Abstrict A desiccant composition containing a deliquescent salt and a modified
starch containing from about 5 to about 95 percent of the deliquescent
salt and from about 5 to about 95 percent of the modified starch.
Claims 1. A desiccant composition comprising a deliquescent salt and a
modified starch, wherein the deliquescent salt comprises at least
about 5 to about 95 percent of the composition by weight and the
modified starch from about 5 to about 95 percent of the composition.
2. The desiccant composition of claim 1 wherein the deliquescent
salt comprises from about 20 to about 95 percent of the composition
by weight and the modified starch from about 5 to about 80 percent
of the composition by weight.
3. The desiccant composition of claim 1 wherein the deliquescent
salt comprises from about 50 to about 80 percent of the composition
by weight and the modified starch from about 20 to about 50 percent
of the composition by weight.
4. The desiccant composition of claim 1 wherein the modified starch
comprises a modified corn starch.
5. The desiccant composition of claim 1 wherein the deliquescent
salt is selected from the group consisting of alkali, ammonium,
alkali earth, earth and transition metal halides, sulfates, sulfites,
thiosulfates, nitrates, nitrites, phosphates, carbonates and carboxylates.
6. The desiccant composition of claim 1 wherein the deliquescent
salt is selected from the group consisting of LiCl, LiBr, LiI, ZnCl.sub.2
ZnBr.sub.2 LiI, Ca(NO.sub.3).sub.2*2H.sub.2O, NaHSO.sub.4 Mg(NO.sub.3)*6H.sub.2O,
KI, NaI, NaNO.sub.2 KBr, (NH.sub.4).sub.2SO.sub.- 4 Na(C.sub.3H.sub.3O.sub.2)*3H.sub.2O,
Na.sub.2S.sub.2O.sub.3 NH.sub.4Cl, KHSO.sub.4 Na.sub.2CO.sub.3*10H.sub.2O,
ZnSO.sub.4*7H.sub.2O, K.sub.2HPO.sub.4 Na.sub.2SO.sub.3*7H.sub.2O,
NaF, K.sub.2(CO.sub.3).sub.2*2H.sub.2O, Zn(NO.sub.3).sub.2 NH.sub.4H.sub.2PO.sub.4
and MgCl.sub.2.
7. The desiccant composition of claim 1 wherein the deliquescent
salt comprises magnesium chloride.
8. The desiccant composition of claim 1 wherein the deliquescent
salt is selected from the group consisting of zinc chloride and
lithium chloride.
9. The desiccant composition of claim 1 wherein the deliquescent
salt is selected from the group consisting of ammonium chloride,
ammonium sulfate and ammonium carbonate.
10. A desiccant composition for application under conditions where
the relative humidity is less than about 20 percent comprising a
deliquescent salt selected from the group consisting of ZnCl.sub.2
LiCl, ZnBr.sub.2 LiBr, ZnI.sub.2 LiI and a modified starch, wherein
the deliquescent salt comprises at least about 5 to about 95 percent
of the composition and the modified starch comprises from about
5 to about 95 percent of the composition.
11. The desiccant composition of claim 10 wherein the deliquescent
salt is selected from the group consisting of zinc chloride and
lithium chloride.
12. A desiccant composition for application under conditions where
the relative humidity is greater than about 20 percent, comprising
a deliquescent salt selected from the group consisting of Ca(NO.sub.3).sub.2*2H.sub.2O,
NaHSO.sub.4 Mg(NO.sub.3)*6H.sub.2O, KI, NaI, NaNO.sub.2 KBr, (NH.sub.4).sub.2SO.sub.4
Na(C.sub.3H.sub.3O.sub.2)- *3H.sub.2O, Na.sub.2S.sub.2O.sub.3 NH.sub.4Cl,
KHSO.sub.4 Na.sub.2CO.sub.3*10H.sub.2O, ZnSO.sub.4*7H.sub.2O, K.sub.2HPO.sub.4
Na.sub.2SO.sub.3*7H.sub.2O, NaF, K.sub.2(CO.sub.3).sub.2*2H.sub.2O,
ZN(NO.sub.3).sub.2 NH.sub.4H.sub.2PO.sub.4 and MgCl.sub.2 and a
modified starch, wherein the deliquescent salt comprises at least
about 5 to about 95 percent of the composition and the modified
starch comprises from about 5 to about 95 percent of the composition.
13. The desiccant composition of claim 12 wherein the deliquescent
salt comprises magnesium chloride.
14. The desiccant composition of claim 12 wherein the deliquescent
salt is selected from the group consisting of NH.sub.4Cl, (NH.sub.4).sub.2SO.sub.-
4 and (NH.sub.4).sub.2CO.sub.3.
15. A desiccant composition for application under conditions where
the relative humidity is greater than about 50 percent, comprising
a deliquescent salt selected from the group consisting of calcium
chloride, magnesium chloride, potassium chloride and zinc nitrate
and a modified starch, wherein the deliquescent salt comprises at
least about 5 to about 95 percent of the composition and the modified
starch comprises from about 5 to about 95 percent of the composition.
16. The desiccant composition of claim 15 wherein the deliquescent
salt is selected from the group consisting of calcium chloride and
magnesium chloride.
17. A desiccant container comprising a desiccant composition secured
within a water vapor permeable film product, wherein the desiccant
composition comprises a deliquescent salt and a modified starch,
wherein the deliquescent salt comprises at least about 5 to 95 percent
of the composition by weight and the modified starch from about
5 to 95 percent of the composition by weight.
18. The desiccant container of claim 17 wherein the deliquescent
salt comprises from about 20 to about 95 percent of the desiccant
composition by weight and the modified starch from about 5 to about
80 percent of the composition by weight.
19. The desiccant container of claim 17 wherein the deliquescent
salt comprises from about 50 to about 80 percent of the desiccant
composition by weight and the modified starch from about 20 to about
50 percent of the composition by weight.
20. The desiccant composition of claim 17 wherein the deliquescent
salt comprises magnesium chloride.
21. The desiccant composition of claim 17 wherein the deliquescent
salt is selected from the group consisting of zinc chloride and
lithium chloride.
22. The desiccant composition of claim 17 wherein the deliquescent
salt is selected from the group consisting of ammonium chloride,
ammonium sulfate and ammonium carbonate.
23. A process for manufacturing a desiccant container comprising
(a) preparing a water vapor permeable film product, (b) preparing
a desiccant composition wherein the desiccant composition comprises
a deliquescent salt and a modified starch wherein the deliquescent
salt comprises at least about 5 to 95 percent of the composition
by weight and the starch from about 5 to about 95 percent of the
composition by weight, (c) placing the desiccant composition between
layers of the water vapor permeable film product, and (d) sealing
edges of the water vapor permeable film product around the desiccant
composition to produce the desiccant container.
24. The process of claim 23 wherein the deliquescent salt comprises
magnesium chloride.
25. The desiccant composition of claim 23 wherein the deliquescent
salt is selected from the group consisting of zinc chloride and
lithium chloride.
26. The desiccant composition of claim 23 wherein the deliquescent
salt is selected from the group consisting of ammonium chloride,
ammonium sulfate and ammonium carbonate.
Description CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This is a continuation-in-part of application Ser. No. 09/348397
filed Jul. 7 1999 now U.S. Pat. No. 6217701 and application
Ser. No. 08/748362 filed on Nov. 13 1996 now U.S. Pat. No. 5935304
and application Ser. No. 08/715067 filed on Sep. 19 1996 now
U.S. Pat. No. 5743942.
BACKGROUND OF INVENTION
[0002] 1. Field of Invention
[0003] This invention relates to desiccant containers. More specifically,
this invention relates to a composition of material for use in a
desiccant container comprising a combination of a deliquescent salt
and a modified starch.
[0004] 2. Prior Art
[0005] Desiccant containers which absorb water vapor, water, liquids
and the like are well known in the art. Generally, these containers
are comprised of a water or water vapor permeable packaging material
formed from fibrous or film products securely sealed together at
the edges of the packaging. The packaging material encapsulates
a desiccant material, such as silica gel. The volume of water or
water vapor absorbed by the desiccant container is generally determined
by the absorbent capacity of the desiccant material contained within
the container and the temperature and relative humidity level of
the surrounding air.
[0006] One type of desiccant container absorbs both water vapor
and liquid water by permitting both to pass through the packaging
material to be absorbed by the desiccant material. In some circumstances,
the packaging material for this type of product dissolves to permit
the desiccant material contained within the desiccant container
to have direct contact with the liquid.
[0007] Another type of desiccant container absorbs water vapor
but not liquid water. The packaging material for this type of desiccant
container is designed to prevent water absorbed within the desiccant
container as water vapor from being released from the desiccant
container in the form of liquid water.
[0008] There are many common products that are utilized as desiccating
agents. Among the most common used include silica gel, calcium sulfate,
calcium fluoride, activated charcoal, molecular sieves, lithium
chloride, calcium chloride and other such products. A common list
of drying agents is contained, for example, in Kirk-Othmer, Encyclopedia
of Chemical Technology, Volume 7 pages 378-398. Common desiccating
agents for use in conventional desiccant containers are also disclosed
in U.S. Pat. No. 5114003 which discloses the use of a montmorillonite
clay, silica gel, molecular sieve, calcium oxide, calcium sulfate
and calcium chloride. The use of silica gel, alumino silicate, alumina,
activated charcoal and molecular sieves as desiccating agents are
disclosed in U.S. Pat. No. 4464261.
[0009] Commercial grade calcium chloride is a widely used desiccant
due to its low cost and high degree of hygroscopicity. Calcium chloride
compacted in the form of particles or beads is used as a drying
agent, for example, in U.S. Pat. No. 3923944.
[0010] Mixtures and combinations of other materials have been blended
with calcium chloride to form desiccating products.
[0011] For example, polyethylene glycol was mixed with calcium
chloride to form a desiccant product in U.S. Pat. No. 3779936.
In addition, U.S. Pat. No. 3334468 discloses the use of sodium
chloride or sodium carbonate with calcium chloride. Further, the
combination of calcium chloride with magnesium, lithium or ammonium
salts is disclosed, for example, in U.S. Pat. No. 3885926. The
use of calcium chloride with a metal, for example, iron fillings,
is disclosed in U.S. Pat. No. 1798862. Further, the use of activated
carbon with calcium chloride as a desiccant product is disclosed
in U.S. Pat. No. 2027093.
[0012] U.S. Pat. No. 3390511 discloses the use of calcium chloride
placed on a carrier material for use as a gas dryer desiccant. The
preferred material that is utilized as the carrier for the calcium
chloride is sodium chloride. See also, U.S. Pat. No. 3334468.
The desiccant product in U.S. Pat. No. 3390511 preferably comprised
about 90 to 97 percent sodium chloride as the carrier and about
10 to about 3 percent calcium chloride. In addition, sodium dichromate
and trisodium phosphate in minor amounts may be included in the
product. While the preferred carrier for the calcium chloride was
sodium chloride, other disclosed carriers included sugar, potassium
chloride, potassium nitrate, sodium nitrate and starch. See column
3 line 33. The percentage of calcium chloride used in this product
was percent or less, because the major component of the product
was the carrier.
[0013] One of the problems in the utilization of calcium chloride
as a desiccating agent is that when the water is absorbed, it forms
a liquid mixture on the surface of the calcium chloride. This is
discussed in U.S. Pat. No. 3334468. With conventional desiccant
products this liquid may leak from the packaging which can cause
problems, for example, if the desiccant product is used in storage
containers.
[0014] There are situations where absorption of moisture by a desiccant
product even at low humidity and low water vapor pressure is necessary,
such as when the product protected by the desiccant product can
be damaged by moisture. Usually traditional desiccants, such as
desiccant clays, silica gel, molecular sieve and calcium sulfate
are used in this situation. However, for some applications the capacity
for absorption of moisture of these desiccant products is too low.
An example where this problem can occur is the shipment of steel
products overseas. In order to avoid the rusting of these steel
products, it is important that the relative humidity level in the
container holding those steel products be maintained below about
40 percent at 25.degree. C. for as long as several weeks. While
conventional desiccant products, such as silica gel, can be effective
in absorbing moisture in some situations, they do not have the high
capacity for absorption that is necessary for extended periods of
time. Desiccant products with a higher capacity for absorption at
humidity levels below 40 percent relative humidity are needed in
this situation.
[0015] In other situations conventional desiccant products begin
to absorb moisture at relative humidity levels which are unnecessarily
low. In these situations a considerable portion of the absorption
capacity of the desiccant product is wasted because moisture is
absorbed at humidity levels where no damage can occur to the products
being shipped with the desiccant product. In addition, if the humidity
level then rises, there is a risk that these conventional desiccant
products will not have sufficient remaining absorption capacity
to absorb water vapor and protect the products being shipped.
[0016] In addition, it is sometimes difficult to utilize conventional
desiccant products with products which inherently have a high moisture
content, such as cocoa, coffee, tobacco and dog food. If the desiccant
product absorbs too much moisture at relatively low humidity levels,
these products may be damaged. Further, the high capacity of some
desiccant products to absorb moisture is wasted in these situations.
In addition, there is a risk that not enough absorption capacity
will be available during the entire shipping process, especially
when the humidity level rises.
[0017] While certain references disclose the use of calcium chloride
and other deliquescent salts as a desiccant either alone or in combination
with a number of different compositions, there is still a need for
improved desiccant products utilizing calcium chloride and other
deliquescent salts.
[0018] In addition, there is a need for a desiccant composition
which can be useful in both low humidity and high humidity applications.
[0019] Therefore it is an object of this invention to disclose
a desiccant composition containing calcium chloride and/or other
deliquescent salts as its major component.
[0020] It is a still further object of this invention to disclose
a desiccant composition containing calcium chloride or other deliquescent
salts mixed with a significant amount of a modified starch to form
the desiccant composition.
[0021] It is a still further object of the invention to disclose
a desiccant composition contained within a packaging material, wherein
the desiccant composition is a combination of calcium chloride or
other deliquescent salts and a modified starch.
[0022] It is a still further object of this invention to disclose
a desiccant composition containing calcium chloride or other deliquescent
salts where water absorbed does not leak from the desiccant container.
[0023] It is a still further object of this invention to disclose
a desiccant composition contained within a packaging material wherein
the desiccant composition prevents leakage of water from within
the package by use of a modified starch.
[0024] It is a still further object of the invention to disclose
a desiccant composition contained within a packaging material which
is designed for absorption of moisture in order to maintain a relatively
low humidity level.
[0025] It is a still further object of the invention to disclose
a desiccant composition contained within a packaging material which
is designed for absorption of moisture in order to maintain a relatively
high humidity level.
[0026] These and other objects and features of the present invention
will become apparent to those skilled in the art from a consideration
of the following detailed description, drawings and claims. The
description, along with the accompanying drawings, provides a selected
example of the construction of the product and process to illustrate
the invention.
SUMMARY OF INVENTION
[0027] In accordance with the present invention there is provided
a desiccant composition comprising calcium chloride and/or other
deliquescent salts and a modified starch, wherein the calcium chloride
and/or other deliquescent salts comprises at least about 5 to about
95 percent of the composition by weight and the modified starch
from about 5 to about 95 percent of composition. In the preferred
embodiment calcium chloride and/or other deliquescent salts comprises
from about 20 to about 95 percent of the composition by weight while
the modified starch comprises from about 5 to about 80 percent of
the composition by weight.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] This invention will now be described with reference to the
accompanying drawings in which:
[0029] FIG. 1 is a perspective view of the desiccant container.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0030] Although the invention is adaptable to a wide variety of
uses, it is shown in the drawings for the purpose of illustration
as embodied in a desiccant container (10) for absorbing and immobilizing
a liquid comprised of a desiccant packaging material (12) encapsulating
a liquid absorbing and immobilizing desiccant material (14). See
FIG. 1.
[0031] The desiccant packaging material (12) may comprise any conventional
packaging material. Preferably, it comprises a laminated film layer
(16) with an inner (18) and outer (20) surface preferably formed
from an uncoated microporous or nonwoven film layer sealed to an
uncoated, water vapor permeable laminate film (22) with an inner
(24) and outer (26) surface. The inner surface of the layers are
sealed at the edges as shown in FIG. 1.
[0032] Conventional microporous or nonwoven films used for the
manufacture of a laminated packaging material have been formed into
a composite film bonded to another layer of material. Conventionally,
the bonding of the two layers is accomplished by the use of an adhesive
which coats one or both of the inside surfaces of the layers. It
has been surprisingly discovered that strong, laminated desiccant
packaging materials can be produced from uncoated microporous or
nonwoven films.
[0033] The uncoated microporous or nonwoven film (16) comprises
a film having a plurality of fine openings, which film is gas permeable,
but water impermeable when there is no difference between the air
pressure outside of the film and inside of the film. The size of
the openings is preferably in the range of about 0.01 to 50 microns.
The uncoated microporous or nonwoven film may constitute a single
film layer or may comprise a laminate of separate microporous film
layers. Preferably the film is a single layer microporous film formed
from a polyolefinic material, such as polyethylene, polypropylene,
poly(fluorinated ethylene), ethylene vinyl acetate, ethylene acrylic
ester and the like. The uncoated microporous or nonwoven film may
be prepared by any conventional film forming process including cold
orientation of the film, orientation of different substance-containing
films, extraction of different substances from different substance-containing
films, extraction of different substance-containing film followed
by orientation of the treated film, cross-dispersing of a bundle
of fibers followed by heat-pressing the resulting film and any other
conventional procedures utilized for the formation of a microporous
film. Many such microporous films are commercially available and
are sold, for example, under the name Celgard.RTM. (Hoechst Celanese
Corporation), GORE-TEX.RTM. (Gore & Co. Gmbh) and Tyvek.RTM.
(E.I. DuPont). The preferred microporous film has a Gurley-type
air permeability of about 0.01 to 10000 sec./100 milliliters, preferably
1 to 1000 second/100 milliliters and most preferably less than
about 400 seconds/100 milliliters. Preferably, the microporous film
is a polyethylene or polypropylene-based microporous film and most
preferably a polyethylene spun-bonded paper such as Tyvek.RTM. 1025
BL, 1059B or 107337B manufactured by E.I. DuPont, or a polypropylene
based film, such as GDT II and GDT IV manufactured by San Ai, Ltd.
of Osaka, Japan.
[0034] The second layer of the desiccant packaging material is
preferably formed from the uncoated laminate film (22). The laminate
film can be formed of conventional polymeric materials. The critical
aspect of the composition of the laminate film is that its inner
surface (24), which is bonded to the inner surface (18) of the uncoated
microporous or nonwoven film layer at the edges of the packaging
material, must be comprised of materials which are compatible with
the composition of the inner surface of the microporous or nonwoven
film layer. Materials that can be used to form this laminate film
include conventional polyolefinic materials such as polyolefinic
polypropylene, polyolefinic polyethylene, polyesters and the like.
Preferably, the uncoated laminate film has a lower moisture vapor
transmission rate than the microporous or nonwoven film. Also preferably
the softening temperature of the uncoated laminate film is lower
than or equal to the softening temperature of the inner surface
of the uncoated microporous film. Preferably the laminate film is
comprised of a laminated film comprising a high melting or softening
point material, such as polyester, located on one side laminated
to a lower melting point material, such as polypropylene on the
opposite side. Examples of acceptable laminate film include, for
example, RPP91-1964 or RPP-31-1007a manufactured by RollPrint.
[0035] The outer surface (26) of the laminate film are preferably
formed from materials which are incompatible with the microporous
layer, such as materials having a higher melting or softening point
than that of the inner surface of the microporous film, such as
polyester material. In contrast, the inner surface of the laminate
film (24) must be formed from a material which is compatible with
the inner surface (18) of the microporous film. By having the two
inner surfaces formed from compatible materials, a strong bond is
formed between those layers when they are heat sealed together.
[0036] "Compatible" means that the materials mix on a
molecular scale and will crystallize homogeneously. Thus, while
such layers may not have precisely the same softening point, they
should have softening points which are consistent, so that the materials
will mix on a molecular level. Compatible bonds generally have a
bond strength of at least about 5 lb./in. or more. For example,
the compatible materials may include high density, low density,
or linear low-density polyethylenes as well as nonoriented, bi-axially
oriented or laminated polypropylenes. In contrast, the outer surface
of at least the laminate film should be manufactured from incompatible
materials such as polyester or nylon or a polyethylene or polypropylene
material with a higher softening point than the inner surface of
the laminate film material.
[0037] In addition, it is also critical that the inner surface
of both the laminate film and the microporous or nonwoven film be
uncoated with an adhesive. Coated film, when sealed to other coated
or uncoated films, frequently form poor quality, weak seals. In
addition, the sealing machines used for sealing coated films are
also more expensive and more difficult to operate, resulting in
greater expense for the manufacture of sealing coated films. Further,
uncoated films are generally less expensive than coated films, sometimes
by as much as 50 percent.
[0038] Suitable materials for use as the desiccant material to
be incorporated into the desiccant package include conventional
desiccating material such as silica gel, clays, natural or synthetic
zeolites, calcium chloride, alkali metal carboxylate salts of starch--polyacrylonitrile,
sodium polyacrylate, various deliquescent salts, wherein the anions
include nitrate, nitrite, chloride, bromide, fluoride, sulfate,
sulfite, thiosulfate, carbonate, carboxylate, phosphate and iodide
and wherein the cations include ammonium, alkali, alkaline earth,
earth and transition metals such as lithium, sodium, potassium,
rubidium, cesium, magnesium, calcium, strontium, barium, aluminum,
zinc, and iron and other desiccating products that absorb, gel or
thicken upon contact with water or water vapor. If low humidity
applications are desired (relative humidity less than about 20 percent),
the deliquescent salts include zinc chloride, lithium chloride,
zinc bromide, lithium bromide, zinc iodide and lithium iodide. When
medium to high humidity applications are desired (greater than 20
percent relative humidity), the deliquescent salts may include CaCl.sub.2
MgCl.sub.2 Zn(NO.sub.3).sub.2 and K.sub.2(CO.sub.3)*2H.sub.2O.
When high humidity applications are desired (higher than 50 percent
relative humidity), the deliquescent salts may include (NH.sub.4).sub.2SO.sub.4
NH.sub.4Cl, Ca(NO.sub.3).sub.2*2H.sub.2O, Mg(NO.sub.3)*6H.sub.2O,
K.sub.2HPO.sub.4 NH.sub.4H.sub.2PO.sub.4 KHSO.sub.4 Na.sub.2CO.sub.3*10H.sub.2O,
ZnSO.sub.4*7H.sub.2O, Na (C.sub.3H.sub.3O.sub.2)*3H.sub.2O, Na.sub.2S.sub.2O.sub.3
KBr, Na.sub.2SO.sub.3*7H.sub.2O, KI, NaI, NaNO.sub.2 NaF and NaHSO.sub.4.
[0039] It has been surprisingly discovered that a preferred desiccant
material can be produced from a mixture of a deliquescent salt,
such as those previously discussed, and a modified starch, most
preferably a modified corn starch, such as MIRA-SPERSE.RTM. 623
626 and 629 produced by A.E. Staley Manufacturing Company. The composition
of this desiccant material is preferably about 5 to about 95 percent
the deliquescent salt mixed with about 95 to about 5 percent of
the modified starch. Preferably, the deliquescent salt comprises
about 20 to about 95 percent while the modified starch comprises
about 80 to about 5 percent of the composition. Most preferably
the deliquescent salt comprises about 50 to about 80 percent while
the modified starch comprises about 50 to about 20 percent of the
composition.
[0040] In low humidity applications (less than 20 percent relative
humidity) the preferred deliquescent salts in order of preference
are: LiCl>ZnCl.sub.2>ZnBr.sub.2>LiBr>ZnI.sub.2>LiI.
In medium to high humidity applications (greater than 20 percent
relative humidity) the deliquescent salts in order of preference
are: CaCl.sub.2=MgCl.sub.2 >K.sub.2(CO.sub.3)*2H.sub.2O>(Zn(NO.sub.3).sub.2.
In high humidity applications (greater than 50 percent relative
humidity) the deliquescent salts in order of preference are: NH.sub.4Cl,
Na.sub.2CO.sub.3*10H.sub.2O- , (NH.sub.4).sub.2SO.sub.4 Ca(NO.sub.3).sub.2*2H.sub.2O,
Mg (NO.sub.3)*6H.sub.2O, K.sub.2HPO.sub.4 NH.sub.4H.sub.2PO.sub.4
ZnSO.sub.4*7H.sub.2O, Na(C.sub.3H.sub.3O.sub.2)*3H.sub.2O, Na.sub.2S.sub.2O.sub.3
KBr, Na.sub.2SO.sub.3*7H.sub.2O, KI, NaI, NaNO.sub.2 NaF, KHSO.sub.4
and NaHSO.sub.4.
[0041] The modified starches that are utilized in this invention
can include conventionally modified starches, oxidized starch, enzyme-converted
starches and modified starches containing functional groups such
as hydroxyl, carbonyl, amino and amino groups. The term "starch"
therefore as used throughout this specification and claims is intended
to include any member of the family of starches, or mixture of two
or more starches. The preferred starch is a modified starch, such
as an oxidized, enzyme-converted starch. The modification to the
starch may be chemical, such as by crosslinking or substitution,
or physical, such as by granulation.
[0042] Ordinary starch, such as pearl starch, is not commonly utilized
in its raw state because of its high viscosity and retrogradation,
which is a particular problem with unmodified starches. These problems
are reduced substantially with modified starches, such as hydroxyethylated
starches. As such, most industries convert their unmodified starches
to modified starches, such as oxidized, enzyme converted, phosphated
or hydroxyethylated starch. Alternatively, a further modified starch,
in the form of a cationic starch, can be used. However, the cost
of such cationic starch is significant in comparison to either unmodified
or starch. Critical to the choice of starch is its ability to absorb
water, preferably cool water, i.e., less than about 40-50.degree.
C.
[0043] In a preferred embodiment the modified starch when combined
with water must have a viscosity greater than water alone. When
measured as Brookfield viscosity, the viscosity should be at least
about 1.0 cps. The critical function supplied by the modified starch
is the ability to mix with water and thicken or gel water or the
deliquescent salt/water composition formed during the absorption
of water by the deliquescent salt.
[0044] The deliquescent salt/corn starch desiccant composition
can be used not only with the desiccant container outlined above,
but also with any conventional desiccant container utilized for
the absorption of water or water vapor.
[0045] The process for the formation of the desiccating container
comprises a number of steps. The desiccant packaging material is
first formed. To form the desiccant packaging material of the instant
invention, the uncoated microporous and nonwoven film (16) is first
formed or acquired from conventional sources. In a preferred embodiment
the microporous film is an uncoated microporous or non-woven film
such as Celgard.RTM. produced by Hoechst Celanese Corporation, Tyvek.RTM.
Nos. 1025 BL, 1059B and 1073B produced by E.I. DuPont or certain
other polypropylene-based non-woven films such as GDTI, II, IV produced
by San Ai of Osaka, Japan. As stated above, the permeability of
this microporous film should be in the range of about 1 to about
1000 Gurley seconds per 100 milliliters and preferably less than
about 400 seconds per 100 milliliters.
[0046] Following the formation of the uncoated microporous or nonwoven
film, the uncoated laminate film (22) is formed. As stated above,
this uncoated laminate film can be comprised of different layers
of the same or different materials laminated together. However,
the critical element of the composition of this material is that
the film must be uncoated and the inner surface (24) of the laminate
film, which is sealed to an inner surface (18) of the microporous
material, must be formed of a material which is "compatible"
with the inner surface of the uncoated microporous or nonwoven film.
In one preferred embodiment, the laminate film is a laminated film
containing a polyester material on the outer surface with a polypropylene
material on the inner surface, such as RPP 91-1964 made by RollPrint.
Another preferred embodiment is RPP 31-1007A, a polyethylene-based
material also manufactured by RollPrint.
[0047] Following the formation of the two layers, the edges of
the layers are sealed together by a conventional heat sealing procedure.
One of the advantages of this product is that the bond formed between
the two compatible, uncoated materials has a significantly greater
strength than conventional bonds utilizing an adhesive coating.
By utilizing the capability of compatible materials to form a strong
seal without using an adhesive, the strength of the desiccant packaging
material is significantly increased over conventional packaging
materials. In addition, these uncoated materials have a lower cost
of production and run better through the sealing equipment.
[0048] The preferred desiccant material is then placed within the
desiccant packaging. By using the preferred desiccant material (14)
formed from a deliquescent salt and a modified starch, lesser quantities
of the desiccating material may be necessary than is used in conventional
desiccating containers and still achieve the same level of moisture
absorbency.
[0049] The mixture of the deliquescent salt and modified starch
is prepared by placing the two components in a conventional mixing
apparatus, such as tumble mixer or the two components can be fed
directly into the desiccant packaging from two separate feeds. Other
than the physical mixing of the materials, no additional processing
is necessary for the deliquescent salt/modified starch composition.
This simple mixing of the two materials produces a desiccant composition
with great utility.
[0050] Following the addition of the desiccant material to the
desiccant packaging material, the remaining unsealed edges of the
desiccant container are sealed to complete the formation of the
desiccant container.
EXAMPLES
Example 1
[0051] The water absorbing capability of a desiccant combination
comprising corn starch with calcium chloride was tested. 133 grams
of a 3 to 1 mixture of calcium chloride to Mirasperse 629 modified
waxy corn starch sold by Staley Food Ingredients, Decatur, Ill.
was placed in a conventional desiccant bag for a desiccant product,
which product is sold by United Desiccants and known as "CONTAINER
DRI.RTM.". The desiccant bag was placed in environmental chamber
of 80 percent relative humidity at 25.degree. C. for about two months.
The results of this test are shown in attached Table 1.
Example 2
[0052] The same tests were run on a composition of 1 to 4 corn
starch to calcium chloride utilizing the same type of Mirasperse
624 modified corn starch as was discussed in Example 1. The water
absorption over time is shown in the attached Table 1.
Example 3
[0053] The water absorbance of a conventional 500 gram CONTAINER
DRI.RTM. desiccant product produced by United Desiccants was compared
with the products of Examples 1 and 2 using the same procedures
as were used in Example 1. The water absorption capability of this
product over time is also shown in Table 1.
[0054] In addition, the capacity of a 1/4 ratio modified starch/calcium
chloride product of Example 2 was compared with the conventional
500 gram CONTAINER DRI.RTM. product. The capacity at 40 percent
relative humidity, moisture uptake at 40 percent relative humidity,
capacity at 80 percent relative humidity and moisture uptake at
80 percent relative humidity after two months are shown in Table
2.
1TABLE 1 1:4 Corn Starch 1:3 Corn Starch to to Calcium Typical
Calcium Chloride Chloride ratio, Container Dri, Time, hr ratio,
% CAPACITY % CAPACITY % CAPACITY 5.5 8.252063 10.16 1.8 22.5 31.28282
36.4 2.5 24 36.53413 43.2 2.88 28.5 38.4096 45.04 10.59 94.5 54.83871
58.64 33 120 60.54014 64.4 38.06 150 92.04801 96.08 41.58 169 100.9002
104.08 46.11 174 108.8522 114.32 47.43 198 121.9805 116.3158 48.61
265 150.2626 147.0677 55
[0055]
2 TABLE 2 MOISTURE MOISTURE CAPACITY UPTAKE (g) CAPACITY UPTAKE
(g) at 40% RH at 40% RH at 80% RH at 80% RH 1:4 RATIO 111.4 151.7
339.4 462.1 MODIFIED STARCH/ CaCl2 IN 5 3/4 .times. 7" BAG
NORMAL 29.9 149.6 66.1 330.7 500 g CONTAINER DRI Bag
[0056] As is clear from these examples, greater water absorption
is shown for a composition of corn starch and calcium chloride in
comparison with the conventional desiccant material. This water
absorption capability is at least as good as conventional desiccant
packages conventionally sold. In addition, the desiccating composition
of Example 2 was compared with the CONTAINER DRI.RTM. product after
265 hours. Because of the capability of the starch to absorb the
water and the liquid calcium chloride on the surface of the calcium
chloride product, water did not leak from the container even after
three months.
Example 4
[0057] 100 g of calcium chloride was mixed with 25 g of modified
starch (Mirasperse 629 manufactured by Staley Food Ingredients)
and placed in a bag manufactured according to U.S. Pat. No. 5743942.
The absorption capacity measured at 25.degree. C., 80 percent relative
humidity (r.h.) after 14 days was 230 percent by weight. The bag
did not show any signs of leakage through the microporous films
or seals, and the bag contained a firm gel (viscosity 33 Pas at
5 rpm, 15 Pas at 50 rpm).
Example 5
[0058] 100 g of magnesium chloride was mixed with 25 g of modified
starch (Mirasperse 629 manufactured by Staley Food Ingredients)
and placed in a bag manufactured according to U.S. Pat. No. 5743942.
The absorption capacity measured at 25.degree. C., 80 percent r.h.
after 14 days was 305 percent by weight. The bag did not show any
signs of leakage through the microporous films or seals, and the
bag contained a firm gel (viscosity 60 Pas at 5 rpm, 23 Pas at 50
rpm).
Example 6
[0059] 100 g of magnesium chloride was mixed with 20 g of modified
starch (Mirasperse 629 manufactured by Staley Food Ingredients)
and placed in a bag manufactured according to U.S. Pat. No. 5743942.
The absorption capacity measured at 25.degree. C., 80 percent r.h.
after 14 days was 307 percent by weight. The bag did not show any
signs of leakage through the microporous films or seals, and the
bag contained a firm gel (viscosity 32 Pas at 5 rpm, 21 Pas at 50
rpm).
[0060] As is clear from Examples 4 through 6 greater water absorption
occurs with a composition of a modified starch blended with magnesium
chloride than the same modified starch blended with calcium chloride.
This increased absorption capacity per weight can find great utility
when high moisture absorption capacities are required.
Example 7
[0061] 100 g of CaCl.sub.2 ZnCl.sub.2 LiCl, (NH.sub.4).sub.2CO.sub.3
NH.sub.4Cl and NaHSO.sub.4 were individually mixed with 25 g of
modified starch (Mirasperse 629 manufactured by Staley Food Ingredients)
and placed in a bag manufactured according to U.S. Pat. No. 5743942.
The absorption capacity was measured at 25.degree. C., 80% r.h.,
25.degree. C., 20% r.h. and 25.degree. C. and 90% r.h. after 48
hours.
[0062] The following table summarizes the experimental results:
3TABLE 3 Absorption at Absorption at Absorption at Salt 20% r.h.
80% r.h. 90% r.h. CaCl.sub.2 19% 127% 270% ZnCl.sub.2 25% 84% N.d.
LiCl 30% 146% N.d. (NH.sub.4).sub.2CO.sub.3 0% 11% 70% NH.sub.4Cl
0% 12% 140% NaHSO.sub.4 0% 56% N.d. N.d. = Not determined
[0063] All except one bag did not show any signs of leakage through
the microporous films or seals, and the bags contained firm gels
(viscosity >25 Pas at 5 rpm, >15 Pas at 50 rpm). The mixture
with NaHSO.sub.4 did not form a gel, due to the chemical breakdown
of the starch used.
[0064] The table clearly shows that a combination of ZnCl.sub.2
or LiCl with starch is preferable if high capacity is needed at
low relative humidity levels.
[0065] If low absorption under humidity conditions less than about
80% r.h. is required, mixtures of starch with NH.sub.4Cl and (NH.sub.4).sub.2CO.sub.3
are preferred, as they do not start to absorb significant amounts
of moisture at less than 80% r.h. but show considerable absorption
at higher humidity levels near the dew point. |