U.S. patent number 3,801,011 [Application Number 05/289,786] was granted by the patent office on 1974-04-02 for humidity control means and packages containing the same.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to Paul F. Guehler, David A. Hofacker.
United States Patent |
3,801,011 |
Guehler , et al. |
April 2, 1974 |
HUMIDITY CONTROL MEANS AND PACKAGES CONTAINING THE SAME
Abstract
The disclosed humidistasis (i.e., humidity control) means
comprises a sheet-like carrier with a partially exposed layer of
water-containing capsules adhered thereto. The water-containing
capsules are preferably spheroids less than about 3,000 microns in
diameter and have vapor-transmissive walls. Prior to use, the
humidistasis means can be stored in a moisture-tight bag. In use,
the humidistasis means is preferably adhered to an inside surface
of a container, thereby providing a humidistatic environment for
dehydration-sensitive materials.
Inventors: |
Guehler; Paul F. (St. Paul,
MN), Hofacker; David A. (St. Paul, MN) |
Assignee: |
Minnesota Mining and Manufacturing
Company (St. Paul, MN)
|
Family
ID: |
23113089 |
Appl.
No.: |
05/289,786 |
Filed: |
September 18, 1972 |
Current U.S.
Class: |
239/34; 239/36;
239/53; 261/104; 206/205; 312/31.1 |
Current CPC
Class: |
A24F
25/02 (20130101) |
Current International
Class: |
A24F
25/00 (20060101); A24F 25/02 (20060101); A24f
025/00 (); A61l 009/04 () |
Field of
Search: |
;239/53X,55,54,36X,34
;206/.5 ;312/31.01,31.02,31.03,31.04,31.05,31.06,31.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: King; Lloyd L.
Attorney, Agent or Firm: Alexander, Sell, Steldt &
Delahunt
Claims
What is claimed is:
1. Humidity control means comprising:
a sheet-like carrier means on one major surface of which is
disposed a plurality of capsules 10 - 4,000 microns in diameter,
said capsules comprising a shell wall fully surrounding and
enclosing an aqueous fill liquid, said capsules being free of flaws
or pores, in said shell wall, visible to the naked eye, said
capsules being capable of releasing water vapor without rupture of
said shell wall.
2. Humidity control means according to claim 1 wherein said
capsules are less than about 3,000 microns in diameter and wherein
said shell wall comprises at least a first solid phase comprising a
first material and a second solid phase comprising a second
material, said first and second materials being miscible and
capable of forming a single phase when both materials are in a
liquid state, but capable of forming separate phases upon being
cooled to a solid state, the percent of contraction in volume upon
being cooled greater for the first material as compared to the
second material, the first material being present in a quantity
sufficient to provide micropores which extend completely through
said capsule wall.
3. Humidity control means comprising:
a sheet-like carrier means and a plurality of substantially
spherical capsules 10 - 4,000 microns in diameter, said capsules
being adhered to a major surface of said carrier means at least at
their points of tangency upon said major surface, each of said
capsules containing about 5 .times. 10.sup.-.sup.7 to about 5
.times. 10.sup.-.sup.2 cubic centimeters of aqueous fill liquid
fully surrounded and enclosed by a vapor-transmissive shell wall,
at least 30 percent of the area of said vapor-transmissive shell
wall being exposed to the ambient atmosphere to be controlled by
said humidity control means, said capsules having the following
water vapor release characteristics, determined under constant
ambient relative humidity conditions:
an encapsulated water half life of at least three days at 5.5
percent ambient relative humidity and a substantially constant net
release rate of less than about 2.5 percent by weight of the total
amount of encapsulated water per day at 97 percent ambient relative
humidity, said substantially constant net release rate being
measured after the fifth day of 97 percent ambient relative
humidity.
4. Humidity control means according to claim 3 comprising a
monolayer of said capsules, said carrier means being a solid
polymeric film vacuum formed upon one major surface of said
monolayer of capsules.
5. Humidity control means according to claim 3 wherein said carrier
means comprises a pressure-sensitive adhesive layer.
6. Humidity control means according to claim 5 wherein said carrier
further comprises a cloth layer adhesively bonded to the same major
surface to which said capsules are adhesively bonded, said capsules
being positioned within the openings between fibers of said cloth
layer.
7. Humidity control means according to claim 3 wherein said
humidity control means is enclosed within a container further
containing dehydration-sensitive material.
8. Humidity control means according to claim 3 wherein said
humidity control means is enclosed within a moisture-tight
container.
9. Humidity control means according to claim 3 wherein said aqueous
fill liquid is substantially entirely water.
10. Humidity control means according to claim 3 wherein said
aqueous fill liquid comprises a saturated aqueous solution of a
water soluble metal or ammonium salt.
11. A package containing a tobacco product and a humidistasis
means, said humidistasis means comprising
a sheet-like carrier means adhesively bonded on one major surface
to an inside surface of said package;
a plurality of capsules at least substantially hemispherically
exposed to the inside of said container and adhesively bonded, at
least at their points of tangency, to the exposed surface of said
sheet-like carrier means, said capsules being less than about 3,000
microns in diameter and comprising a substantially spherical
vapor-transmissive shell completely surrounding and enclosing an
aqueous liquid, said capsules having the following water vapor
release characteristics, determined under constant ambient humidity
conditions;
an encapsulated water half life of at least three days at 5.5
percent ambient relative humidity and a substantially constant net
release rate of less than about 2.5 percent by weight of the total
amount of encapsulated water per day at 97 percent ambient relative
humidity, said substantially constant net release rate being
measured after the fifth day of 97 percent ambient relative
humidity.
Description
FIELD OF THE INVENTION
This invention relates to humidistatic or hygrostatic means which
remove or emit water in order to control or maintain a humidity
level in an environmemt which can contain perishable or
dehydration-sensitive material. An aspect of this invention relates
to a package containing a humidistatic means, wherein the
humidistatic means can be stored for long periods of time prior to
use. A further aspect of this invention relates to the use of the
humidistatic means in a package containing dehydration-sensitive
material requiring some degree of humidity control, e.g.,
perishable goods or articles containing material sensitive to
excessively low or excessively high humidity conditions.
DESCRIPTION OF THE PRIOR ART
It has long been recognized that certain materials, e.g., foods
(including confections and produce), tobacco products, cut flowers
and other plant life, articles such as photographic film, and other
goods which are perishable or sensitive to excessively dry
conditions should be stored within a humidistatic environment.
Thus, humidity control or humidistasis is an important field unto
itself, particularly as it relates to packaging.
One very common problem in the art of humidistasis (i.e., keeping
humidity within prescribed bounds) is encountered when one attempts
to provide conveniently packaged perishable or
dehydration-sensitive goods with an adequate shelf life through the
use of a means for replacement of moisture losses. Typically, it is
inconvenient or undesirable to provide a package of tobacco
products, fruits, vegetables, confections, films, etc., with an
effective hermetic or moisture-tight seal. Typically, the contents
of the package are, in effect, exposed to ambient relative humidity
(R.H.) conditions potentially varying from a few percent R.H.
(e.g., in heated warehouses during the winter) to over 90 percent
R.H. Either extreme can be damaging to tobacco products,
confections, and other goods which are at optimum quality only
under very narrowly circumscribed R.H. conditions. For example,
cigars are economically and efficiently packaged in small cardboard
boxes encased or wrapped in cellulosic film, but the cellulosic
wrapping is water vapor transmissive, thus permitting the water
vapor to pass quite freely from the inside of the box to the
ambient atmosphere or vice versa.
A second, somewhat related problem is encountered when goods are
stored under purely temporary moisture-tight conditions. For
example, pipe tobacco containers are subject to frequent opening
and closing. Even if the container is well sealed while closed, the
humidistasis is disturbed with each opening and must be
re-established by some means; see, for example, U.S. Pat. No.
1,552,877 (Phillipps et al.) issued Sept., 1925, and U.S. Pat. No.
2,262,327 (McKinnon) issued Nov. 11, 1941.
A third problem is encountered even when the goods are kept under a
substantially permanent moisture-tight seal. If the goods are to be
kept at a preselected R.H. level, it is generally not practical to
first introduce an atmosphere of controlled moisture content into
the package prior to sealing and then maintain the sealed package
at a constant temperature. The usual prior art approach involves
introducing a mechanical or chemical means within the package which
can serve as a source and/or a sink for humidity, as the internal
conditions (e.g., temperature) dictate. It has been suggested, for
example, that an invert sugar solution, a Glauber's salt solution,
a semipermeable envelope containing sodium bicarbonate, a mixture
of Glauber's salt and borax, or the like can be used as the
humidifying or humidistasis element; see, for example, U.S. Pat.
No. 2,270,603 (Ridder), issued January, 1942, No. 2,329,908
(Johnson), issued September, 1943, and No. 3,320,697 (Larsen)
issued May 23, 1967; see also O'Brien, "The Control of Humidity by
Saturated Salt Solutions" in J. Sci. Instruments, March, 1948.
The demands placed upon a humidifying element by the manufacturer,
grower, seller, or packager can be very severe. The water is
preferably not bound up either too loosely or too securely within
the humidifying element and preferably should be released or
releasable at a variable rate, depending upon conditions within the
package. If the R.H. within the package were to drop below, say, 10
percent, a very rapid release rate would be needed--yet not so
rapid that the contents would be excessively moistened by a
humidity surge or that the humidifying element would be
irreversibly dried out and rendered substantially inoperative after
a short period of storage.
Further demands upon the humidifying element are made by the
techniques and specifications of packing and shipping goods. Water
vapor pervious bags or porous chambers can add weight or occupy a
great deal of space, thereby detracting from the amount of material
storable in the package. For the typical package, the humidifying
element would preferably have very little bulk. However, a small,
light-weight element would perhaps be the most subject to humidity
surges or rapid irreversible dehydration.
Furthermore, it especially is difficult to introduce a saturated
salt (constant humidity) solution into a closed environment; the
salt may percipitate out or the solution may not be convenient to
enclose in a spill-proof, but humidistatically effective,
container.
Techniques for encapsulating water or other fill liquids within
solid shell walls have been available since about the mid- 1950's.
See Flinn et al., Chem. Eng., Dec. 4, 1967, pages 171-178. Among
the techniques for encapsulating aqueous liquids in capsules 10 to
4,000 microns in diameter is the process disclosed by Arens et al.,
U.S. Pat. No. 3,423,489, issued January 1969. Ordinarily, the water
is sealed into the capsules and cannot be gotten out without
rupturing the capsule walls, but capsules with a slow, apparently
constant water vapor release rate have been made; see Example XXIV
or the Arens et al patent. A controlled soil-moistening capability
has been noted when the soil is mixed with so-called water-in-air
emulsions or "powdered water," i.e., water encapsulated within
silane-treated, fumed silicon dioxide particles.
The application of water encapsulation technology to solve the
problems of humidistasis is not straightforward. First, the
capsules are fragile and ought to be protected from breakage.
Second, the capsules should ideally be disposed so as to permit
maximum exposure and should be able to release or absorb water
vapor at a rate responsive to the demands of the system.
Realization of this ideal would be contrary to the reasonable
expectations of the humidistasis art. Experience with humidifying
elements such as saturated blotters or sponges suggests that the
element might be subject to excessively rapid dehydration under low
ambient humidity conditions (e.g., less than 10 percent R.H.). This
difficulty would appear to apply with great force to
water-containing capsules. The amount of water in each individual
capsule is very small. If this small amount is lost, the capsule
could become totally dry and inoperative as a humidifying
element.
Accordingly, this invention contemplates providing a humidistatic
element comprising water-containing capsules which release water
vapor to an environment at a very high rate when the environment is
characterized by a low relative humidity, but which release or
absorb water vapor at a slow rate (or remain at equilibrium) when
the environment is characterized either by high humidity or by the
desired preselected relative humidity. This invention further
contemplates a structure for providing a layer, preferably a
monolayer, of water-containing capsules whereby the structure
maximizes the exposure of the individual capsules and yet produces
them from breakage or dislodgement. This invention further
contemplates a combination comprising a layer of water-containing
capsules adhered to a backing means, whereby the combination
includes a means to prevent loss of moisture from the capsules
until they are used in a packaging operation.
BRIEF SUMMARY OF THE INVENTION
It has now been found that water-containing capsules with water
vapor transmissive walls can be included in a humidifying or
humidistasis element with the result that the element has a
demand-response capability extremely well suited to the
preservation of perishable or dehydration-sensitive materials and
articles. By "water-containing capsule" is meant a discrete amount
of an aqueous liquid completely surrounded by a solid wall of wax,
natural or synthetic gum or polymer, inorganic material, or the
like. The "aqueous liquid" comprises a significant amount of water
or a water phase, but can contain less than 50 wt. percent water,
as is the case with an aqueous saturated KOH solution. Typically,
aqueous solutions or liquids of this invention contain at least 10
percent by weight of water. The preferred form of capsule is a
substantially spherical droplet of water or aqueous liquid at least
10 microns in diameter, but less than about 0.5 ml. in volume,
surrounded and encapsulated by a substantially spherical, water
vapor transmissive wall. For convenience of packaging, each capsule
preferably contains about 5 .times. 10.sup.-.sup.7 to about 5
.times. 10.sup.-.sup.2 ml or cc of fill liquid, the fill liquid
comprising at least about 50 percent by volume of the capsule. The
demand-response capability appears to be the result of the vapor
permeable walls which can apparently release or absorb water vapor
by any one or a combination of mechanisms. The simplest mechanism
appears to be gas-through-solid diffusion, in this case water vapor
diffusing through the solid, but thin, capsule wall. The driving
force for this mechanism is a non-equilibrium condition
characterized by differences in partial pressure of water vapor on
opposite sides of the capsule wall. Other more complicated
mechanisms appear to be involved also, particularly when the
capsule is full. One such mechanism appears to involve wicking of
liquid water through or into pores, cracks, or irregularities in
the inner surface of the capsule wall (by capillary action or some
similar effect) followed by evaporation of the water thus
entrapped. The preferred capsules used in this invention have
porous walls and are preferably capable of a slow, substantially
constant net release rate. The "net release rate" is the rate
measured while the capsules are losing more water than they absorb.
The rate can be expressed as a percent loss of the total
encapsulated water per unit time, i.e., 100.DELTA.W/W.DELTA.t,
where W is the total amount of encapsulated water and t is time. In
some embodiments of the invention, capsules with at least two net
release rates are used, a fast rate predominating so long as the
capsule has released less than about 20 to 60 percent by weight of
its contents, and a slow net rate predominating at least after the
capsule has released more than 60 percent by weight of its
contents, e.g., more than 10 wt. percent for the "slower" capsules
and more than 55 percent for the "faster" ones. The fast net rate
can usually be accurately measured during the first 24 to 48 hours
of a reproducible test wherein the capsules are permitted to
release water vapor to an ambient atmosphere fixed at 5.5 percent
R.H. The test conditions can be provided by a dessicator containing
saturated sodium hydroxide. Ambient temperature conditions for the
test are preferably in the range of 20.degree. - 25.degree. C. The
slow net release rate can typically be measured after about the
twentieth day in the 5.5 percent R.H. atmosphere or after about the
fifth day in a 97 percent R.H. atmosphere, conveniently provided by
a potassium dihydrogen phosphate solution. The capsules themselves
can contain aqueous salt solutions, so that they will reach an
equilibrium vapor release/absorbtion condition in a given R.H.
environment. If the percent water released vs. time curve has a
linear (constant rate) portion, the constant fast vapor release
rate should preferably be less than about 15 wt. percent of
encapsulated water per day at 5.5 percent ambient R.H. If the curve
is nonlinear, the capsule half life should preferably exceed three
days, i.e., at least 3 days of release time should be required to
obtain a net release of 50 percent by weight of the encapsulated
water. The slow net release rate has been found to be substantially
constant and is less than 5 percent by weight per day of
encapsulated water; at 97 percent R.H. the slow release rate is
preferably less than 2.5 percent per day. By selecting appropriate
deliquescent or hygroscopic fill liquids, the net release rate can
be set at zero (i.e., equilibrium) or as slow as desired, even in a
low ambient R.H. atmosphere. It can reasonably be assumed that at
equilibrium the rates of vapor release and vapor absorption are
equal.
In the preferred structures of this invention, the capsules are
firmly adhered to a backing or carrier which can be cut into wide
or narrow sheets or strips of any desired size which can, if
desired, be coiled into overlapping convolutions for storage prior
to use. The capsule-containing sheets are preferably stored in
moisture-tight bags or containers, wherein the capsules reach
equilibrium after losing, at most, a few percent of their contents.
In use, these sheets can be removed from their moisture-tight
containers and inserted in or integrally bonded to the inside of a
container such as a shipping carton, package, overwrap, twist-tied
bag, or the like, which container need not be moisture-tight unless
either a substantially saturated or a precisely determined level of
humidity is to be maintained within it. The preferred carriers or
backings for the capsules include a vacuum-formed layer of organic
polymer or a pressure-sensitive adhesive on a tape backing or
release liner.
DESCRIPTION OF THE DRAWING
This invention can be more clearly understood by referring to the
accompanying Drawing, wherein:
FIG. 1 is a perspective view of a storage stable humidifying or
humidistasis means of this invention with parts broken away.
FIG. 2 is a cross-sectional view, greatly enlarged, of one
embodiment of a humidifying or humidistasis means of this
invention.
FIG. 3 is a cross-sectional view, drawn to the same scale as FIG.
2, of another embodiment of a humidifying or humidistasis means of
this invention.
FIG. 4 is a perspective view of the upper portion of an open
package, illustrating the use of a humidistasis element of this
invention to help extend the shelf life of a tobacco product.
In the various figures of the Drawing, like numerals denote like
elements of the described structure.
DETAILED DESCRIPTION OF THE DRAWING
A typical humidistasis means of this invention is illustrated by
FIGS. 1, 2, and 4 of the Drawing, and an alternative embodiment of
this means is illustrated in FIG. 3. FIG. 1 illustrates how a
storage stable packaged humidistasis means 10 can be in the form of
a humidistasis tape 20 wound into a roll 11 and stored in a
moisture-tight bag 19. Tape 20 comprises a narrow, strip-like
backing or carrier 13 to which capsules 15 have been adhered. Tape
20 is wound in overlapping convolutions upon a core 17 to form the
roll 11. Roll 11 is stored in a substantially water-impervious bag
19 sealed with closure element 18. Bag 19 can comprise a film of
thick (e.g., up to 4 mils or 0.1 mm) hydrophobic polymer or the
like so that closing bag 19 with closure element 18 provides a
moisture-tight environment for roll 11. Packaged humidistasis means
10 is a preferred form in which the humidistasis tape 20 can be
sold to manufacturers, shippers, growers, packagers, and others who
may be making up humidstatic packages.
An enlarged cross-sectional view of tape 20 is shown in FIG. 2,
wherein it can be seen that capsules 15 comprise an aqueous fill
liquid 29 surrounded and enclosed by a capsule shell wall 27,
described in more detail subsequently. FIG. 2 also illustrates a
preferred form of carrier strip or backing 13, which comprises a
layer of pressure-sensitive adhesive (hereinafter referred to as
PSA) 24 deposited as a coating upon a major surface of release
liner 21 and a fabric-like capsule positioning means 22 adhered to
the exposed major surface of PSA layer 24. Positioning means 22 is
preferably a cloth mesh or scrim with hexagonal openings of
approximately the same size as capsules 15. Means 22 helps to
securely position capsules 15 in neat rows and columns, diagonal
with respect to the length of tape 20, thus facilitating quality
control over manufacture of tape 20 and also helping to guard
against dislodgment or breakage of capsules. Capsules 15 are
substantially spherical and are more than hemispherically exposed
by virtue of being adhesively bonded substantially at their points
of tangency with the exposed surface of PSA layer 24. In practice,
a few percent of the area of the shell walls 27 can be embedded in
PSA layer 24. This small amount of embedding is, however, adequate
to securely anchor capsules 15, particularly with the additional
reinforcement of positioning provided by means 22. As will be
apparent from the subsequent discussion of FIG. 4, means 22 can be
omitted from the structure of backing 13. Pressure-sensitive
adhesive layer 24 is preferably of the type having sufficient
integrity to be handled and used as a transfer adhesive; see, for
example, Kalleberg et al., U.S. Pat. No. 3,062,683, issued Nov. 6,
1972. Thus, PSA layer 24 and release liner 21 comprise a
conventional adhesive transfer tape. Removal of release liner 21
permits the adhesive transfer film 24 to be adhered directly to an
inside surface of a shipping carton or container, e.g., the inside
of lid 47 of cigar pack 40 (FIG. 4).
Thus, FIG. 4 illustrates a typical composite structure of the type
shown in FIG. 2 in use. In FIG. 4, about 1 to about 3 grams of
capsules 15 are adhered to lid 47 by means of PSA layer 24 to keep
cigars 41 at the proper R.H. level. The capsules 15 are reasonably
well secured to layer 24 and are not likely to be dislodged during
shipment or handling of cigar pack 40; therefore, the positioning
means 22 (FIG. 2) has been omitted from the humidistasis means used
in humidifying the inside of cigar pack 40.
The humidistasis means 30, shown in FIG. 3, comprises a monolayer
of capsules 15 through which a vacuum has been drawn, causing a
hot, plastic polymer to be vacuum formed into a tough backing film
33. Adherence of the capsules 15 to the resulting vacuum-formed
backing film 33 is particularly firm in this embodiment, and a
capsule positioning means is generally superfluous. Capsules 15 are
substantially hemispherically exposed. However, variations in
exposure and contact with the backing film 33 from as little as 30
or 40 percent of the surface of the capsules exposed to as much as
80 or 90 percent exposed is not detrimental to either the moisture
transmission or capsule anchoring features of the invention. As a
general rule, however, in both embodiments 20 and 30, the capsules
15 are preferably at least hemispherically exposed.
A further alternative embodiment (not shown) involves the
substitution of a double-coated tape for the adhesive transfer
tape. Since the use of a double-coated tape involves an additional
pressure-sensitive adhesive layer and an additional release liner,
this embodiment is not preferred. When adherence to an inner
surface of a container is not required, as, for example, in the
case where the humidistasis element is inserted loose into the
inside of a carton or container, the backing 13 can comprise a
conventional pressure-sensitive adhesive tape with no adhesive
transfer capability.
Either of the embodiments 20 or 30 of a humidistasis element of
this invention can be cut into a narrow strip, wound upon a core in
overlapping convolutions, and thereby formed into a compact roll
which can be stored almost indefinitely by the packager or
manufacturer (as in FIG. 1) until ready for use in a humidistatic
package, e.g., of the type shown in FIG. 4.
During storage, the capsules 15 in tape roll 11 lose some water
vapor to the environment within plastic bag 19. However, since
substantially no moisture is lost from bag 19 to the ambient
atmosphere, an equilibrium condition is soon reached. If capsules
15 contain a saturated salt solution, the equilibrium condition
within bag 19 will be determined by the humidistatic effect of the
solution. To cite two possible extremes, the atmosphere inside bag
19 could level off at 97 percent R.H. for capsules which contain
saturated aqueous potassium dihydrogen phosphate. Alternatively,
the R.H. within bag 19 could actually drop to 5.5 percent if the
aqueous fill in capsules 15 were saturated aqueous sodium hydroxide
(in this case there would be some danger of rupturing some of the
capsules due to stress on the inside of capsule walls resulting
from the large water absorption). If the aqueous fill in capsules
15 is pure water, the equilibrium is reached at about 99 percent
R.H.
The conditions of capsule equilibrium during storage are generally
applicable to the performance of the capsules in use in a
humidistatic package. As will be apparent from the foregoing
discussion of the prior art, there are various uses for
humidistasis means 20 or 30. The first type of use is illustrated
in FIG. 4. Five-pack 40 is a moisture-pervious package which, under
typical conditions of storage, is likely to permit net loss of
moisture from cigars 41 to the ambient atmosphere external to pack
40. Capsules 15 on lid 47, after lid 47 has been closed, serve a
humidity replacement function. The net rate of loss of moisture
from cigars 41 is variable, and capsules 15 advantageously supply
humidity at a controlled rate substantially in response to the
demands of the system. For this type of
moisture-replacement-on-demand, it is adequate and even preferred
to use capsules 15 which contain substantially pure water rather
than a saturated salt solution. However, saturated salt solutions
can be used, e.g., saturated sodium chloride.
Humidistasis means 20 or 30 is also useful in tightly closed
environments which are intermittently opened, e.g., to remove part
of the contents. In this use, and in uses involving moisture-tight
environments which are not intermittently opened, a desired
equilibrium R.H. level within the environment can be prescribed
within narrow limits by selecting an appropriate aqueous fill for
capsules 15. Typically, the aqueous fill 29 is a saturated aqueous
solution of one of the metal salts disclosed in O'Brien, J. Sci.
Instruments, pp. 73-76 (March, 1948). If a fixed level of about 99
percent R.H. is desired, the aqueous fill 29 can be pure water.
Humidistasis means of this invention are surprisingly efficient in
restoring equilibrium R.H. conditions even when humidistasis is
temporarily disturbed by intermittent opening and closing of a
relatively moisture-tight container. A sealed moisture-tight
environment not subject to even temporary disturbances can be
provided by means known in the packaging art, e.g., wax coatings in
or upon cartons or packages; polyolefin film overraps, liners, or
packages; heat-sealed polymeric films or aluminum/polyolefin
laminates; etc.
For the typical five-pack of cigars, about 0.5 to 3 square inches
(3.2 - 19 cm.sup.2) of humidistasis means 20 or 30 is adequate to
protect the freshness of the cigars and insure a shelf life of a
year or longer. For cigar boxes containing 50 cigars, larger
humidostasis means are generally desirable, e.g., about 10 square
inches (65 cm.sup.2).
The preferred capsules 15 are preferably made according to the
teachings of Arens et al., U.S. Pat. No. 3,423,489, issued Jan. 21,
1969, the fill liquid being preferably a predominantly aqueous
liquid which can contain, if desired, dispersoids or solutes such
as dissolved inorganic salts. The shell material is preferably made
from a mixture of 20 - 70 wt. percent polyethylene, 15 - 50 wt.
percent natural or synthetic polyterpene or other amorphous organic
resin, up to 40 wt. percent (preferably at least 2 wt. percent) of
a wax such as a hydrocarbon wax, and, if desired, a minor amount of
a suitable plasticizer or the like. This type of composition forms
a single phase at elevated temperatures, but is subject to phase
separation effects upon cooling. The separation of phases creates
microscopic pores in capsule walls 27. These pores permit
transmission of water vapor to and from the interior of the capsule
by one or more vapor transport mechanisms.
FURTHER DESCRIPTION AND EXAMPLES
As will be apparent from the foregoing description, a variety of
carrier means or backing means can be used in this invention,
provided that the capsules are securely anchored to it and are
sufficiently exposed for good moisture release. The carrier means
itself can be any suitable sheet-like structure, including woven or
non-woven webs, waterlaid sheets such as paper, polymeric film,
metal foil or polymeric film coated with adhesive, a coherent
adhesive (such as an adhesive transfer film), a sheet of foamed
synthetic organic resin, or the like. Coherent, flexible carriers
with an exposed major surface suitable for capsule anchoring are
most useful, and planar carriers ("planar" meaning either a flat or
curved plane), which can be cut to any desired width are preferred.
The carrier means is preferably 10 - 2,500 microns (0.4 - 100 mils)
thick, though up to about 5 mm (about 200 mils) can be used if the
carrier is a thick layer of foamed synthetic resin, e.g.
polyurethane foam. Corrugated or embossed carriers can be used.
When a cloth mesh or scrim is employed as in FIG. 2 of the Drawing,
the openings in the scrim can be square, hexagonal, or the like,
provided the widest dimension of the opening is slightly smaller or
slightly larger than the diameter of the capsules positioned by the
scrim. The scrim can be made from monofilament or multifilament
fibers of nylon, polyester, or the like.
The water-containing capsules used in this invention are preferably
made by the "biliquid column" technique of Arens et al., U.S. Pat.
No. 3,423,489, issued Jan. 21, 1969. In the Arens et al. technique
a jet or column of the liquid fill material is surrounded and
enclosed by a concentric stream of shell forming material. This
composite or "biliquid" stream is directed in a trajectory with a
horizontal component such that the stream of shell-forming material
constricts along its length into spheroids, each spheroid enclosing
a core of the fill material. This process can produce capsules
ranging in size from 10 to 4,000 microns in diameter. In the
present invention, capsules less than 3,000 microns in diameter are
preferred, and it is generally convenient to use capsules larger
than 100 microns in diameter.
Although it is desirable in some embodiments of this invention to
use a capsule fill comprising pure water, the viscosity of pure
water is less than ideally suited for the Arens et al process of
making capsules. Therefore, it is preferred to introduce a
viscosity modifier or builder into the aqueous fill liquid to
facilitate capsule manufacture. As pointed out in the Arens et al.
disclosure, a few percent of a copolymer of maleic anhydride and
methyl vinyl ether and/or a hydroxy terminated
polyoxyethylene/oxypropylene copolymer can be used as a viscosity
builder. Other conventional additives to the aqueous fill include
latex solids and strongly colored dyes, where desired. Up to about
90 percent by weight of the aqueous fill liquid can comprise a
solute, a water-miscible liquid, a dispersoid, a suspensoid, or
mixtures of these. For careful control of humidity in a reasonably
moisture-tight container, it is preferred to use a saturated
aqueous solution of a suitable solute which will stabilize the R.H.
level at less than 99 percent. Among the solutes known to be useful
for control of humidity by saturated aqueous solutions are various
oxides and metal or ammonium salts. The oxide which has been most
fully investigated is phosphorus pentoxide. Typical metal salts are
the salts of elements of Group I-A and II-A of the Periodic Table
and lead, zinc, and thallium. Typical ammonium salts include
ammonium nitrate, ammonium dihydrogen phosphate, ammonium sulphate,
ammonium chloride, etc. Aqueous solutions of water-soluble organic
compounds such as urea have also been used in humidity control.
If the aqueous fill liquid contains one of the previously mentioned
solutes, the viscosity modifier or builder should be selected with
some care so as not to precipitate the solute or radically alter
the water vapor pressure of the aqueous solution. For example, a
saturated sodium chloride solution can be used in a closed
atmosphere to maintain a relative humidity level of 75 - 77
percent. Some of the conventional viscosity builders do tend to
precipitate sodium chloride or alter the vapor pressure of
saturated NaCl. It has been found that high molecular weight
polysaccharide gums made by fermentation, e.g. "Kelzan" (trademark
of Kelco Company) or "Biopolymer XP-23" (trade designation of
General Mills) do not have these undesired effects upon a saturated
sodium chloride solution.
In making capsules useful in this invention, any suitable shell
wall material (including synthetic polymers, hydrocarbon or ester
waxes, natural or synthetic resins, gums, gelatinous materials,
etc.) can be used, provided that the shell wall will permit
moisture vapor to pass from the interior of the capsule without
rupturing the capsule walls. One method for providing moisture
transmission is to control the capsule-forming conditions so as to
provide walls thin enough for vapor loss by diffusion. Another
technique is illustrated by Example XXIV of Arens et al, wherein
the aqueous contents of the capsule diffused into a 40 percent
R.H., 23.degree. C. environment at a rate of 0.2 percent per day,
thus providing a half life of 241 days for the capsule contents.
The pores in the walls of the capsules made according to this
technique were, however, in the nature of cracks and were generally
grosser than the type of porous structure preferred for capsule
walls in this invention. Cross cracks or pores in capsule walls are
generally not too detrimental when the capsule contains
substantially pure water. However, if the capsule contains a
saturated salt solution, solute can leak out of the capsule wall in
solution and be deposited outside the capsule, where it will no
longer have a humidistatic effect upon the ambient atmosphere.
Accordingly, it is preferred that capsules used in this invention
have shell walls which are free of gross flaws, cracks, etc., which
are large enough to be seen by the naked eye. Stated another way,
flaws or pores in the capsule wall should not be large enough to
permit outflow of an aqueous liquid by mechanisms other than
capillary action. In addition to loss of solute, severe leaks can
result in the capsule fill having a half life of only a day or two.
Once empty, capsules with grossly flawed walls are generally not
able to reabsorb water.
Another technique for providing moisture transmissive
water-containing capsules involves the use of silane-treated fumed
silicon dioxide. This material, which is an extremely fine powder,
is so hydrophobic that it tends to surround and encapsulate
droplets of water, thus forming "water-in-air" emulsions or
"powdered water." Hydrophobic, silane-treated, fumed silica is
obtainable from Cabot Corporation, Boston, Massachusetts, under the
trademark "Silanox." When "Silanox" is mixed with relatively large
quantities of water under high shear conditions, the water appears
to be converted to a free-flowing powder which comprises, for
example, 61 percent air, 34 percent water, and 5 percent "Silanox"
by volume. Moisture is lost from this "powdered water" or
"water-in-air emulsion" at a substantially constant rate for a
given R.H. According to "Silanox" literature, an "emulsion" of 90
percent water, 10 percent "Silanox" lost about 5 percent of the
water per day for the first 10 days in a 0 percent R.H. ambient
atmosphere -- a half life of 10 days. From the tenth to the
fifteenth day, an additional 20 percent of the water was lost.
Under 10 percent R.H. conditions, the rate of loss was 4 percent
per day for the first 5 days, slowing to 3 percent per day or less
for the next 10 days, resulting in a half life of about 15 days.
The 47 percent R.H. curve showed a rate of 3 percent per day or
less, the 15-day loss being about 35 percent. Under 85 percent R.H.
conditions, the loss rate was only about 0.7 percent per day. Thus
though "Silanox" is particulate, it appears to form a porous,
hydrophobic wall about droplets of water, and the resulting
structure behaves like water-containing capsules with moisture
transmissive walls.
The preferred technique for providing the capsule shell walls for
vapor transmissivity involves the Arens et al process with
selection of the shell wall-forming materials such that these
materials will have certain liquid phase and solid phase
relationships, that is: At least a first solid phase comprises a
first material, and a second solid phase comprises a second
material, the first and second materials being miscible and capable
of forming a single phase when both materials are in a liquid
state, but capable of forming separate phases upon being cooled to
a solid state. The percent of contraction in volume upon being
cooled in greater for the first material as compared to the second
material, and it appears that contraction of the first material,
upon cooling of the shell-forming composition, contributes to the
formation of micropores which extend completely through the
resulting capsule wall. An example of the combination of materials
which produces this microporosity is a mixture of an olefinic
polymer, an amorphous organic resin, a wax, and, optionally, a few
percent of a plasticizing material such as mineral oil.
In the Examples which follow, typical shell-forming compositions
and their net water vapor release rates will be illustrated. These
non-limiting Examples will also serve to illustrate the principle
and practice of this invention.
EXAMPLE A
WATER VAPOR-RELEASING CAPSULES
Nine lots of capsules averaging 2,000 microns in diameter were made
from aqueous fill liquids and polyolefin-containing shell-forming
materials according to the teachings of Arens et al., U.S. Pat. No.
3,423,489. The nine lots of capsules are designated hereinafter as
Lot A-1 through Lot A-9. In Lots A-1, A-2, and A-7, the aqueous
liquid fill material was 97 percent by weight of water, 3 percent
by weight of a viscosity-building copolymer of maleic anhydride and
methyl vinyl ether ("Gantrez" [trademark]). In Lots A-3, A-4, A-5,
and A-6, the aqueous liquid fill material was 85 percent water, 15
percent polyoxyethylene glycol. The aqueous liquid fill material
for Lots A-8 and A-9 was made from water thickened with a high
molecular weight polysaccharide gum made by fermentation ("Kelzan,"
trademark of Kelco Company), in which sodium chloride was
dissolved.
The procedure for making the liquid fill for Lot A-8 was as
follows: Three liters of a 0.1 percent (by wt.) "Kelzan" in water
solution was prepared and allowed to stand overnight with some
mixing. Then 1.2 kg of NaCl was added, and the solution was mixed
for 2 hours. The solution was then allowed to stand for one hour.
The majority of it was decanted into a vacuum receiver and degassed
at 27 mm Hg pressure. Three drops of "Triton X 200" were added
before mixing had ceased. "Triton X 200" is the sodium salt of an
alkylaryl polyether sulfonate in isopropanol.
The liquid fill for Lot A-9 was prepared by mixing 0.056 lb. of the
"Kelzan" with 28 lbs. of water to give a 0.2 wt. percent "Kelzan"
solution. Twelve pounds of NaCl were then mixed in to provide the
desired solution.
The shell-forming materials for all nine lots were blended to form
a single molten phase at elevated temperatures which cooled to a
solid, vapor pervious shell during capsule manufacture. All of
these blends were made from the following materials:
1. Polyolefin: Polyethylene "AC 617" (trade designation of Allied
Chemical Co. for a low molecular weight polyethylene, melting point
= 102.degree. C., specific gravity = 0.92)
2. Amorphous resin: "Wingtack--95" (trademark of Goodyear Tire and
Rubber Co. for amorphous hydrocarbon resin with softening point of
95.degree. C. and a specific gravity of 0.93)
3. Wax: "Shellwax 700" (trademark of Shell Chemical Co. for
hydrocarbon wax, melting point = 84.degree. C., specific gravity =
0.94 at 15.degree. C.)
4. plasticizer: Mineral oil
Capsules made according to this Example were checked for gross
flaws by soaking them in solution-type black ink. Stained gross
flaws or darkened capsules were noted, and only a few percent of
the capsules were found to have flaws readily visible to the naked
eye. (The flawed capsules can be discarded for purposes of this
invention.) The proportions of shell-forming materials in parts by
weight are set forth below:
PARTS BY WEIGHT Capsule Poly- Amorphous Mineral Lot olefin Resin
Wax Oil A-1 60 15 25 2 A-2 55 15 30 2 A-3 45 35 20 2 A-4 45 40 15 2
A-5 40 35 25 2 A-6 45 20 35 2 A-7 40 35 25 2 A-8 45 40 15 2 A-9 40
35 25 2
the above capsule shell formulations for Lots A-1 through A-9 were
formulated and used in the Arens et al process by following the
teachings of German laid-open Pat. application 2,019,724 (Hofacker)
published Nov. 5, 1970.
Capsules of Lots A-1 through A-7 were placed in desiccators
containing
a. saturated NaOH (5.5 percent ambient R.H.) and
b. saturated KH.sub.2 PO.sub.4 (97 percent ambient R.H.).
All desiccators were kept at 20.degree. to 25.degree. C.
For all lots except Lot A-4 (which had a substantially linear
cumulative-percent-water-release vs. time, even at 5.5 percent
R.H.), at least two, generally three, different rates of release at
5.5 percent R.H. were noted. Typically, there was a fast initial
rate of release, which was extrapolated back to time = zero (total
amount of encapsulated water released = 0 percent). This initial
rate is referred to in the following table as the "t.sub.o rate,"
"t" being time in days. A slow release rate was observed during the
fifteenth to the twenty-fifth day. This rate is called t.sub.20,
since it was determined approximately by taking the slope of the
cumulative-percent-release vs. time curve at t=20 (time = 20 days).
A rate transitional between the t.sub.o rate and the t.sub.20 rate
was typically observed at t = 5 days, referred to hereinafter as
the t.sub.5 rate. Rates of release at 97 percent R.H. were
substantially constant for all capsule lots after the first few
days; so for 97 percent R.H. only a time = 6 (t.sub.6) rate is
given. The 5.5 percent R.H. rates (t.sub.o, t.sub.5, t.sub.20) are
believed to be accurate to about .+-. 0.1 percent/day. The 97
percent R.H. rate (t.sub.6) is believed to be accurate to about
0.05 percent/day.
Net Release Rates in % by Weight of Encapsuled Water Lost Per
Day
t.sub.0 t.sub.5 t.sub.20 t.sub.6 Capsule rate at rate at rate at
rate at Lot 5.5% 5.5% 5.5% 97% R.H. R.H. R.H. R.H. (%/day) (%/day)
(%/day) (%/day) A-1 5.0 1.2 0.4 0.70 A-2 2.5 0.8 0.2 0.20 A-3 1.6
1.6 0.3 0.25 A-4 0.2 0.2 0.2 <0.05 A-5 3.6 2.6 0.4 0.50 A-6 9.2
3.8 0.2 0.25 A-7 3.2 2 to 3* 0.6 0.90 *t.sub.5 for Lot A-7 fell on
a portion of the curve where the slope was changing from about
2.8%/day to about 2%/day.
At 5.5 percent R.H., Lot A-6 had the shortest half life: 50 percent
by weight of the total amount of water encapsulated within the test
sample of Lot A-6 was released to the ambient atmosphere in 9.5
days. The half-lives of Lots A-1 through A-5 and A-7 at 5.5 percent
R.H. were all longer than 25 days. The 5.5 percent R.H. half-life
of Lot A-4 was the longest: 227 days (by extrapolation).
EXAMPLE B
ENCAPSULATION OF WATER WITH SILANE-TREATED
FUMED SILICA
Ten grams of "Silanox" were mixed with 90 ml of a saturated aqueous
solution of sodium chloride. The mixture was mixed in a high speed
Waring blender for 30 seconds. A white flowable powder resulted,
4.6 grams of which were placed in a 250 ml. desiccator along with a
Taylor "Humiguide." A constant relative humidity of 73 percent was
achieved within 24 hours. The Taylor "Humiguide" was not
calibrated; therefore, 73 percent is not an absolute number, but it
agrees fairly well with the theoretical value of 75 - 76 percent
R.H.
During the humidistasis test in the desiccator, the temperature was
kept at 71.degree. - 73.degree. F. The Taylor "Humiguide" had an
initial reading of 66 percent R.H. at 73.degree. F. Forty-eight
minutes later the reading had dropped to a low point of 44 percent
R.H. An hour after this low point was reached, the reading was up
to 52.5 percent. The readings continued to rise steadily until, at
seven hours elapsed time, the reading was 69.5 percent R.H. At 24
hours elapsed time the 73 percent R.H. value had been attained and
remained within 1 percent of this value until the test was
discontinued two days later.
EXAMPLE C
COMPARISON WITH HYDROPHILIC SPONGE
A hydrophilic sponge was made by the following procedure: 1,000
parts by weight of polyoxyethylene glycol of molecular weight 1,000
(sold under the trademark "Carbowax" 1,000) was reacted with 351
parts tolylene diisocyanate (an 80/20 mixture of the 2,4-
2,6-isomers) under substantially anhydrous conditions for 2 hours
to provide a hydrophilic diisocyanate prepolymer. The prepolymer
dissolved in, and rapidly reacted with, water with considerable
carbon dioxide evolution to form a hydrophilic foam. A portion of
the foam was soaked in water and became saturated almost
immediately. The saturated, spongelike foam was placed in
desiccators under 5.5 percent R.H. and 97 percent R.H., as in
Example A. Constant release rates were observed at both humidity
levels. These rates were:
5.5 percent R.H.: 28 percent/day
97 percent R.H.: 4 percent/day (average of two curves)
Thus, the hydrophilic sponge had a tendency to dry out even at 97
percent R.H., as is illustrated by the half-life data:
5.5 percent R.H.: 50 percent by wt. of water released in <2
days.
97 percent R.H.: 50 percent by wt. of water released in <13
days.
EXAMPLE 1
CONSTANT HUMIDITY MEANS
The capsules of Lot A-8 (see Example A) were found to be in
equilibrium with an ambient atmosphere controlled by a saturated
salt solution in the following experiment:
Lot A-8 capsules were sealed inside a substantially moisture-tight
chamber in the presence of a saturated aqueous NaCl solution, and
the weight loss from the capsules was monitored. The weight loss
was found to be negligible and was attributed to minor
imperfections in the moisture tight seal.
A construction as shown in FIG. 2 of the Drawing was prepared using
Lot A-8 capsules as the capsules 15 of the tape 20. This tape was
found to be useful for storage of tobacco in moisture-tight
containers.
EXAMPLE 2
INTERMITTENT DISTURBANCE OF HUMIDISTASIS
A 10-inch desiccator chamber was cleaned and thoroughly dried. A
Taylor "Humiguide" which had previously been calibrated as reading
about 9 to 10 percent low was placed in the chamber. Twenty-five
grams of Lot A-9 constant humidity capsules of Example A were
placed in an aluminum weighing dish in the middle of the support
plate. The top was closed. The temperature of the desiccator,
except as noted, was kept at 71.degree. - 72.degree. F. The
following data were obtained:
Uncalibrated Day Time "Humiguide" Reading (% R.H.) 1st day 2:38
P.M. 13 7:00 P.M. 57 9:00 P.M. 60 2nd day 8:15 A.M. 64 8:16 opened
chamber and closed it (dry air introduced) 8:21 A.M. 57 1:00 P.M.
54 5:00 P.M. 59 9:00 P.M. 62 3rd day 7:45 A.M. 65 11:15 A.M. 63*
4:45 P.M. 63* 4th day 10:20 A.M. 65* 6th day 8:05 A.M. 63* 7th day
8:30 A.M. 65 5:15 P.M. 64 8th day 8:50 A.M. 65 9th day 7:59 A.M. 65
12:20 P.M. 63 10th day 8:15 A.M. 65** 13th day 7:25 A.M. 65** 14th
day 8:15 A.M. 65** 15th day 8:45 A.M. 65** *Temperature: 69.degree.
F. on part of 3rd day, 69.degree. on 4th day, 70.degree.F. on 6th
day.**Corrected reading: 74.3% R.H.
these data demonstrate that the capsules can raise the relative
humidity of a dry closed chamber to a given level and hold it
there. It also demonstrates that the capsules can bring the
environment back to its original condition if it is distributed by
dry air.
The Lot A-9 capsules were applied to a tape and found to be useful
for storing pipe tobacco in a humidor which was subject to weekly
openings and closings.
EXAMPLE 3
HUMIDITY-ON-DEMAND SYSTEM
The capsules of Lot A-6 (see Example A) were incorporated in a
humidistasis means of this invention and were found to be useful
for application to the inside of a shipping box for cut flowers.
The capsules released water vapor on demand for a period of
weeks.
* * * * *