-sustaining starch base
pyridine, quinoline, acridine, hydrazine, the hy
50 ?lm containing a plasticizer and clari?ed by the
droxyl amines and the oximes, and having incor
porated' therein an agent inhibiting organic dis
presence of a reaction product of the starch with
a clarifying agent of the substituted ammonia
type capable of digesting and dispersing the
starch shells of the starch.
6. A new article of manufacture consisting of
a transparent ?exible self-sustaining starch base
?lm containing a plasticizer and clari?ed by the
presence of a reaction product of the starch with
a clarifying agent of the substituted ammonia
60 type capable of digesting and dispersing the shells
integration of said starch base ?lm, said agent ,
being compatible with and incapable of substan
tially reducing the transparency of the starch
base ?lm, one face of said ?lm having adhesive 55
properties and the other face carrying a water
proo?ng ?lm, said ?lms being bonded together
by a common non-volative solvent present in
both ?lms and acting as a 'plasticizer for both
?lms.
of the starch, one face of said ?lm being ad
13. The process of producing ‘a transparent
hesive in character and the other face of said
1 ?exible self-sustaining carbohydrate ?lm com?
?lm carrying a waterproo?ng ?lm.
7. A new article of manufacture consisting of prising cooking a water soluble carbohydrate in
an alkaline medium adapted to confer adhesive 65
65 a transparent ?exible self-sustaining carbohy
drate ?lm formed of a member of the group con- ' properties upon the resulting plastic and ?lmv
sisting of starch derivatives, saccharides, starch produced therefrom adding after coolnn'g a plas
gums-carbohydrate gums, pentoses, ethers and ticizer, and a. clarifying agent selected from the
esters thereof, one face of which has adhesive group consisting of amines, amides, imides, ani.
70 properties, and the other face of which carries a lines, anilides, the cyclic nitrogen compounds in 70
waterproo?ng ?lm.
8. A new article of manufacture consisting of
a transparent ?exible self-sustaining starch ?lm,
one face of which carries a waterproo?ng ?lm
76 the latter being bonded to the starch ?lm by a
cluding pyridine, quinoline, acridine, hydrazine
the hydroxyl amines and the oximes, casting
the cooked plastic material in the form of a self
sustaining ?lm, and applying to one of‘ the ad
hesive surfaces of the ?lm a waterproo?ng agent. 75
7
2,187, 188
14. The process of producing a transparent
?exible self-sustaining starch ?lm comprising
cooking the starch material in'an alkaline medi
‘um to confer adhesive properties upon the starch
plastic and ?lm produced therefrom adding after
cooking a plasticizer, and a clarifying agent se
lected from the group consisting of amines, am
17. The process of producing a transparent
?exible self-sustaining starch ?lm comprising
cooking the starch material to a plastic mass in
an alkaline medium adapted to confer adhesive
properties upon the starch plastic and the ?lm
produced therefrom, adding after cooking a com
pound of the substituted ammonia class to the
plastic to clarify the same, said substituted am
‘ compounds including pyridine, quinoline, acridine, monia product also acting as a plasticizer for the
10 hydrazine, the hydroxyl amines and the oximes, starch ?lm, casting the cooked plastic into self
casting the cooked starch plastic in the form of a sustaining ?lm, and applying to one of the ad
self-sustaining ?lm, and applying‘ to one of the - hesive surfaces of the ?lm a waterproo?ng agent.‘
adhesive surfaces of the ?lm a waterproo?ng
18. The process of producing a transparent
agent.
?exible self-sustaining starch ?hn comprising
15
15. The process of producing a. transparent cooking the starch material to a plastic mass in 15
?exible self-sustaining starch ?lm comprising an alkaline medium adapted to confer adhesive .
cooking the starch material to a plastic mass in properties upon the starch plastic and the ?lm
a medium of sumcient alkalinity to confer ad
produced therefrom, adding an ethanol amine to
hesive properties upon the starch plastic and the clarify and plasticize the starch plastic, casting
?lm produced therefrom, adding after cooking a the cooked plastic into self-sustaining ?lm and
plasticizer and a compound of the substituted applying to one of the'adhesive surfaces of‘the
ides, imides, anilines, anilides, the cyclic nitrogen
_ ammonia class to the plastic to clarify the same; ?lm a waterproo?ng agent.
casting the cooked plastic in self-sustaining ?lm
form and applying to one of the adhesive sur
faces of the ?lm a waterproo?ng agent.
»
19. The process of producing a transparent
?exible self-sustaining ‘starch ?lm comprising
cooking the starch material having present gran
16. The process of producing a transparent ' ules of starch and granular shells in an alkaline
?exible self-sustaining starch ?lm comprising -medium adapted to confer adhesive properties
cooking the starch material to a plastic mass in upon the starch plastic, adding to the plastic
after cooking a plasticizer and‘ a substituted am
a medium of sufficient alkalinity to confer ad
hesive properties upon the starch plastic and the monia compound having the capacity of digest
ing and dispersing the shells of the starch gran
?lm produced therefrom, adding after cooking a ules
to thereby eliminate in the plastic and in the
plasticizer and about 1% to 10% by weight of ?nal ?lm the slight cloudiness resulting from the
the starch of a compoundof the substituted am
presence of said granules, casting the so-treated
monia class to the plastic to clarify the same, starch plastic into self-sustaining ?lm and ap 35
casting the cooked plastic into self-sustaining plying to one of the adhesive surfaces ‘of the ?lm
?lm and applying to one of the adhesive, sur
a waterproo?ng agent. ~
faces of the ?lm a waterproo?ng agent.
HAROLD ALVIN LEVEY.
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