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Патент USA US2137169

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Patented Non-15, 1938
Harold Alvin Levey, New Orleans, La.
No Drawing. Application June 10, 1936,
Serial No. 84,563
' 11 Claims.’ ((1167-84)
The present invention relates to a ?exible self
without the addition of any of the addition prod- '
-sustaining transparent medicinal dressing mate- ucts herein set forth, a transparent ?lm. ' This
rial, comprising a carbohydrate ?lm, the term ?lm when coated with a correctly formulated
“sell-sustaining" being used to denote a ?lm
5 which is capable 01" physical existence as such
without being carried or supported upon any sur
’ lace upon which it is spread. '
The ?lm may be made from any of the water
soluble carbohydrates from the starches down
10 through most of the sugars, as for example
“amylin”, the dextrines, the starch gumsbthe
saccharides, the water-soluble carbohydrate
gums, such as acacia or the like, the pentoses,
and ethers and esters thereof and many poly
15 hydric alcohols of relatively high’ molecular
In one form of the invention,"it is desirable to
provide a water-soluble carbohydrate trans
parent self-sustaining ?lm which is inherently
20 adhesive, said water-soluble carbohydrate ?lm
lacquer or coating composition will form a com
posite ?lm or glass-like transparency.
Preferably. the ‘self-sustaining ?lm in the form
of an adhesive medium, such as an adhesive tape
or a medicinal dressing material, is made from a
starch. derivative, or, stated diilerently, from a
starch base, as for example starch hydrate, hy- l0
drolyzed starch, dextriuized starch, water solu
ble starch. esters and water-solublestarch ethers,
such as the methyl, ethyl and benzyl starch
ethers. Starch acetate, starch nitrate and starch
xanthate are examples oi.’ water-soluble starch l5
esters. The adhesive medium of the present ap
plication‘may be made from a mixture of var
ious water-soluble carbohydrates ii’ the constitu
ents of the mixture are compatible ‘with each
other. For. example, a mixture of starch bases ‘20'
may be utilized to make the
A mixture 01'
being coated preferably on one side with a water
a starch base, such as dextrinized starch and
proofed protective transparent coating to in
crease the general utility of the ?lm. A ?lm of ' starch nitrate, or a starch base and starch ace
the character above described is well adapted for tate, or a starch base,- as for example, dextrinized
25 use as an adhesive tape or medium. If the tapes starch and starch ethers, maybe used’lto provide 25
are not waterproofed on one side, the handling the?lm, provided these starch derivatives are '
water-soluble and, therefore, compatible with
of these tapes become dimcult and an uncom
iortable task. . In addition, in the manufacture,
the starch hydrate oi the present invention.
At this point, it is desired‘, to state that the
of ‘the adhesive tape in accordance with the»
30 present invention, the tape is preferably wound term “starch base”. includes starch derivatives 30
on spools, and it one side of the ?lm were not _. and ' starch degradation products. The term
adhesive in character, it would not be necessary “starch derivative” is intended to cover any prod- to wind a strip of waxed paper or the like be vuct which may be obtained from starch as a
tween laminations to prevent adhesion of the
35 laminae to each other.
starting point and which contains in its molecule a
more’or less modi?ed form of starch. The term 35
“starch derivative" includes such products as
While a water-soluble starch base is the pre-.
starch-esters and; starch ethers, dextrines and
ferred material for forming the ?lm, it is de
sired to point out that all water-soluble carbo ‘sugars may be classi?ed as “starch degradation
hydrates which have the property of producing products". Starch hydrate and partially hdro-_
40 self-sustaining ?lms may be utilized, and in the lyzed starch, which is really starch itself, re- 40
preferred form of the invention, it is desired that sponds to the blue iodine test, which appears to
these self-sustaining ?lms be transparent. Cel
lulose is the only‘ carbohydrate which ,is , not
water-soluble to any degree whatsoever. Sever
45 a1 forms of hemi-celluloses are water-soluble.
Further, gama-cellulose which results from the
alkali treatment of all forms of natural cellulose,
produces a water-soluble carbohydrate. Certain
of the sugars also are waterg-soluble to only a
50 minor extent. Starch, before it is cooked, is in
be the criterion to determine the presence of
starch. The degradation products whichmay
be completely or partially degraded, do not give
the blue iodine test.
For example, a degraded 45
product consisting of so-called erythro dextrine
gives a red iodine coloration, while totally dex
trinized starch ‘gives no color reaction ‘with iodine.
Further, on complete hydrolysis by acid treat
men't‘or with enzymes ‘or bacteria of the proper 50 ,
soluble in water. It is only after the cooking op
type, a theoretically one hundred per cent (100%)
eration that the starch bedlomes water soluble.
yieldoi' dextr'o glucose should result.
The term -._“starch hydrate” as used in the
present speci?cation, ‘covers the product which
as bohydrate, as for example starch, will produce. results from the heating of the vegetablevstarches 55
It is desired to further point out that a prop
erly selective and processed water-soluble car
.52 :
carbohydrates which'will form a self-sustaining
neutral solution to the bursting of the granules, fairly transparent medicinal dressing ?lm.
Any of the available starches may be used for
and continued heating at substantially the burst
ing temperature until the plastic mass clari?es. preparing the ?lm, although preference is given
Research work' indicates that starch treated as to the root starches rather than to the cereal
above set forth is the 'least degraded form of starches. Examples of suitable starches are those
starch. The molecular aggregate is very high derived from corn, potato, arrow-root, rice,
and gives the characteristic blue iodine test and cassava, or the like. The use of cassava starch
is highly desirable, as this produces the toughest,
almost a theoretical yield of glucose.
It is desired to state that when the starch is . clearest and strongest self -sustaining ?lms.
treated with alkali, such as caustic soda, in rela ' ' Utilizing cassava starch, the latter is mixed
tiyely small amounts, as for example, in amounts with about six (6) to ten (10) times its weight of
‘less than six per cent (6%), the degradation of water, to which may be added an alkali which will.
the starch is relatively small, as shown by the. assist in bursting the granules of starch to pro
with a substantial amount of water in a nearly
15 blue iodine'coloration. Practically none of the
starch is converted into dextrines or sugars.
In one form of the present invention the starch
hydrate base may have affixed thereto a starch
nitrate coating to provide a composite ?lm which
20 has inherent adhesive properties or one which
does not have any adhesive properties. The above
is an example of a composite self-sustaining‘
transparent water-soluble
carbohydrate film
which does not have a waterproof coating.
If de
sired, . either the starch hydrate face or the
starch nitrate face may be provided ‘with a water
such as cassava starch, is treated so as to cause
proofed coating. While in the present speci?ca
the granules of starch to swell and disintegrate.
and produce a gelatinous mass, which clari?es
tion, it is indicated that the coating which is
applied to the starch, and preferablya starch base
30 which is inherently adhesive, is desirably a water
proofed coating, it is to be understood that any
coating may be applied which will function to
destroy the inherently adhesive properties of the
exposed facing of the film. The adhesive prop
35 erties, as later on pointed out, may be destroyed
without providing any coating whatsoever.
If any of the addition products hereinafter set
forth tend to have a disintegrating effect upon the
starch plastic, then the production of a continu
into a more or less transparent stringy plastic.
Therefore, any agent may be used which performs 30
the above function. Instead of using caustic
soda, potassium hydroxide, ammonium hydroxide,
lithium hydroxide and similar compounds may
be used.
Instead of using alkalies, the amines, such as 35
di-methyl amine and related homologs of this
series may be used. Instead of using caustic
?lm may be coated on one side with a water
alkalies, other alkalies may be used, such as
sodium carbonate. Basic salts and readily hy
drolyzable salts of Weak acids may also be used. 40
Generally stated, the starch solution or any
water-soluble carbohydrate may be mixed with
water, or any material which will perform the
same function as water, and a small amount of
proo?ng coating, exempli?ed by a nitrocellulose
acid, base, salt, oxidizing agent, catalyst, e'nzy
40 ous self -sustaining ?lm involves mechanical dif?
In order to eliminate the latter, the
product of the present invention may be made in
the form of two laminations. A normal starch
duce a gelatinous mass. Any alkali may be used 15
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 adhesive
ness of the ?nal starch hydrate ?lm, and it gen
erally may be stated that the caustic soda may be 20
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.
Broadly, in order to produce the medicinal
starch ?lm of the present invention, the starch, 25
lacquer, and on the other side with a starch
lamination carrying the desired medicinal ma
terial. This gives a three lamination composite
?lm comprising a ?lm of starch and ,medicinal
on the outside surface, an intermediate base ?lm
of normal starch, and a waterproo?ng ?lm, as
for example, a cellulose derivative.
In one form of the invention, one surface or
side of the medicinal dressing or ?lm carries a
55 ?exible waterproo?ng coating, and the other side
is free of the waterproo?ng coating, but is pref
erably, although not necessarily, adhesive in
character so that it will easily bond itself to any.
surface to which it is applied.
The medicinal dressing material of the present
invention may be used as an adhesive tape, as a
medicated tape, or as a surgical dressing tissue.
There may be incorporated in the carbohydrate
?lm pharmaceutical products, medicinals and
65 antiseptics. Generally speaking, almost any type
of liquid or solid medicinal may be incorporated in
the ?lm, said medicinal being adapted to act on
the skin or through the skin to produce a desired
physiological and/or pharmacological reaction.
The following is a speci?c example of the prep
aration of the medicinal dressing material in ac
cordance with the present invention. While the
preparation of‘ a starch ?lm is set forth, it is to
be understood that the procedure set forth is
75 applicable to the treatment of all water-soluble
matic SubstanCeLbacteria, or any material which
Will break down the starch or water-soluble car
bohydrate material into a more or less transpar
ent mass.
The amount of alkali or equivalent agents used
will determine the adhesiveness of the starch
hydrate ?lm. Using alkalies other than caustic
soda, or other treatment agents, so much there
of will be added which will produce a pH or alka
linity in the cooking operation equivalent to that
produced by the caustic soda in the amount speci
The starch ‘mass which has been treated with
the alkali is heated, preferably, in a water jacket
with continued stirring to about 160° F. This is 60
the preferred temperature in the case of cassava
starch. For other starches, the temperatures
will be different. '
The time that the starch is’ treatedwith the
disintegrating agent will, of course, vary with the 65
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 70
starch is carried out in a one gallon cylindrical~
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 75
temperature is, preferably, althoughnot neces-. after, the‘other additives-are incorporated in the
sarilyrmaintained approximately constant dur
ing the cooking .operation.
mass and the ?lm is formed.
It is within the province of the present inven- '
The excess alkali present in the starch solution‘
is preferably neutralized with any suitable neu
tralizing} agent, ‘but preferably with phosphoric
acid, using phenol phthalein as an indicator‘.
Nearly all of the inorganic. acids and organic
acids are the chemical equivalents of, phosphoric
10 acid as a neutralizing agent,'except those acids
which have an oxidizing effect, such as nitric acid,
chloric acid, per chloric acid, chromic acid, and
similar compounds. Phosphoric. acid is pre
tion to produce an adhesive medicinal dressing" '
starch hydrate ?lm, or a ?lm from the starch
carbohydrate which has both faces of the ?lm
adhesive, and 'de-adhesify one side of the ?lm to
produce an article having an adhesive face and
a non-adhesive face. This may be accomplished
by applying a soap, oil or wax solution on the 10
face it is desired to de-adhesify.
Those ?lms which ‘have little or no adhesive .
properties may have the adhesive properties in
ferred, since it appears to produce a plastic with
However, in view of
tensi?ed by incorporating in the ?lm- an adhesive.
agent. Any agent which‘ will mix well with a 15
the fact that only a few per cent of the neutral
starch hydrate solution and become an integral
izing agent is necessary, sulphuric, hydrochloric, soluble part thereof may be‘ incorporated in any
acetic and oxalic acids may well be used.
suitable manner in the starch mass.’ Similarly,
' A medicinal dressing ?lm‘ produced from the any water-soluble carbohydrate which is not in
20 above mass is inherently adhesive because .the
herently adhesive, may have its adhesive qualities 20
starch has been cooked under alkaline conditions. increased by adding thereto an adhesive increas
In other words, an alkaline cook produces an ing agent. Examples of suitable adhesives are
adhesive ?lm, the adhesive qualities of which vthe dextrines and carbohydrate gums, such as
vary within limits in accordance with the amount arabic, tragacanth, karaya, gum ghatti, irish
25 of alkali produced.
moss, quince seed, and locust bean, as well as 25
15 better ?owing properties.
Under some conditions, it may be desirable to
produce an adhesive medium such as an adhesive
tape or a medicinal dressing ?lm which does not
possess an adhesive surface to produce a starch
30 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,
glue, gelatin, casein, alginic compounds, includ
ing alginates, and blood and egg albumen.
Where it is desirable to increase the adhesive
qualities of the starch hydrate ?lm, the adhesive
ingredient may be added in'various amounts, gen‘ 30
erally in amounts from ten to forty per cent (10%
to 40%) of the weight of the ?lm. Broadly,
however, it may be stated that the adhesive in
creasing agent may be introduced into the
that is, maintain a pH as near 7 as possible. In .
35 all events, it .is important to avoid an alkali cook ‘ plastic mass in amounts varying from ten per cent 35
when it is desired to produce a ?lm with a non
(10%) to ninety per cent (90%) of the'ultimatev
a'dhesive surface. For some kinds of starch or
weightv of the ?lm. When the protein products,
water-soluble carbohydrates, it may be best to such as gelatin, casein, albumen and the like are
cook under alkaline conditions to produce an
introduced into the starch hydrate ?lm, the
amount should not exceed approximately about
make it non-adhesive. Any prior sort of art ‘fifteen per cent (15%) based on the dry weight
material which will effect this operation'can be of the starch, since around this percentage the
used.‘ For example, the surface may be treated transparency of the resulting ?lm is substan
with anhydrous methanol or saturated solution of , tially reduced, and borders on translucency. Any
40 adhesive surface,=and then treat the surface to
the alums or similar saline baths. While many
salts will effect a de-adheslfying action, about 4%
tein adhesive increasing agents may be intro
to 10% of borax, based on the weight of the starch,’
duced into the mass,
produces a very non-adhesive starch '?lm. Bo
rax appears to be most e?ective of all the com
-50 pounds and ‘salts which have been used as de
adhesifying agents.
amount below ?fteen per cent ( 15%) of the pro
It is desired to point out that it is within the
province of the present invention to produce a
non-adhesive water-soluble carbohydrate ?lm, as 50
for example, a water-soluble starch ?lm, and ap
These agents for de-adhesifying the adhesive gply another layer of water soluble carbohydrate
surface inhibit the transparency of the ?lm rela
tively' little, but leave a matt surface.
?lm over the ?rst layer, said second layer, such
If sub- ' as starch, possessing ‘adhesive properties. ' The
stantially complete transparency is not necessary,
‘ most all of the adhesive properties of the ?lm can
outer starch lamination may be prepared from an
alkali treated starch to produce» an inherently
be removed by the addition of the higher alcohol ‘ adhesive material, while the initial base ?lm of
sodium sulphate soaps‘, which may be added to starch material may be made by a neutral cook.
the starch cook. v_ These soaps, as well as fats,
60 oils and waxes may be added to the starch plastic
before the ?lm-forming; operation.< The last
mentioned groups, however, reduce the transpar
It is desired to further point out that a non
adhesive water soluble carbohydrate ?lm may be
prepared by utilizing a neutral‘co'ok, as for ex
ample, treating starch under the conditions herein
ency of the ?lm to apoint almost approaching _ set forth, the starch being non-adhesive, casting
turbidity. The following is an illustrative ex - the water-soluble carbohydrate into a ?lm, coat
ample of a composition of- a starch hydrate ing one} side thereof with a waterproo?ng medium" 65
medicinal dressing ?lm which is non-adhesive;
_. Percent
Gum arabic_v.~___~_________________________ __ 15
Cassava starch;
teriai which will convert the uncoated surface
3- ' from a non-adhesiveto an adhesive condition.
Sodium palmityl sulphate ________ _~___'_'__.‘...
and then treating the uncoated side-with a ma- '
__ '70
Many methods of carrying ‘out the above will sug
gest themselves to those skilled in the art. How 70
'- ever, the result desired may be obtained by direct
ing a steam. jet carrying. a few percent of am-:
The starch is‘, cooked to bursting of the granules,
and the temperature is maintained until the plas
' which will render- thesurface\of the ?lm tackyi
tic starch clari?es as herein described. There
‘and. adhesive. ‘Any of the composite ?lms re-‘75
monia, the latter functioning as the volatile alkah
ferred to in the present speci?cation which do
not have an adhesive surface or which were pre
pared initially with one or both sides non~ad~
ment effected to bring the insoluble compound
into the soluble form. Further, the insoluble
compounds may be introduced in the vform of an
heslve, may be converted into self sustaining ?lms ' emulsion. Additional examples of the preserva-v
having an adhesive face by the procedure above tives are the water soluble inorganic salts of such
set forth.
To the plastic solution either with or without
the adhesive-increasing agent, there is added a
suitable plasticizing agent in amounts equivalent
10 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 ex
ample, ethylene glycol, propylene glycol, di
ethylene glycol and similar polyhydrlc alcohols,
15 as well as the various sugars including the mono—,
di- and tri-sacchroses, the pentoses and pentosan
gums. It is desired to state‘ that glycerol is
especially valuable as a plasticizing agent in the
production of transparent self-sustaining water
soluble carbohydrate ?lms, as for example, starch
?lms, because glycerol of all the plasticizers, re
duces the transparency of the ultimate ?im the
Practically all of the water soluble carbo
hydrates have a de?nite plasticizing value for the
starch ?lm.' If the carbohydrate is substantially
hygroscopic, its- effectiveness as a plasticizing
agent is‘correspondingly greater than those carbo
hydrates which are less hygroscopic.
As illustrative of the mono-sacchroses, refer
erence is made to glucose and fructose.
As representative of the di-sacchroses, refer
ence is made to sucrose and maltose.
As representatives of the tri-sacchroses, ref
35 erence is made to mellitose and raf?nose.
Zylose and arabinose are representatives of the
pentoses, and mannan and. araban are repre
sentative of the pentosan gums.
In addition, various natural gums above re
40 ferred to, and which contain substantial amounts
of the pentosan gums are very well suited for this
work. These natural gums are gum tragacahth;
arabic, karaya, and the like,
In the preferred form of the invention, it is
45 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,
-50 sodium benzoate, sodium salicylate, sodium ortho
phenylphenate, beta-naphthol and the like.
These compounds are set forth by way of exam
ple, and not limitation. The amount of preserva
tive added will depend on a number of factors
55 including the character of the starch and the
kind of preservative agent used. However, when
using borax an amount equal to four per cent
(4%) of the weight of the dry starch gives sat
islfactory results.
When using sodium-ortho
60 ‘henylphenate, it is desirable to add one-third
(1/3) of one per cent (1%) based on the weight of
the dry starch.
Any preservative which will inhibit the decay
of organic matter, retard the growth of mold,
65 fungi, bacteria and protozoa-will maintain the
utility and value of the starch ?lm. Most all
of the inorganic salts possess varying degrees
of effectiveness in this role, and most of the
aromatic organic compounds may be introduced
metals as copper, arsenic, mercury, thallium.
antimony, and the like. Other effective organic
agents inhibiting decay are substantially all of
the aromatic alcohols and all of the turpene alco
hols, of which cresol, resorcinol, thymol, are rep
resentative, and are mentioned merely as repre
sentative of the aromatic alcohols; and pineol
and borneol, which are representative of. the
terpene alcohols and are mentioned merely as
representative of the terpene alcohols.
In general, it may be stated that the amount
vof preservative agent will vary in accordance with
the toxicity of the preservative agent, and some
what in accordance with the character of the ma
terial treated, that
whether the basic material
is starch, a starch nitrate, a starch acetate or
some other water soluble carbohydrate. In the
case of highly toxic materials, amounts varying
from about one-thirtieth (1A0) to one-?fth (1/5)
of one per cent (1%) based on the weight of the
dry ?lm, will inhibit decay, while for the less
active agents, such as borax, more will be neces
sary, and as much as up to four per cent (4%)
may be desirable to inhibit decay in~a warm
humid atmosphere.
The starch plastic, including
agent and a preservative, is spread
This may be done by providing a
surface of metal, such as nickel,
aluminum and the like or nonmetallic surfaces,’
such as polished Bakelite, glass, rubber, and
equivalent surfaces.
Any smooth polished surfaces of the character
above set forth may be coated with a thin ?lm
of wax; such as carnauba wax, candelilla, paraf 40
fin, and the like, or instead of using wax, oils may
be used, such as cotton seed oil, corn oil, oleo
stearine, etc. The starch plastic is extruded or
poured on this surface and gauged down to the
desired thickness by a doctor blade or scraper
which moves over strips of such thickness as
will produce an ultimately dried- ?lm of the
desired'dimenaions. The dried ?lm may vary
in thickness, depending upon its speci?c use.
When the material is used as- a medicinal dress
ing ?lm its thickness should vary between 0.001"
and 0.003”, which is also the preferred thick
ness when the material is used for mending pur
poses. Under some circumstances the ?lm may
be even thinner, and of the order of 0.0001 of
an inch.
The carrier surface and the thin ?lm starch is
dried in an oven at about 160° to 185° F. for about
ten (10) minutes or more. ,If lower temperatures
are used for drying, the drying period is corre
spondingly longer. The temperature of drying
may vary greatly, so long as the temperature is
not sufficient to burn or damage the ?lm.
It may be stated that the time of drying varies
with the thickness of the ?lm, the temperature
and the relative humidity of the drying air, the
velocity with which the air passes over the drying
sheet, the amount of water evaporated from the
sheet, and the tendency of the starch hydrate
?lm to oxidize or “skin over’i, The time of dry
70 into the starch hydrate mass as a water solution, . ing may vary from two and three-fourths (2%)
or if these or any other compounds are not solu
ble in water, soluble derivatives may be formed
and these introduced into the mass.
For exam
ple, the aromatic hydrocarbonsv and their deriva
75 tives may be sulphonated, or some other treat
a plasticizing
into ?lm form.
clean polished
stainless steel,
The optimum
conditions for a ?lm of one-thousandth (%o0) of
minutes to more than an hour.
an inch thick are a moisture content of eighty
per cent (80%), a temperature of about 185° F.
lulose esters, of which the cellulose acetates, the
dry bulb, and 135° wet bulb, and an air velocity
of about 200 linear feet per minute. These conditions will prevent “skinning over” of a normal
starch cook.
The ?lm, after drying, is stripped from the
spreading surface when the moisture conterit has
been reduced su?iciently to produce a fairly dry
?lm. As an'example, it has been found that the
?lm is satisfactorily dried when it has had its
10 moisture content reduced so that the moisture
content varies from twelve (12) to twenty (20)
nitrates and benzoates are typical examples; cel- '
lulose ethers in general, of which cellulose methyl
ethyl, and benzyl ethers are examples; solutions
of natural resins such as dammars, kaurls, copals
and the like; synthetic resins in generalof which
the phenol aldehydes, the glyceryl phthalates, the
cumars, formaldehyde-ureas, the vinyl esters and
the like are examples. The waterproo?ng coat
ing may be derived from rubber solutions made 10
from chlorinated rubbers, rubber hydrochloride,
per cent of the weight of the dried starch com
synthetic rubber solutions, such as “Thiokol.”
position ?lm.
“Thiokol” is prepared by the polymerization
of chlorinated ole?ns with polysul?des. In the
preferred form ‘ethylene di-chloride is heated at 15
The removal of the ?lm from the carrier sur
15 face is effected by picking the ?lm from the
spreading carrier surface, and then winding the
?lm upon a roll of from about one-quarter ($41)
of an inch to several inches in diameter, depend
ing upon the type of device used and the rate
(NazSr) , in which it is used in the proportion of
about two and one-half (21/1)v times the amount
of ethylene di-chloride. The reaction is com
pleted in about six (6) hours.
20 of removal.
The ?lm should be promptly unwound where
short spreading‘ is made, and if the operation is
continuous,_ the ?lm should pass only partly
around the roll onto the other equipment for the
around its boiling point with sodium polysul?de
Carbon _
__ 15
I Hydrogen
subsequent operations.
The combustion analysis of thiokol is:
The ?lm produced as above set forth may have
one of its surfaces coated to render the same
Sulphur ____
____ ..
One surface of the starch ?lm may be rendered
waterproof, leaving the other surface uncoated
waterproof and non-adhesive by coating the
so as to take advantage of the adhesive char
same with a thin ?lm derived from natural and
hesivetape. It is within the province of this
invention to omit the waterproof ?lm and pro
synthetic waxes which may be applied from 30
either a solution of the same, or by application
.in the molten state of the wax. These coating
vide an adhesive tape which has an adhesive
surface, said surface bonding itself to the skin
compositions are plasticized with ‘suitable soften
ing agents to make the resulting waterproo?ng
30 acter of the surface and’ thereby provide an ad- .
?lm on the starch sui?ciently ?exible and plastic 35
When coating one face or surface of the ?lm, - so that the ?nal starch ?lm carrying the water
35 surface to which it is applied.
the coating composition may be applied prior
to the removal of the starch ?lm from its car
rier surface, and the application may be by means
40 of a spray gun, by a brush, or the composition
may be ?owed on or printed on the surface by
means of a suitable printing roll.
The waterproofed coating composition may be
applied to the carrier surface and the composition
.45 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 waterproo?ng coat
proo?ng composition may be used for any of the
herein described purposes.
_ An adhesive tape produced as herein disclosed
may be used for various purposes including band
age closures and wound coverings. The self-sus
taining starch ?lm'may have applied to the 'ad
hesive side of the material any of the usual vsur
gical dressing tissues to form a composite dress
ing tissue having a self-sustaining starch ?lm 45
backing. The dressing tissue need not be ap
plied to the entire adhesive surface of the starch
?lm, but certain portions, and preferably the end
ing which is in effect a laminated sheet com- ‘ portions of the surface ?lm, may be free and ex-_
50 prising the starch ?lm and the waterproo?ng posed so as to adapt the composite dressing ma 50
?lm thereon may be lifted from the carrier sur
terial to easily bond itself. to the skin surface
face. The material may then be wound upon
rolls, which are trimmed to the desired width by
means of suitable cutting knives already in use
55 for this general type of production.
These rolls
to which it is applied.
The starch ?lm produced in accordance with
the herein set forth method may have incorpo
rated therein any solid or liquid material which 55
may then be cut into- smaller widths while coiled ' is suited to act on the skin or through the skin
or the rolls may be unwound and passed between to effect upon‘ a predetermined area of the body
slitting wheels or slitting knives and subsequent
a desired physiological or pharmacological \re
ly wound in coils to provide an adhesive tape of _~ action. Various pharmaceutical products, medi
60 the desired width and diameter. The ?lm mayv cinals and antiseptics may be incorporated in so.
be supplied in large stock size sheets of standard the starch plastic prior to ?lm formation. {in
dimensions, or in suitable smaller cut-to-size di
general, vany of the liquid or solid products tabu
mensions. In stacking these sheets, which have lated in the United States Pharmacopoeia and
only one side coated or waterproofed and the National Dispensatory, may be incorporated in
the starch ?lm. One of the particular class of 65
65 other side of-an adhesive character, itis ob
viously necessary to avoid two starch surfaces medicinals which may be incorporated in the
coming in contact with each‘ other, as the ad
starch vplastic are antiseptics such as phenol,
hesive nature of this material will prevent sub
thymol, menthol, the’ benzoates, salicylates, re
sequent separation without destruction of the sorcinol, ichthyol, cresol and the like. Exam
ples‘ of inorganic antiseptics are borax, boric 70
70 composite ?lm.
' The waterproo?ng composition may be formed acid and bichloride of mercury. Some of these
from any suitable known waterproo?ng medium. products which are compatible with the'starch"
‘However, in general the waterproo?ng lamina- ' plastic will result in retaining the transparency
tion may consist of a coating resulting from
applying to the starch ?lm, solutions of the cel
of the starch ?lm, while those which are incom
patible will result in a translucent or turbid starch 75
lamination. The inorganic medicinal compounds
waterproo?ng coating the following composition
may be added to the starch plastic in amounts ‘
is prepared: a
varying from 1/100 of 1% up vto 15%. For ex
ample, using bichloride of mercury, about 1/100
of 1% will be added to the starch plastic, based
on the weight of the dry starch.
For boric acid, it is advisable to add to the
starch plastic up to 5% based on the weight of
the dry starch.
For the organic antiseptics and related com
pounds, the preferred range of percentages are
from 0.5 to_4% based on the. weight of the dry
starch. However, the above examples are merely
illustrative and are not'to be taken as a limita
15 tion upon the amount of medicinal material
which may be added to the starch plastic. It is
obvious that the amount of medicinal which is
added will vary with the character of the medici
nal used, the type of skin to which the medi
Table II
Cellulose nitrate (10 sec. viscosity) ________ __ '75
Dibutyl phthalate _______________________ __ 25
solids ___________________________ __ 100
The mixture set forth in Table II are dissolved 10
in ?ve unit Weights in a solvent mixture of the
following composition:
Table III
acetate ___________________________ __
Benzol __________________________________ __
Methanol _______________________________ __
Butyl acetate __________________ __ ________ __
20 cated ?lm is applied, and the particular purpose
for which the medicated ?lm is applied.
In general, it may be stated that the medici
nals are incorporated in the starch plastic after
the plasticizing agent and preservative agents
25 have been added to the starch, and prior to the
extrusion of the starch in ?lm form. The me
dicinals may be incorporated in the starch by
mascerating or triturating the solid forms in
either water or glycerol to form a paste and
then mixing this paste with the starch plastic.
As stated, various plasticizers or softening agents
may be used including glycerol, di-ethylene gly-_
col, ethylene glycol-mono-methyl ether.
centrated sucrose solution may also be used as
35 a plasticizer for the starch plastic.
It is preferred when liquid medicinals including
pharmaceuticals are used, that the same be in
troduced by dispersion in the starch plastic.
This may be readily accomplished by agitating
40 the starch plastic with any mechanical device
which will result in the complete and uniform
dispersion of the liquid or oily type of medici
na-ls through the starch plastics. Any mechani
cal device of the egg beater type functions well
45 to accomplish the dispersion.
Total ________________________________ __ 100
The dried ?lm is coated on one surface with
the cellulose nitrate coating which carries aplas
ticizer such as di-butyl phthalate.
The following table sets forth an additional
example of the preparation of a medicated starch
Table IV
Starch _______________________________ __
Glucose ________________________________ __
soda _____ __-___________________ __
Phosphoric acid ____________ _T____ To neutralize
Zinc oxide ____________________________ __
Borax __________________________________ __
In preparing the above ?lm, the caustic soda
is dissolved in water and the starch is added. The
mix is then heated to the bursting point of the
starch granules, cooked to clarity and maintained
at the temperature which is adapted to burst the
granules for twenty (20) to thirty (30) minutes.
Thereafter, the cook is neutralized with phos
phoric acid until the alkalinity is brought to a
pH of approximately 10. Borax is dissolved in
water and added to the plastic, the zinc oxide
isthoroughly wetted with water and added to
The following is a speci?c example of the prep
aration of a medicated starch ?lm. The mate
rials entering into the starch films and the the plastic. The total water content approxi
amount of each material is set forth in the fol- ‘ mates twelve (12) times the weight of the dry
50 lowing table:
Table I
Starch ________________________________ __
Di-ethylene glycol ______________________ __ 25
Caustic soda ___________________________ __
salicylate _____ __‘ ______________ __
Thymol ____________________ __' ____ __'_____
The above mixture is mixed with 600% of wa
starch. Due to the high opacity of the zinc 50
oxide pigment, this ?lm is not transparent. It
is to be noted that the transparency is prevented
not by the ?lm itself, but by an added ingredi
ent, If the amount of zinc oxide is reduced, a
translucent ?lm can be produced.
The plastic produced from the above mass is
dried and formed into a ?lm, all as heretofore de
scribed, and then provided on one side with a
waterproo?ng coating. In order to produce the
60 ter, and the mixture neutralized with phosphoric . waterproo?ng material, the following composi
acid until the alkalinity is brought to pH 1°. The
speci?c steps of producing the plastic starch
tion is utilized:
mass has previously been set forth. It is noted
in the above that the plasticlzer is di-ethylene
Cellulose acetate (5 sec. viscosity) _____ __'___
Ethyl-para-toluene-sulfonamide ____-_ ____ __
65 glycol.‘ The medicinal or pharmaceutical is thy
In this particular case, the thymol also
acts as a preservative. A film produced from
such a mixture is inherently adhesive. This
mixture may have its adhesive properties in
70 tensi?ed by mixing the samewith an adhesive
increasing agent, all as previously speci?ed.
The plastic starch produced from the above
solution is dried and formed into a ?lm, all as
described, and then provided on one side with a
75 waterproo?ng coating. In order to produce the
Table V‘
Per cent
The mixture set forth in Table V is dissolved in
(5) unit weights of the following solvent mixture
to produce the ?nal waterproo?ng coating mate
Acetone ________________________________ __
Diac'etone alcohol _______________________ __
Instead of using a cellulose ester lacquer, the fol- 75
lowing waterproo?ng coatings may be prepared
On the other hand, ii.’ the above substances or
their substantial equivalents are to be‘ used in v
Per cent the starch- film as a plasticizer and a bonding
1‘. Cellulose nitrate ______________________ __ 15 > agent, then it is preferred to have present in the
and used.
Ethyl acetate ________________________ .._
Di~butyl phthalate____________ __'_____'__
Butyl acetate ________________________ __
Methanol __________________ __-____"______
starch film an amount equal to about 30% of the
weight of the starch.
Corn removers, mustard plasters and the like
may be made by incorporating lnthe starch plas
2. In the above composition, the cellulose nitrate
may be substituted by a ‘cellulose ether, in
cluding those speci?cally hereinbefore men
' Per cent
3. Natural resins ____________ _; __________ .._'
Butyl acetate ____________________ _-_____'_
Acetone _______ _l_-______-_ _____________ __
with a corn removing compound such as salicylic
Benzol ____ __‘ _________________________ __
acid. The latter should be present, preferably in
an amount equal to about 5% based on the weight 20
of the dry starch. This material is made in the
form of a ?lm, as hereinbefore described, and
waterproofed with any of the waterproo?ng solu
_ Methanol ____________________________ __'
The solvent mixture of the above set forth com
position may be modi?edv to meet the require
ments of the various’ types of natural resins in
order to produce a clear transparent ?lm. It‘
~25 will also serve for most of the synthetic resins.
Other solvents such as carbon bi-sulphide, ace
tone, solvent naphtha, etc. may be used in place
of the above depending upon the particular form
of rubber used in formulating the coating com
Per cent
5. Waxes _________________________ __‘.____
Solvents ~
tions herein described.
Not only may the present ?lm be used as ‘a me
dicinal tape, but it may also be used as an adhe
Per cent
4. Rubber solutions (solids) _________ _'___...__..
Ethylene di-chloride __________________ __
tic, after the cooking operation has been com
pleted, a small percentage of the medicinal which 10
gives the desired result. of course, the free alka
li is neutralized with phosphoric acid or its equiva
lent, prior to the incorporation of the medicinal
compound. A com removing ?lm may be pro
duced by cooking about 67%% of starch with 2%
of caustic soda and incorporating therewith di
ethylene glycol as a softening agent, together
The solvents or solvent mixtures will depend
For para?in, sol
vent naphtha may be used; for halowaxes or chlo
40 upon the particular wax used.
rinated naphthalenes, ethylene dichloride may be
used; for true waxessuch as vspermacetti, car
nauba and the like varying mixtures of acetone,
45 ethyl acetate and the like may be used.
It is desired to point out that in one form of.
the present invention, it is desirable to use the_
same plasticizer for the starch ?lm as is used for
the waterproo?ng composition. For example, di
sive binding material, forexample, as a mend
ing tape, said mending tape being. preferably, pro- »
duced in usual spool form.
Instead of making .the ?lm of ,a carbohydrate 30
material, such as a starch derivative, the ?lm
may be made from a protein material such as
gelatin, casein, albumen and the like, this pro
tein ‘material may be treated in all respects
like the carbohydrate material'and- may have'a
plastici'zer introduced therein, if the same is
necessary. It is also highly desirable to intro
duce intothe protein film‘ a preservative to in
hibit' decay of the ?lm. The protein ?lm may
have introduced into the same an adhesive in
tensifying agent if the protein ?lm lacks this
quality, or is de?cient in this quality. The ?lm
may be waterproofed with any of the prior art
waterproo?ng compositions, but preferably with
a "cellulose compound which is. soluble in’ the ».
. organic compounds of the type herein set forth.
While the procedure herein set forth for the
preparation of the water soluble carbohydrate
?lm, and especially the starch base ?lm, produces
50' ethylene glycol may be used to plasticize the
a substantially transparent ?lm, the transparent
starch ?lm and the nitro-cellulose coating com
position. It may be stated'that when both the
starch ?lm and the coating composition contain
‘the same plasticizing agent, that this plasticiz
55 ing agent which is common to each lamination
of the ?lm tends to improve the bond between the
two dissimilar laminations. Instead of using di
ethylene glycol as a plasticizer for both the starch
qualities of the ?lm may be improved by the
addition of‘ a clarifying agent to the plastic mass.
?lm and the coating composition. ethylene-glycol
60 mono-methyl-ether may be used.
While it has been stated that the common plas
ticizer may be used in a starch ?lm lamination -
and in the waterproo?ng lamination, it is within
the province of the present invention to use dif
65 ferent plasticizers in these two laminations and
use a separate bonding agent between the starch
?lm lamination and the waterproo?ng lamination
and di-ethylene glycol and ethylene-glycol-monm‘
methyl-ether may be used as bonding agents.
If plasticizers are already present in the starch
?lm composition and in the waterproo?ng com-‘
position, then about 10% of the above compounds,
based on the weight of, the‘ starch ?lm, may be
'used to improve the vbonding of the two lamina
75 tions.
Where the adhesive ?lm does not carry any me
dicinal agent, or its equivalent, it is usually de
sirable to add to the plastic mass a clarifying 65
agent.‘ If the ?lm does carry a medicinal agent
or any addition agent which will react with the
clarifying agent,‘ then the latter should, of course.
be removed. Suitable clarifying agentsare the
amino compounds. I Most amines react with
acetic pharmaceuticals adapted to be used in one
form of the present invention. For example, in
the corn remover ?lm herein set forth, the sail
cylic acid would react with the amines, and,
therefore, the amino clarifying agent should not
vbe used. In general, it may be stated that the sub
stituted ammonias, and their addition‘ products,
are ‘suitable as clarifying. agents.
Included in
this generic term are the amines, amides, imides,
anilines, anilides, the cyclic nitrogen compounds,
such as pyridine, quiniline, acridine and the like,
as well as the hydrazines, hydroxyl amines and
the oximes.
It may be stated that the more alkaline the
amine, the less the amount required. However,
there appears to be other aspects to the clarify
ing of the plastic than the alkalinity alone. Ex
periments indicate that the amines have the
capacity of digesting and dispersing the shells
of the starch granules which appear to be a form
of hemi-cellulose, and thereby eliminate the
slight cloudiness which results from their pres
ence. Alkalinity alone does not produce this
The amount of clarifying agent added depends
on the character of the starch and the particular
amino compound used. Using the amines, satis
factory results are obtained by adding from one
per cent (1%) to ten per cent (10%) of the weight
15 of the dry starch. ‘When using tetra substituted
amines (such as tetrone B) and treating cassava
of application, and the elimination of the dim
culties which arise from the application of the
lacquer to the book cover itself, that is, the run
ning of the ink in the printing, due to the solvent
action of the nitrocellulose solvents, and the
warping effect of'the book cover resulting from
the shrinkage of the nitrocellulose lacquer in the
drying operation.
The present invention provides a ?lm made
from a water-soluble carbohydrate material which 10
is initially and inherently adhesive and so the
?lm itself is adhesive. One face of this ?lm is
made non-adhesive, as by providing it with a
waterproofed protective transparent coating com
The medicated tape herein disclosed may be
starch, one per cent (1%) of this quaternary ' used for most of the forms of local skin treat
substituted amine, based on the weight of the ment. This includes-the various skin disorders,
except those which are systemic. In addition, the
dry starch, is used.
When using tri-ethanol amine and treating water soluble carbohydrate ?lm may have incor 20
cassava starch, ten per cent (10%) of this amine, porated therein a reactive agent or agents func
tioning to remove hair. These depilatory com
_ based on the weight of the starch is ‘used.
Amino derivatives, such as the acet-amines, as positions are well known in the art. The inven
for example, acct-amide, acet-‘anilide, and the
like, as well as the alcohol amines, such as mono-,v
tion does not reside in the particular depilatory
compositions which are used.
The ?lm of 'the 25
present invention may also have incorporated
therein the acceptedv pharmaceuticals for 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 > stimulation of hair growth. When oils or other
of the‘ glycerol above referred to as a suitable incompatible agents are mixed into the starch 30
. ~plastic, a translucent to opalescent ultimate ?lm
30 plasticizer for the starch ?lm.
“Tetrone B” marketed by Rohm and Haas of results. As herein pointed out, the adhesive sur
Philadelphia is a quaternary or tetra substituted face of the starch ?lm may be treated with a
material having a solvent action upon said sur
ammonium with alkyl groups and with a molecu
lar weight of approximately 170. This product face to render the same non-adhesive. In cer
35 is so active in its solvent power that it dissolves tain of the claims, this expression or equivalent
cellulose present in the starch, and as ‘a result expressions have been used, and it is to be inter
it is only necessary to add about one per cent ' preted as covering the herein disclosed organic
(1%) to obtain the desired result. On the other and inorganic compounds such as methanol and
hand, less active amino compounds must be vthe higher alcohol sodium sulphate soaps and
alums and borax, or their equivalents.
40 added in greater quantities, for example, if suc
What is claimed is:—
cinamide is used, it should be added in an amount
-l. A composite medicinal bandage comprising
equal to about ten per cent (10%) based on the
weight of the dry starch.
It is desired to state that the adhesive mate
rial which may take the form of an adhesive
binding substance or an adhesive tape which is
coated on one side with a suitable transparent
waterproo?ng solution, as for example, cellulose
nitrate lacquer, provides a ?lm, the transparency‘
50' of which is so nearly complete that the carbohy
drate ?lm, and more particularly the starch base
?lm itself, is almost invisible. Usually, all that
can be seen is the surface sheen of the lacquer
employed, as for example, cellulose nitrate. Such
55 adhesive tape is adapted for a variety of uses and
particularly for the mending of printed matter in
general, including sheets of music.
Another use for which the adhesive material of
the present invention is adapted, is for the cov
80 ering of books. The water soluble carbohydrate
?lm having one face which has adhesive prop
_ erties in view of the inherent adhesive properties
of the material, and another face which has been
made non-adhesive, either by treatment with a
65 material which de-adhesi?es or which provides
a thin ?exible starch ?lm, one face of which
carries a waterproo?ng coating, and the other face
has a?ixed thereto a ?exible adhesive alkali»
cooked starch ?lm carrying a medicinal agent
adapted to act upon a predetermined area of the
body to effect the desired physiological action.
2. A composite medicinal bandage comprising
a thin ?exible ?lm composed predominantly of
chemically neutral and non-adhesive starch, one
face of said neutral starch ?lm carrying a water
proo?ng coating, and the other face having af
?xed thereto a ?exible adhesive alkali cooked
starch ?lm carrying a medicinal agent adapted 55
to act upon a predetermined area of the body to
effect the desired physiological action.
3. A composite transparent adhesive binding
material comprising a ?exible self-sustaining ?lm
consisting of a mixture of a water soluble carbo 60
hydrate provided with ?lm-forming properties
and a protein compound adapted to mix with said
carbohydrate and become an integral soluble part
a non-adhesive coating overthe adhesive face,
thereof and impart adhesive properties thereto,
the water-soluble carbohydrate being present 65
in a predominating proportion and the protein
serves admirably as a wrapping material, and
particularly for books. ' In using the material,
the uncoated side of the composite starch sheet
is moistened with a damp rag and the ,so-mois
stantial reduction in the transparency of the
?lm, one face of said ?lm carrying a non-adhesive
waterproo?ng coating, and the other face of the 70
tened adhesive sheet- is then applied with the
adhesive face directly next to the covers of the
book. When dry, the covers of the book have an
- appearance equivalent to a duco or nitrocellulose "
75 lacquer job, with the advantage of low cost, ease
being present in an amount inhibiting any sub- .
?lm having adhesive properties.
4'. A thin ?lm-like medicinal bandage su?i
ciently ?exible and self-sustaining to be applied
directly to the skin, said bandage comprising pre
dominately a water soluble alkali cooked carbo 75
comprising a mixture of a water-soluble carbo
hydrate material having self-sustaining. ?lm
i’orming properties, one face of said bandage, hydrate provided with film-forming properties,
having adhesive properties and the other face and a protein capable of imparting an adhesive
thereof being non-adhesive, said bandage having characteristic to the ?lm, the protein constituent
incorporated therein a medicinal agent adapted being present in an amount not exceeding 15%,
to act upon a predetermined area of the body one face of said ?lm carrying a non-adhesive
waterproof coating, and the other face of the ?lm
to e?ect the desired physiological reaction.
having adhesive propertiesr
5. A thin ?lm-like medicinal bandage suffi
9. A composite,‘ transparent adhesive binding
ciently ?exible and self-sustaining to be applied
directly to the skin,- said bandage comprising material comprising a ?exible self-sustaining ?lm 10'
predominately a water soluble alkali cooked comprising a mixture of starch and a protein ca
carbohydrate material having self-sustaining pable of imparting an adhesive ‘characteristic to
film-forming properties, one face of said bandage the ?lm, the protein constituent being present in
being adhesive in character and the other face an amount not exceeding 15%, one face‘of said
“ carrying a protective transparent waterproof ?lm carrying anon-adhesive waterproof coating, 15
coating, said bandage having incorporated therein and the other face of the ?lm having adhesive
a medicinal agent adapted to act upon a pre
determined area of the bodyto effect the desired
10. A thin ?lm-like medicinal bandage suffi
ciently ?exible and self-sustaining to be applied
directly to the skin, said bandage consisting pre 20
physiological 'reaction.
6. A thin ?lm-like medicinal bandage suffi
ciently ?exible and self-sustaining to be applied dominately of a water-soluble alkali treated car
directly to the skin, said bandage comprising. bohydrate selected from the group consisting of
predominately an alkali cooked starch base hav
ing self-sustaining ?lm-forming properties,‘ one
face of said bandage having adhesive properties,
and the other face thereof being non-adhesive,
said bandage having incorporated therein a me
dicinal agent adapted to act upon a predeter
mined area of the body to effect the desired
reaction. ,
7. A thin ?lm-like medicinal bandage suffi
ciently ?exible and self-sustaining to be applied
directly to the skin, said bandage comprising pre
dominately an alkali cooked starch base having
self-sustaining film-forming properties, one face
of said bandage being adhesive in character, and
starch derivatives, saccharides, starch gums, car
bohydrate gums, pentoses, ethers and esters
thereof, one face of said bandage being adhesive 25
in character and the other face carrying a trans
parent waterproof coating, said bandage having
been incorporated therein up to 15% of a medici
nal agent adapted to‘act upon apredetermined
area of the body to effect the desired physiological 30
11. A thin ?lm-like adhesive surgical tape su?i
ciently ?exible and self-sustaining to be applied
directly to the skin, said tape comprising pre
dominantly a water-soluble alkali treated carbo
the other face carrying a protective transparent
hydrate material having self-sustaining ?lm
forming properties and characterized by the prop
waterproof coating, said bandage having incor
erty of inherent adhesiveness, one face of said
porated therein a medicinal agent adapted to act
40 upon a predetermined area of the body to effect‘
the desired physiological reaction.
surgical tape being adhesive in character adapted
to bond itself to the skin, and the other face car
rying. a protective transparent water-proof coat
8. A composite transparent adhesive binding - 1118
material comprising a ?exible self-sustaining film _
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