U.S. patent application number 13/480222 was filed with the patent office on 2012-11-22 for method of rapid carbon dioxide absorption.
This patent application is currently assigned to MULTISORB TECHNOLOGIES, INC.. Invention is credited to John Crump.
Application Number | 20120294996 13/480222 |
Document ID | / |
Family ID | 44709960 |
Filed Date | 2012-11-22 |
United States Patent
Application |
20120294996 |
Kind Code |
A1 |
Crump; John |
November 22, 2012 |
METHOD OF RAPID CARBON DIOXIDE ABSORPTION
Abstract
The invention provides for a method of absorbing carbon dioxide
comprising providing a package containing a product that gives off
carbon dioxide, placing calcium hydroxide into the package, and
sealing the package to form a sealed package.
Inventors: |
Crump; John; (Buffalo,
NY) |
Assignee: |
MULTISORB TECHNOLOGIES,
INC.
Buffalo
NY
|
Family ID: |
44709960 |
Appl. No.: |
13/480222 |
Filed: |
May 24, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13028740 |
Feb 16, 2011 |
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13480222 |
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12984230 |
Jan 4, 2011 |
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13028740 |
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12751583 |
Mar 31, 2010 |
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12984230 |
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Current U.S.
Class: |
426/324 ;
206/205; 53/400 |
Current CPC
Class: |
B65D 81/267 20130101;
B65D 81/268 20130101 |
Class at
Publication: |
426/324 ; 53/400;
206/205 |
International
Class: |
B65B 55/00 20060101
B65B055/00; B65D 81/26 20060101 B65D081/26 |
Claims
1. A method of absorbing carbon dioxide comprising providing a
package containing a product that gives off carbon dioxide, placing
calcium hydroxide into the package, and sealing the package to form
a sealed package.
2. The method of claim 1 wherein the calcium hydroxide is in a
sachet that contains between 38 and 66% by weight calcium hydroxide
with the remainder silica gel.
3. The method of claim 2 wherein the calcium hydroxide is
granular.
4. Method of claim 1 wherein the calcium hydroxide has a grain size
of between 200 and 300 millimeters.
5. The method of claim 1 wherein a container for the calcium
hydroxide is formed of a carbon dioxide permeable film.
6. Method of claim 1 wherein the calcium hydroxide is embedded in a
film.
7. The method of claim 1 wherein the calcium hydroxide is extruded
with a polymer material to form a ribbon.
8. The method of claim 1 wherein the product is cheese.
9. The method of claim 1 wherein the product is selected from the
group consisting of kimchi, coffee, and fermented food.
10. The method of claim 1 wherein material to absorb oxygen is also
placed into the package.
11. A method of absorbing carbon dioxide comprising placing a
packet containing carbon hydroxide and silica gel inside a package
where it is desired to absorb carbon dioxide.
12. The method of claim 11 wherein the package further contains at
least one material selected from the group consisting of cheese,
kimchi, ground coffee, a fermented product, and electrical
components.
13. The method of claim 11 wherein the package contains between 38
and 66% by weight calcium hydroxide.
14. The method of claim 11 wherein the calcium hydroxide is
granular.
15. Method of claim 11 wherein the calcium hydroxide has a grain
size of between 100 and 300 millimeters.
16. The method of claim 11 wherein the container is formed of a
carbon dioxide permeable film.
17. A source supply container comprising a generally air and carbon
dioxide impermeable outer covering and inside the source supply
container are a multiplicity of carbon dioxide absorbing packets,
wherein the carbon dioxide absorbent packets comprise calcium
hydroxide and silica gel in a container that has at least a portion
of the surface permeable to carbon dioxide.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of U.S.
patent application Ser. No. 13/028,740 filed Feb. 16, 2011, which
is a continuation-in-part of U.S. patent application Ser. No.
12/984,230 filed Jan. 4, 2011, which is a continuation-in-part of
U.S. patent application Ser. No. 12/751,583 filed Mar. 31, 2010,
each of which is expressly incorporated by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] None.
REFERENCE TO A "SEQUENCE LISTING"
[0003] Not applicable.
BACKGROUND OF THE INVENTION
[0004] 1. Field of the Invention
[0005] The invention primarily relates to the absorption of carbon
dioxide in a food product in a storage container or package.
[0006] 2. Description of Related Art
[0007] In the packaging of foods, it is known that some food
deteriorates by reacting with oxygen during the time it is stored.
This has been treated by evacuation of packages to reduce and/or
remove oxygen before sealing, providing wax coatings on food, and
by lowering the temperature of storage. It is also known to utilize
oxygen scavengers in the packaging of vegetable and animal based
food material. There has been a particular interest in the
preventing of oxidation of ground coffee as oxidation decreases the
aroma and taste of the product. Coffee has been vacuum-packed or
packed in nitrogen to remove as much oxygen as possible.
[0008] Certain foods and manufactured goods also may emit CO.sub.2
or other volatiles either through respiration or baking or
roasting. Coffee, roasted nuts, cheese and electrical products
produce a significant amount of carbon dioxide. Roasted coffee
producers must let coffee off-gas carbon dioxide prior to packaging
or include a vent so that the package will not swell and/or burst.
The time that is necessary to off-gas carbon dioxide also
potentially allows volatile flavor compounds to escape. Employing a
carbon dioxide scavenger will allow coffee to be packaged soon
after roasting without accumulation of carbon dioxide gas. This
lack of staging/exposure for off-gassing will not only eliminate
this economically negative processing time but will also
consequently result in retaining co-offgassing compounds/volatiles
that by their nature impart desirable characteristics of the
organoleptic profile of the coffee product. There is also a problem
with carbon dioxide swelling bags of food products, such as
cheese.
[0009] Additionally, instant coffee and instant tea are quite
aromatic and pleasantly so. Because these desirable flavor
aromatics are volatile, any time lost between formation and
packaging diminishes flavor and consumer acceptance. A method of
adsorbing CO.sub.2 would allow instant coffee, instant tea, and
other foods to be packaged and preserve aroma and flavor.
[0010] In addition to ground coffee and leaf tea where residue of
used coffee grounds and tea leaves are present, there are
substantially soluble materials to make hot and cold drinks that
present storage difficulties. Instant tea, instant juices, and
instant coffee may lose flavor and aroma as well as be subject to
water absorption which will cause clumping or solidification of the
material. Other hot drinks such as cocoa, grain beverages, and hot
cold remedy beverages also suffer from storage difficulties. It
would be desirable if these materials could be stored in such a way
as to prevent their caking or agglomeration. Further, it would be
desirable if such materials could be stored in single use
containers with protection from clumping and maintaining flavor and
aroma while being ready for instant conversion to a beverage.
[0011] There is a need to provide oxygen removal, carbon dioxide
removal system, and desiccant system which is relatively
inexpensive and which is sufficiently potent to remove oxygen,
carbon, and water vapor from instant and soluble beverage
components.
[0012] In particular, there is a need for improvement in storage
techniques for single use instant beverage containers. The single
use containers are not always subject to good inventory control and
therefore may sit on shelves for a long period of time. Further, it
is not economical to package a single use containers in
sophisticated, very low oxygen, water vapor, or nitrogen
atmosphere. Typically, single use containers have about 3-5% oxygen
by weight in the atmosphere of the container and a varying content
of water vapor during packaging and shipping.
[0013] There is need for more rapid absorption of carbon dioxide in
order to prevent package swelling and flavor loss.
BRIEF SUMMARY OF THE INVENTION
[0014] The invention provides a method of absorbing carbon dioxide
comprising providing a package containing a product that gives off
carbon dioxide, placing calcium hydroxide into the package, and
sealing the package to form a sealed package.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0015] FIG. 1 and FIG. 2 are top and side views of a container for
use in the invention.
[0016] FIG. 3 is a cross-section on line A-A of FIG. 2 of a prior
art ready-to-brew coffee container.
[0017] FIG. 4 is a cross-section of a single use container with a
washer shape absorber.
[0018] FIG. 5 is an illustration of the invention utilizing a
sachet containing oxygen scavenger or carbon dioxide scavenger,
humidity regulator or a combination of scavengers and humidity
regulators.
[0019] FIG. 6 is an illustration of the invention wherein a film
having absorber properties attached to the lid of a single use
container.
[0020] FIG. 7 is an illustration of the invention where a ring,
strip, or bead of oxygen scavenger (or carbon dioxide scavenger,
humidity regulator or a combination thereof) is placed at the
bottom of the container.
[0021] FIG. 8 is a view of a carrier containing oxygen scavenger or
carbon dioxide scavenger, humidity regulator or a combination of
scavengers and humidity regulators in grooves.
[0022] FIG. 9 is a cross-sectional view of the invention carrier of
FIG. 8.
[0023] FIG. 10 is a cross-sectional view of the carrier of FIG. 8
with absorber in the grooves.
[0024] FIG. 11 is a cross-section view of a carrier of FIG. 9 in a
container.
[0025] FIG. 12 and FIG. 13 are top and cross-section views of a
carrier with a cup for containing absorber.
[0026] FIG. 14 is a cross-sectional view of a carrier with a sachet
containing at least one of an oxygen scavenger, carbon dioxide
absorber, or water vapor absorber.
[0027] FIG. 15 is a cross-sectional view of a ready to brew
container with the carrier of FIG. 14.
[0028] In FIG. 16 and FIG. 17 it is illustrated that the edges of
the carrier could be irregular.
[0029] FIG. 18 and FIG. 19 illustrates another embodiment with a
concave support having an integrally molded cup.
[0030] FIGS. 20, 21, and 22 are views of alternative bottom resting
carrier of the invention.
[0031] FIG. 23 is a cross-sectional view of a container with the
bottom-resting carrier.
[0032] FIGS. 24 and 25 are graphs showing oxygen absorption in the
examples.
[0033] FIGS. 26 and 27 are top and bottom views of a carrier of the
invention.
[0034] FIG. 28 is a cross-sectional view of the carrier of FIG. 27
on cross-section line D-D.
DETAILED DESCRIPTION OF THE INVENTION
[0035] The invention has numerous advantages over prior practices
in the art. The invention allows the formation of packaging systems
where the active component effectively maintains the freshness of
the food or medical product. The invention allows the formation of
single serving containers with an extended shelf life, while not
changing the function or design of the containers. Further, the
containers of the invention are low in cost, and the containers of
the invention further may utilize biodegradable materials for the
absorber and the container. The absorber may be provided in a form
that is particularly desirable for different food containers
depending on their need for oxygen scavenging, carbon dioxide
scavenging, and/or moisture absorbing. These and other embodiments
of the invention will be apparent from the detailed description and
drawings below.
[0036] The phrase "mammal ingestible" is intended to include
humans, pets such as dogs and cats, and farm animals. The container
of the invention could contain snack drinks, medicine, and food
products for non-human mammals. The non-human mammals could ingest
the same or different materials as the humans.
[0037] The phrase "human ingestible material" is intended to
include food, such as instant soup, instant coffee, instant fruit
and vegetable juices, and instant tea; and medical products that
may be drank or ingested after being withdrawn from the container
of the invention. While water is the liquid normally used to
dissolve or suspend the human ingestible materials, other liquids
compatible with humans, such as juice or plasma, also could be
used. Further, a flavored water or water enhanced with mineral or
vitamins could be used. The term "sorbent" or "absorber" is used to
indicate a material that scavenges (absorbs) carbon dioxide,
oxygen, or water vapor.
[0038] The formation of single serving ready-to-brew coffee that is
stored in cups with lidding films is very successful. The
containers used in single serve ready to brew coffee are quite a
complicated container containing a filter that holds the tea or
coffee which is brewed by water passing through the top of the
container and out of the bottom of the container. It is desirable
to form containers that fit the thousands of ready to brew single
use coffee machines for formation of other hot drinks. Costs could
be lowered if the filter was not utilized. Many other hot drinks
could be formed from the containers at low cost if the filter was
not utilized in the container. However, as the injection of water
and extraction of water in these machines is relatively rapid the
materials stored in the single use containers must be capable of
being rapidly dissolved or dispersed in the brief time the water is
in the cup. Therefore, the materials need to maintain their
particulate character and not form agglomerates, clumps, or cakes
that will not be readily dispersed or dissolved. The invention
provides for container with an absorber for materials that would
have a deleterious effect on the particular nature of materials in
the cup without a filter. Generally, many mammal indigestible
materials and human digestible materials will clump, cake, or
agglomerate by the action of water vapor. The absorption of these
gases in the container would also generally help preserve the
flavor and aroma of human indigestible materials dispensed
utilizing the container. The taste is more consistent and the shelf
life is longer.
[0039] The invention provides a cost-effective solution that does
not require redesign of the ready-to-brew containers. Coffee
machines are designed to accept cups of known design and it is not
practical to change the design of the cup. Further, it is desirable
that biodegradable materials be utilized as the cups are discarded
after one use. The human ingestible materials that do not need to
be steeped in a filter, include material such as instant coffee,
instant tea, fruit and vegetable juices, cold remedies, bullion,
chicken broth, some narcotics, and cocoa. These materials may leave
the container either as a solution or a dispersion in the hot
water.
[0040] FIGS. 1 and 2 show a top and side view of a prior art
ready-to-brew coffee container 10. The container 10 has a lid 12
and exterior sides 14. During use, the lid 12 is pierced as is the
bottom 16. Water is injected through the lid 12 and coffee is
removed from the bottom 16. Cross-sectional line A-A is generally
through the center of the container 10.
[0041] FIG. 3 is a cross-sectional view of a prior art
ready-to-brew container 10. The container 10 has a filter 18 that
is sealed at 22 to the sidewall of the container 14. The ingestible
material level in the containers is represented by M, and in use
the lid 12 of the container is pierced by means not shown and hot
water is injected into the container. The bottom of the container
16 is also pierced, by means not shown, and ingestible material in
water is withdrawn from the bottom. The filter divides the cup into
two spaces A and B. This invention relates to improvements in the
ready-to-brew coffee containers as well as other food and medicine
containers in which no filter is present. In the invention
structures like portions as in the prior art cup are identically
numbered as in FIG. 3.
[0042] FIG. 4 illustrates an embodiment of the invention where a
washer-shaped absorbent 72 is placed in a single use container. The
washer-shaped absorbent has a hole 74. The container will be
pierced in the portion of bottom 16 where the hole is located and
the mammal ingestible fluid will drain from the container 10. The
absorbent washer is a polymer that has the absorbents for at least
one of water vapor, oxygen, and carbon dioxide mixed into the
polymer prior to formation of the washer-shaped absorbent 72.
[0043] The washer-shaped absorbent may be made with the techniques
described below. The washer and other shaped composite polymer and
absorber articles below also may be formed by the technique of U.S.
Pat. No. 7,595,278 to Powers, hereby incorporated by reference.
Note, Examples 3 and 4 of U.S. Pat. No. 7,595,278 disclose a
moisture absorbing composite material containing propylene and
molecular sieve material.
[0044] FIG. 5 illustrates the cross-section of an embodiment in the
invention wherein a sachet 24 has been inserted into the container
10. This sachet 24, which when oxygen absorption is desired,
contains an oxygen absorber 28 such as iron in combination with
salt and electrolyte. The materials in the sachet 24 will rapidly
absorb oxygen during storage. The rapid absorbing of oxygen is
beneficial as instant coffee and cocoa also will absorb oxygen, but
the oxygen scavenger in the sachet is many times greater in rate of
oxygen absorption than the instant coffee. The surface of the
packet 26 is formed material that is vapor permeable but not water
permeable. It maintains its integrity above the temperature of
boiling water. The sachet 24 could be placed either on top of or
below the material M in the container.
[0045] Alternatively or additionally, the sachet may contain a
CO.sub.2 absorber capable of absorbing the CO.sub.2 emitted from
the instant coffee or instant tea thereby minimizing loss of flavor
through volatilization. It is also possible that a carbon dioxide
absorbing sachet could be used in addition to the oxygen absorbing
sachet. Water absorbing material could be in a sachet either alone
or in addition to the other absorbers.
[0046] Alternatively or additionally, the sachet may contain a
moisture regulating formulation capable of maintaining the water
activity of the instant coffee, cocoa, or other food product such
as instant tea, at an optimum level so that it is not too dry or
too moist which can affect the extractability of the flavor
elements.
[0047] In a preferred form for rapid carbon dioxide absorption the
sachet, or other container for carbon dioxide absorbing material,
will contain calcium hydroxide, preferably in combination with
silica gel. At least a portion of the wall of the container will be
permeable to carbon dioxide. It is been found that calcium
hydroxide absorbs carbon dioxide much faster than the
conventionally used calcium oxide. Calcium hydroxide will be
federalized to form calcium hydroxide which will absorb carbon
dioxide. However the delay in acquiring water and reacting with
water to form calcium hydroxide is avoided if the carbon dioxide
absorber is initially charged with calcium hydroxide. The calcium
hydroxide is granular form. In a preferred form the package
contains between 38 and 66% by weight of calcium hydroxide when it
is combined with silica gel. In the preferred ratio about 100
cm.sup.3 of carbon dioxide is absorbed per gram of the calcium
hydroxide and silica gel blend. The ratio of silica gel to calcium
hydroxide will be maintained even if oxygen absorbers and or water
absorbers are also present in the container.
[0048] A suitable grain size of calcium hydroxide is between 100
and 300 mesh (______ and ______ millimeters). A preferred grain
size of calcium hydroxide is about 200 mesh (______ millimeters) as
this has low-cost and will provide good flow ability for
manufacturing. The grain size of the silicon gel is selected to
provide the desired good dry flow characteristics when combined
with the calcium hydroxide. Generally a silica gel size of between
50 and 200 mesh (______ and ______ millimeters) is preferred
because of good full flow when mixed with the calcium hydroxide.
The sodium dioxide absorbs water which is a product of the
absorption of the carbon dioxide by the calcium hydroxide. It has
been surprisingly found that the cost of calcium hydroxide is
similar or lower than the calcium oxide which has been used in the
prior art. The handling of calcium hydroxide grains is also similar
to the handling of the previous calcium oxide. Therefore, the use
of calcium hydroxide provides the benefit of faster carbon dioxide
absorption activity without increasing cost of the product.
[0049] While set forth as utilized with a sachet such as
illustrated in FIG. 5, it is also possible that the calcium
hydroxide could be utilized in the other manners, such as embedded
in a permeable film, extruded in a gas permeable polymer as a
ribbon or film, or placed into a container with a permeable side or
top. The methods of containing the carbon dioxide absorber are
disclosed herein. In any of these methods of using or packaging the
calcium hydroxide it will provide more rapid absorption of carbon
dioxide than calcium oxide. If a slower absorption of carbon
dioxide is suitable then the known calcium oxide may be utilized
successfully.
[0050] The sachets, ribbons or containers containing calcium
hydroxide for carbon absorption may be shipped in source supply
containers. The source supply containers further contain an inner
ceiling bag of substantially air and carbon dioxide impermeable
polymer sheet. Depending on the type of manufacturing utilizing the
calcium hydroxide carbon absorbers they may be in the form of
sachets, ribbons, or containers having at least one permeable side.
Further the sachets may be linked together in a role and severed
immediately prior to use.
[0051] In the embodiment of FIG. 6, the container has been provided
with an absorber film 29 that is adhered to lid 12. The absorbent
film would be adhered to the lid material 12 prior to the lid being
placed on to the container. The film may be cast, laminated or
extrusion coated onto the lid or preformed and attached to the lid
by adhesives, ultrasonic sealing, or heat sealing. This embodiment
has the advantage that absorber film is added to the lid prior to
the packaging of the mammal ingestible material. The absorbent film
29 may consist of multilayer structure in which the absorber is in
the inner layers of the structure. The film may be provided with an
abrasion resistant layer or a slippery layer, not shown, that will
provide abrasion resistance or slippage so that the mammal
ingestible material will not be able to remove the oxygen, carbon
dioxide, and/or oxygen absorbent (scavenger) materials from the
film. The resistance or slippage layer may be formed of
polyethylene, polypropylene, polyamide and their copolymers.
Conventional slip additives may be added into the layer that
contacts the mammal ingestible material to result in a coefficient
of friction of 0.5 or below, preferably 0.3 or below. The film may
be an oxygen absorbing film, it is also possible that the film only
contain CO.sub.2 absorbing materials or only water vapor absorbing
materials. It is further possible that it contain any combination
of carbon dioxide, water vapor, and oxygen absorbing materials.
[0052] In the embodiment of FIG. 7, the oxygen scavenger or other
absorber is placed on the bottom 16 and the bottom edge 34 of cup
10. The scavenger 32 may be placed there by a variety of
techniques, but an extrusion technique, such as utilized for hot
melt adhesive would be quick and could be done during manufacturing
prior to filling the container 10. A preformed scavenger ring of
sorbent film also could be attached to the bottom interior edge 34
of the cup. Placement of the sorbent also could be performed by
other extrusion coating methods. The extrusion materials include
hot melt polymers as well as plastisol materials that would cure in
place.
[0053] FIGS. 8 and 9 are a top view and a cross-sectional view of a
carrier for absorber 23 for use in the container of the invention.
The support has grooves 29 and 33. The support further is provided
with a hole 41. In the cross-sectional view of FIG. 8, carrier 23
has been provided with a gas permeable, water impermeable cover
sheet 35. Further, the grooves 29 and 33 are then filled with at
least one of particulate oxygen scavenger material, carbon dioxide
absorbent material, and water absorbent material. In FIG. 10 is
illustrated the carrier 23 with grooves 33 and 29 filled with
particulate absorber 29. The absorber 29 and carrier 23 are then
covered with a sheet of material that is impervious to water but
will pass gases such as oxygen and carbon dioxide. After placement
on the carrier, the sheet is cut away to open the hole 41 if the
sheet has not been previously cut to size. This embodiment allows
the use of particulate absorber.
[0054] FIG. 11 illustrates the cross-section of an embodiment in
the invention wherein a carrier 23 has been inserted in container
10. This carrier 23 contains an oxygen absorber 45 such as iron in
combination with salt and electrolyte in grooves 29 and 33. The
grooves 29 and 33 are covered by gas permeable and liquid water
impermeable film or cloth 35. The center hole drain 36 provides for
draining of the human ingestible material. Drain hole 41 is not
covered by the permeable film. The materials in the grooves 29 and
33 will rapidly absorb oxygen, carbon dioxide, or water vapor
during storage. The rapid absorbing of oxygen is beneficial as
cocoa and instant coffee also will absorb oxygen, but the oxygen
scavenger in the carrier 23 is many times greater in rate of oxygen
absorption than the instant coffee. The surface film 35 is formed
material that is vapor permeable but not water permeable. It
maintains its integrity above the temperature of boiling water.
[0055] FIGS. 12 and 13 illustrate a carrier 40 that contains a cup
42 in the hole 41 of the carrier. The carrier 40 is provided with a
multiplicity of small drain holes 44. The carrier 44 is provided
with a cup 42 that fits into the hole 41. As shown in FIG. 13, the
carrier has a cup 42 which is covered with a gas permeable cover
48. The cup contains at least one of a particulate oxygen
scavenger, carbon dioxide scavenger, and water vapor absorber 46.
The gas permeable film or cover may be formed of a gas permeable
film or bonded fiber material such as Tyvek or Gore-Tex. In FIG.
14, there is illustrated a carrier containing a cup 42. A sachet 54
that contains particulate absorbent is in cup 42. The sachet is
formed of a permeable film or fabric. In FIG. 15, there is
illustrated the support 40 utilized in a single use container of
the invention.
[0056] The carrier 40 is designed to be held by gravity in the
single use coffee container 10 which narrows towards the bottom 16.
It is also possible that a stop could be molded into the side of
the container on which the carrier would rest. It is also possible
that the carrier 40 could be held in place by adhesive. Further, it
is possible that the carrier could be provided with a jagged edge
or wavy edge to aid in draining of the coffee from a single use
container. FIG. 16 is an illustration of a wavy edge of a carrier
58. FIG. 17 is an illustration of a jagged edge of a carrier 62. It
is also desirable that the grooved carrier 23 be perforated to aid
in drainage. The perforation would normally need to be accomplished
after the grooves have been filled and covered.
[0057] In FIG. 18 is illustrated a concave carrier 64 that has the
cup 42 integrally molded with the carrier 64. The concave carrier
64 is suspended in the package so as to be concave when viewed from
the top of the package. A concave carrier may aid in centering of
the carrier in the container. In the top view of a carrier such as
64 in FIG. 19 shows multiple large drain holes 66 for the liquid
human ingestible material to pass through. The cup 42 may be
covered with fabric after filling the particulate matter.
Alternatively, the cup could contain a sachet, capsule, or polymer
member comprising scavengers and/or absorbents. The cup further
could have a snap fit gas permeable and liquid impermeable lid.
[0058] In FIGS. 20-22 is shown in the embodiment of carrier 70 of
the invention with slots 72 for drainage. FIG. 21 is a top
perspective view of the carrier and FIG. 22 is a bottom perspective
view. The carrier 70 is designed to sit on the bottom of the
container with the bottom 76 of the outer ring 78 on the bottom 16
of the container. The upper surface of ring 78 is surface 77. The
cup 42 may have a gas permeable film attached to surface 82 to seal
in an absorber or scavenger that has placed in cup 42. A snap cap
of vapor with permeable material is a preferred embodiment. Cup 42
is provided to contain at least one of the oxygen scavenger, carbon
dioxide absorber, water absorber or other treatment material for
human ingestible material. A cap 82 for cup 42 alternatively may be
welded to cup 42, snapped in place, or adhesively connected. The
carrier 70 further could be made with an opening and have a
preformed can of treatment material bonded in place, preferably by
spin welding. A gas permeable snap on cap 82 for the cup 42 is
preferred for ease of formation of the carrier.
[0059] FIG. 23 is a cross-section of a container using the carrier
70. As shown, the carrier 70 rests on the container bottom 16 with
surface 76 of the carrier. The cup 42 has permeable cap 82. The cup
42 contains absorbent members 84. The carrier 70 does not interfere
with piercing the middle of the bottom of the container 10 for
drainage.
[0060] While the above illustrations have shown particulate
absorbents it is also possible that the absorbents could be
incorporated into a plastic film, placed in a permeable capsule or
pressure formed into a tablet. The tablet then may be covered with
a gas permeable film or coating. The tablets, pieces of film,
extruded polymer, or sachet as illustrated could be it in the cup
of the carrier.
[0061] The cup 42 is shown as a separate member that is inserted
into the carrier 40. The cup may be held in the carrier by spin
welding, ultrasonic welding or pressure fitting. However, the cup
in another preferred embodiment could be integrally molded with the
absorber carrier. Further, it is possible that the carrier itself
could be formed of a polymer that contains at least one of oxygen
scavenger, carbon dioxide absorber, and dehumidifier material. If
the support itself was formed of a material that absorbs oxygen
and/or carbon dioxide it would only be necessary to form holes in
the support for drainage and/or have irregular edge on the carrier.
No cup would be necessary. Further, while the cup is illustrated in
substantially the same height as the thickness of the support in
several embodiments, it can be made deeper in order to hold more
absorbents. Further the cup could be closed by a plug or a fitted
cover. The cup also could be a preformed gas permeable can that is
bonded to the carrier.
[0062] FIGS. 26, 27, and 28 illustrate carrier 90 in an embodiment
of the invention. Carrier 90 in FIG. 26, which is a top view, has a
reinforcing ring around hole 92. The carrier 90 has a foraminous
area 102 that has holes 96 separated by pieces of polymer 104. The
holes that are in the foraminous portion 102 are numerous leaving
just enough polymer 104 to support the conical shape. In use,
carrier 90 sits on the bottom of the cup on the lower ring 98. The
carrier is convex as seen from the top of the container. When
forming a preferred carrier for water vapor absorption, the
preferred polymer is propylene blended with calcium oxide and/or
molecular sieve material. The carrier 90 also could be utilized for
oxygen or carbon dioxide absorption with absorbers of these gases
in the polymer.
[0063] It is possible to utilize material containers for ingestible
drinks that are quite permeable to gases such as oxygen, water
vapor, and/or carbon dioxide. The containers are then sealed inside
a bag that is impermeable to oxygen and carbon dioxide and water
vapor. The bag has oxygen absorbers and/or carbon dioxide absorbers
and/or water absorbers placed into the bag before it is sealed. The
bag is opened immediately before use so that the ingestible drink
such as cocoa does not lose freshness before use. Absorbers in the
cup would prevent deterioration after the bag is opened and the
individual containers are stored until use. The permeable container
may be formed of a biodegradable material, such as poly lactic acid
(PLA) or a copolymer of PLA and another polymer such as
polyethylene or an acrylic. Alternatively, the cups could be formed
of a thin, low cost or very thin polymer, permeable to oxygen,
carbon dioxide, and water vapor. The bag may be foil, polyvinyl
alcohol, or high-density polyethylene, preferably in layers that
allow the best barrier property to be achieved in the bag.
[0064] Any suitable resin may be utilized in the invention for the
polymer that holds the oxygen scavenger or other sorbent. The
polymer holds the sorbent so that it will not be carried into the
coffee or other food product when the container is used, but allows
gas to reach the absorbent. Polymers useful for making the oxygen
scavenging and absorbent articles can include common polyolefins
such as low-density polyethylene (LDPE), high-density polyethylene
(HDPE), polypropylene (PP), polystyrene (PS), high impact
polystyrene (HIPS), polycarbonates (PC), poly(methyl methacrylate)
(PMMA) and their derivatives or copolymers.
[0065] Polymers suitable for the invention and biodegradable
include common polymers generated from renewable resources and
biodegradable polymers such as polylactic acid copolymers, starch
based polymers such as thermoplastics starch, polyhydroxyalkanoate
(PHA), polyhydroxybutyrate (PHB). Biodegradable polymers that are
petroleum based such as polyethylene oxide and polyvinyl alcohol
(PVOH) are also included.
[0066] The invention uses common plastic article fabrication
processes that include extrusion, injection molding, extrusion
coating, lamination, tableting and compounding to form the sorbent
structures including oxygen scavengers, CO.sub.2 absorbers, and
moisture regulators.
[0067] While the invention is discussed with respect to the
utilization of a food container for instant coffee, instant tea,
and cocoa, the concepts and container of the invention are also
suitable for other uses. The containers disclosed would be suitable
for use in other food products where water or other liquids are
added to the material contained in the container and wherein a
changed liquid is withdrawn after dissolving or dispersing the food
product. Typical of such materials would be tea, soup, milk
components, and soup broth. The containers also could be used for
medical products that are shipped as solid particles or are
concentrated and then a carrier liquid is passed through the cup
and through the concentrated liquid or solid particles to result in
a medicinal liquid. An example of this would be drugs, such as
powdered narcotics, such as morphine and methadone hydrochloride,
and materials utilized as radiology tracers. They could also be
used for alcoholic mixers.
[0068] The calcium hydroxide utilized for absorption of carbon
dioxide may be utilized as discussed in the previous paragraph.
Further the calcium hydroxide may be utilized in absorption of
carbon dioxide from other food materials that are not packaged for
dissolving in a fluid. These would include food materials such as
cheese, kimchi, coffee, and any fermented product. The calcium
hydroxide products for carbon dioxide absorbers also may be
utilized for absorbing carbon dioxide given off by electrical
products. The calcium hydroxide materials may be utilized as a
preferred material for any storage where rapid absorption of carbon
dioxide after packaging is desired.
[0069] The invention method of placing scavenger materials in a
container, as stated above, could be used for packaging of products
that are sensitive to moisture. Such products include many
medicines and food products. Such food products as flour, drink
mixes, gelatin desserts, and salt or other seasonings are subject
to deterioration if moisture is present in the container. Moisture
absorbent materials such as disclosed in U.S. Pat. No.
5,322,701--Cullen, herein incorporated by reference, could be
placed into containers to enable longer storage of such materials.
Suitable moisture absorbent materials include calcium oxide, silica
gel, molecular sieve, and cellulose fibers.
[0070] The following are methods for making a solid oxygen
absorbing composition or coating for use in the invention.
[0071] The oxygen scavenger may be in the form of a powder blend in
a sachet or a pressed solid formed from compressed particles and
binder. A method of making a compressed or pressed oxygen absorbing
disc, tablet, wafer, washer, or capsule is as follows. Forming a
blend of powdered absorbent based on iron powder with sodium
chloride as an electrolyte, silica gel, and a binder that does not
need to be heated very high in temperature. The binder can be a
fine powdered polyethylene that will soften when under a pressure
of between 3,000-50,000 pounds per square inch. The composition can
also be heated to set or cure the binder but it cannot be heated
above the boiling point of water to keep the moisture in the
carrier. A suitable composition by weight would be about 18%
polyethylene, 40% iron powder, 30% silica gel, 8% water and 2%
sodium chloride. It is best to use a resin binder with a softening
point above the boiling temperature of water.
[0072] A method for making an oxygen absorbing compound would be to
put the oxygen absorbing composition in a thermoplastic material so
that the oxygen absorbing compound could be filled into a container
as a liquid ring and allowed to set or harden. This composition
would be by weight about 40% thermoplastic resin, 30% iron powder,
20% silica gel, 9% water and 1% sodium chloride. An additive, such
as CaCO.sub.3, clay, or talc, could be used to increase the
porosity of the resin and to increase the rate of oxygen
absorption. This absorbent composition could be deposited into a
container or made into a tape that could be put onto the inner
sides of the container. The thermoplastic resin can be a vinyl
acetate, ethyl vinyl acetate, polyurethane or combinations
thereof.
[0073] Another method for making an oxygen absorbing composition is
dispersing the oxygen absorbing composition into a
polyvinylchloride plastisol. These plastisols are used as cap
liners and as gaskets in caps and jar lids. This oxygen absorbing
plastisol composition may then be put into the cup as a liner, a
ring or coating along the sides or bottom edge of the cup. This
composition would be semi liquid and could be placed into the cup
and allowed to set. The plastisol may be selected from high-density
polyethylene, high density polypropylene, acrylic vinyl acetate
ethylene copolymer, ethylene vinyl acetate, vinyl acetate
homopolymer, acetate ethylene copolymer, plasticized vinyl
chloride, oxidized polyethylene homopolymer and polyurethane. The
preferred plastisol is polyvinyl chloride as it does not react with
foods and is resistant to the temperature of boiling water. The
oxygen absorption composition can be up to 75% by weight with the
other 25% being the polymer. One composition was 10.35 grams of
polyvinylchloride plastisol, 12.51 grams of iron powder containing
2% by weight sodium chloride.
[0074] Illustrative of a plastisol material is polyvinyl plastisol
in an amount of 10.35 grams was blended with 12.51 grams of 200
mesh iron powder containing 2% by weight sodium chloride. The
blending was done with an electric high-speed mixer. A sample of
the resulting composition was coated onto a container cap. The rate
of oxygen absorption was measured over time.
TABLE-US-00001 Sample 1 Sample 2 Sample 3 Sample 4 Composition 1.47
grams 1.71 grams 1.51 grams 1.56 grams weight CC of oxygen 10. 10.
10. 10. absorbed after 22 hours CC of oxygen 15. 14. 15. 15.
absorbed after 46 hours CC of oxygen 24. 22. 24. 23. absorbed after
96 hours CC of oxygen 37. 32. 37. 35. absorbed after 184 hours CC
of oxygen 37. 32. 37. 35. absorbed after 234 hours CC of oxygen 51.
41. 48. 47. absorbed after 330 hours
[0075] The test vessel contained 500 cc of air or 100 cc of oxygen.
The test was conducted at room temperature with a moisture source
in the test vessel.
[0076] Another invention composition would be to disperse the
sorbent composition in a multiple component carrier such as an
emulsion, dispersion, suspension or other mixtures. By dispersing
the sorbent in such a multi component system the resulting
composition can be more easily applied to a cup as an oxygen
scavenger or sorbent coating. These types of coatings can contain
more of the oxygen absorbing composition and have greater
permeability for oxygen. By not fully drying the water based
systems we can have a self activation and self reacting oxygen
absorbing coating. Glucose oxidase can be used in place of the
iron. A xanthan gum emulsion, alginate emulsion or microcrystalline
cellulose system can also be used. This system can also contain
water in the iron based oxygen absorbing system. Adhesive based
emulsion can also be used such as acrylic polymer emulsions in
water, a polyvinyl acetate in water emulsion, and a vinyl acetate
ethylene copolymer in water emulsion can be used. The oxygen
absorbing composition would be an iron powder with sodium chloride
as an electrolyte and a moisture carrier. The moisture carrier can
be silica gel, hydrogel or any other moisture carrier that can hold
moisture. In oxygen absorbers, it is also possible to not fully dry
the moisture out of the emulsion thereby leaving some moisture in
the coating. An alginate gel would be by weight percent 2.25%
sodium alginate, 1.0% polysorbate 80, 0.2% sodium propionate and
96.55% distilled water. A xanthan gum emulsion would be by weight
2.0% xanthan gum, 43% isopropyl alcohol and 55% water. These two
emulsions could be combined 1 part emulsion with 1 part oxygen
absorbing composition composed of 99% iron powder and 1% sodium
chloride as the electrolyte. The oxygen absorbing composition can
be a fine iron as fine as 2-5 microns in particle size to improve
the clarity of the oxygen absorbing coating or oxygen absorbing
compound. A thin film layer or coating can be put over the final
coating to insure that no oxygen absorbing ingredients or sorbents
migrate out over time. This thin film cover can a cellulose acetate
polymer, vinyl acetate ethylene copolymer, vinyl acetate
homopolymer, acetate ethylene copolymer, plasticized vinyl chloride
polymer, acrylic polymer or an oxidized polyethylene
homopolymer.
[0077] The water absorbers and carbon dioxide absorbers may be
placed into the polymer by a substitute for the oxygen absorbers.
The preferred water vapor absorbers are silica gel and molecular
sieve materials.
[0078] Any suitable transition metal, typically including zinc,
copper, iron, cobalt and zirconia, may be utilized in the oxygen
scavenger of the invention. The preferred oxygen scavenger of
reduced iron powder preferably has 1-200 um mean particle size,
more preferably 5-50 um mean and most preferably 10-40 um mean. The
iron can be mixed with salt or a combination of different
electrolytic and acidifying components. The iron particles can, in
a preferred embodiment, also be coated with electrolyte salt. The
combination and relative fraction of activating electrolytic and
acidifying components coated onto the iron particles can be
selected according to the teachings of U.S. Pat. No. 6,899,822 and
co-assigned published U.S. Patent Applications 2005/0205841 and
2007/020456, incorporated herein by reference. The coating
technique is preferably a dry coating process as described in the
references above.
[0079] The salt can be any salt such as sodium, potassium or
calcium based ionic compounds that are soluble in water. Typical
examples include NaCl, KCl, Na.sub.2HPO.sub.4 and others. A mixture
of separate electrolytic and acidifying salt components can be
advantageously used in the formulation as described in prior art.
Sodium chloride is preferred because it is effective and low in
cost.
[0080] The oxygen scavenging fabricated article may contain
moisture regulators based upon silica gel, molecular sieve,
activated carbon, clay or other minerals. The compounds may contain
various levels of water to achieve water activities ranging from
0.01 to 0.85.
[0081] The film/tape/ribbons/wafers/washers used in the invention
may be a single or multilayer films that are porous or solid, and
consisting of iron-based oxygen scavengers and electrolytes, such
as disclosed in co-assigned U.S. patent application Ser. No.
12/416,685, filed Apr. 1, 2009, hereby incorporated by reference
and U.S. Patent Publication No. 2010-0255231, published Oct. 7,
2010, also hereby incorporated herein by reference. The film
optionally consists of moisture regulators with a chosen water
activity. The film may be in circular or strips that can be fitted
into a container as a bent strip. Multilayer film is preferred with
oxygen scavenger or other absorber embedded inside the film and not
exposed on film surface. Films with some porosity or voids are
preferred to facilitate the rate of oxygen, carbon dioxide, or
water vapor absorption. Moisture regulator can be incorporated into
the film during extrusion or from post-extrusion processing. The
films can be laminated to the lids or container sides.
[0082] The insert may be a ring shaped oxygen scavenging article as
in FIG. 4 with a ring diameter smaller than the bottom of the
container such that the insert can be laid flat inside the
container. The insert can be fabricated by die-cut from the films
above or by other fabrication means such as injection molding and
compression molding
[0083] In the embodiment using strands/paste, such as in FIG. 7 or
in cup 42, a section of elongated or shaped oxygen scavenging
material that consists of oxygen scavenger, salt and moisture
regulators may be utilized. A method of making such a strand is by
melt extrusion. The polymer may be polyethylene, wax, polyethylene
glycol, cellulosic polymers, polylactic acid, and starch-based
copolymers. The moisture regulator may be salts, silica gel, clay,
molecular sieve or like that contains certain levels of
moisture.
[0084] A method to remove CO.sub.2 in the package is described as
follows: using a scavenger specifically designed for CO.sub.2
absorption. A packet made of a gas permeable polyolefin film
containing carbon dioxide absorbing particulates is packaged in a
single use container to absorb the off-gasses. The preferred packet
will have high gas permeation and low water vapor permeation
properties. The absorber will be capable of absorbing a high
concentration of CO.sub.2 and not interfere with the aromatics
components of the human ingestible material. The CO.sub.2 absorber
can contain certain amount of calcium hydroxide, silica gel and
water, with other ingredients. Optionally calcium hydroxide may be
replaced with other hydroxides such as sodium hydroxide and
potassium hydroxide or mixtures of these and other hydroxides.
Optionally, alkaline, alkaline earth or metal oxides may be used in
conjunction with or replacing hydroxides. The oxides include but
not limited to calcium oxide, aluminum oxide and magnesium oxide.
These oxides may be used in mixture format. For reference, the
range and formulations useful as CO.sub.2 absorber are described in
U.S. Pat. No. 5,322,701 assigned to Multiform Desiccants, Inc.,
hereby incorporated by reference.
[0085] As described for the oxygen absorbing materials above the
oxygen and carbon dioxide scavenging formulations may be packaged
in a format other than a packet. The carbon dioxide scavenging
formulations may be enclosed in oxygen or carbon dioxide permeable
capsule or a tablet that may be coated with a permeable or
semi-permeable polymer material. Any resin or polymer permeable to
oxygen and/or carbon dioxide may be used to coat the tablets. Water
base polymer coating of the tablets is preferred. Preferred coating
polymers are hydroxyl propylmethyl-cellulose or acrylic water base
coatings. They may also be fabricated in a compact form, such as a
washer, wafer, disc or platelet, wrapped with a coating or polymer
film that is gas permeable or semi-permeable. The coating method of
making the disc, platelet or tablet can include dip coating, spray
coating, flash coating, spin coating or any other known methods
that are applicable to forming the product. The film method can
include overcoating, lamination, multilayer lay up followed by
die-cutting, and any other known methods that can make film
composite layered articles. The methods of forming oxygen
absorbents above may be used for forming sorbent materials for
CO.sub.2 absorbents and water vapor absorbents.
[0086] Alternatively or additionally, the sachet, grooves, film, or
cup may contain a CO.sub.2 absorber capable of absorbing the
CO.sub.2 emitted from the coffee permitting it to be packaged a
short time after roasting thereby minimizing loss of flavor through
volatilization. It is also possible that a carbon dioxide absorbing
sachet could be used in addition to the oxygen absorbing
sachet.
[0087] Alternatively or additionally, sachet, the grooves, film or
cup may contain a moisture regulating formulation capable of
maintaining the water activity of the instant coffee or other food
product such as instant tea, at an optimum level so that it is not
too dry or too moist which can affect the extractability of the
flavor elements.
[0088] The container may be provided with an oxygen absorbent film
or other sorbent film that is in cup 42. The film may be cast,
laminated or extrusion coated into the cup or preformed and
attached to the cup by adhesives, ultrasonic sealing, or heat
sealing. The oxygen absorbent film may consist of multilayer
structure in which the oxygen absorbent is in the inner layers of
the structure. The film may be provided with an abrasion resistant
layer or a slippery layer, not shown, that will provide abrasion
resistance or slippage so that the filter's movement will not be
able to remove the oxygen absorbent (scavenger) materials from the
film. The resistance or slippage layer may be formed of
polyethylene, polypropylene, polyamide and their copolymers.
Conventional slip additives may be added into the layer that
contacts the coffee to result in a coefficient of friction of 0.5
or below, preferably 0.3 or below. While described with reference
to an oxygen absorbing film, it is possible that the film only
contain CO.sub.2 absorbing materials, or water absorbing materials.
It is further possible that it contain a combination of carbon
dioxide, oxygen absorbing, and water absorbing materials.
[0089] The oxygen scavenger or other gas absorber may be placed in
cup 42 by a variety of techniques, but an extrusion technique, such
is utilized for hot melt adhesive is quick and may be done during
manufacturing prior to the support 40 being put in the cup. The
extrusion materials include hot melt polymers as well as plastisol
materials discussed above that would cure in place.
[0090] Any suitable resin may be utilized in the invention for the
carrier and the absorbent film polymer that holds the oxygen
scavenger, carbon dioxide absorbent, water vapor absorber, or other
sorbent. The polymer holds the sorbent so that it will not be
carried into the instant coffee, cocoa, or other food product when
the container is used. Polymers useful for making the oxygen
scavenging and absorbent articles can include common polyolefins
such as low-density polyethylene (LDPE), high-density polyethylene
(HDPE), polypropylene (PP), polystyrene (PS), high impact
polystyrene (HIPS), polycarbonates (PC), poly(methyl methacrylate)
(PMMA) and their derivatives or copolymers.
[0091] Polymers suitable for the invention container and carriers
and biodegradable include common polymers generated from renewable
resources and biodegradable polymers such as polylactic acid
copolymers, starch based polymers such as thermoplastics starch,
polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB).
Biodegradable polymers that are petroleum based such as
polyethylene oxide, polyvinyl alcohol (PVOH) are also included.
[0092] The invention uses common plastic article fabrication
processes that include extrusion, injection molding, extrusion
coating, lamination, tableting and compounding to form the sorbent
structures including oxygen scavengers, CO.sub.2 absorbers, and
moisture regulators.
[0093] The oxygen scavenging fabricated article may contain
moisture regulators based upon silica gel, molecular sieve,
activated carbon, clay or other minerals. The compounds may contain
various levels of water to achieve water activities ranging from
0.01 to 0.85. In the event that only protection from deterioration
of the mammal ingestible material by action of water vapor is
desired the n the absorber and moisture regulator silica gel,
molecular sieve, activated carbon, clay, or other minerals may be
used without the oxygen scavenger or carbon dioxide absorber.
Silica gel is preferred as it is low in cost, effective, and safe.
Moisture absorbent materials such as disclosed in U.S. Pat. No.
5,322,701--Cullen, herein incorporated by reference, could be
placed into containers to enable longer storage of moisture
sensitive materials.
[0094] The film/tape/ribbons for use in cup 42 of the invention may
be a single or multilayer films that are porous or solid, and
consisting of iron-based oxygen scavengers and electrolytes, such
as disclosed in co-assigned U.S. patent application Ser. No.
12/416,685, filed Apr. 1, 2009, hereby incorporated by reference.
The film optionally consists of moisture regulators with a chosen
water activity. Multilayer film is preferred with at least one of
water vapor absorber, carbon dioxide absorber, or oxygen scavenger
embedded inside the film and not exposed on film surface. Films
with some porosity or voids are preferred to facilitate the rate of
absorption. Moisture regulator can be incorporated into the film
during extrusion or from post-extrusion processing.
[0095] The following examples are used to illustrate some parts of
the invention. The Examples are illustrative and not exhaustive of
the embodiments of the invention. Parts and percentages are by
weight unless otherwise indicated. The examples use ground coffee
as the test material to show the oxygen scavenging effectiveness.
As they are effective with ground coffee, they will also be
effective in the container of the instant invention.
Example 1
Oxygen Scavenging Films Packaged with Coffee
[0096] An extruded film that contained oxygen scavenger
formulations was prepared by following a method described in
co-assigned U.S. patent application Ser. No. 12/416,685, filed Apr.
1, 2009, hereby incorporated by reference, to test the oxygen
scavenging behavior with the presence of coffee. The film was
extruded from a mixture of 17/3/80 weight ratio of iron, sodium
chloride and low density polyethylene from a film extrusion
process. The materials were pre-mixed in a container and fed into a
twin screw extruder with the extruder and die temperatures set at
220.degree. C. Films, approximately 9 mil thick, were extruded from
a 6'' die and collected on a spool. The 9 mil film samples, cut in
approximately 1'' square pieces, were moisturized by placing drops
of water on the surface of the film and blotted to remove dripping
water. The films were placed in 7''.times.7'' plastic barrier bags
with a package of approximately 8.8 gm ground coffee sealed in
Tyvek breathable film bag. The barrier bag was hot sealed and
injected with 150 cc O.sub.2/N.sub.2 mixture to reach an initial
oxygen concentration of 3% or lower. The oxygen scavenging rate was
measured by using MOCON PacCheck Model 450 Head Space Analyzer.
Example 1A
Coffee without Oxygen Scavenger
[0097] As a control, a separate barrier bag that consists of
approximately 8.8 gm ground coffee removed from a container,
conditioned in ambient temperature and environment for more than
one hour, was sealed in Tyvek breathable film bag without
scavenger, and was tested for oxygen concentration change over the
same time period.
[0098] FIG. 24 shows the results of oxygen concentration change
with time for two different scavenger loadings. The oxygen
scavenging rate increases with the net amount of the scavengers
used. In 88 hrs, a sample with a starting O.sub.2 of 1.98% dropped
to 0.04% with 0.52 gm of the scavenger in the film. A sample of
2.21% O.sub.2 dropped to 1.08% with 0.17 gm of the scavenger in the
film. The O.sub.2 concentration of a sample with coffee packet only
without scavenger dropped from 2.45% to 2.37% with some variation
over the same time period. This example demonstrated that the
scavenger gives much higher oxygen absorption rate than the
combination of coffee and the background materials. The oxygen
scavenging capability can be adjusted by the amount of the
scavenger used and the preparation method adopted.
Example 2
Oxygen Scavenging Film Laminated on Coffee Lidding
[0099] Oxygen scavenging film was extruded with a mixture of
5.1/0.9/94 weight ratio of iron/NaCl/PLA in which PLA was
NatureWorks PLA 2002D resin. The iron is the same as in Example 1.
The composition of poly (lactic acid) resin (PLA) was pre-dried in
a desiccant oven at 60.degree. C. for at least 4 hrs before
extrusion. The mixture was extruded in a twin screw extruder to
make 4'' wide and 4 mil thick films. A coffee lidding foil film
peeled from a Green Mountain 55 cc cup coffee was used for
lamination test. Dow Chemical Integral.TM. 801 adhesive film was
used as an adhesive for lamination test. The extruded Fe/PLA film
was stacked with the Integral film and the lidding film to form
Fe/PLA-adhesive-lidding sandwich structure. The structure was heat
pressed in a heat sealer to form an oxygen-scavenging lidding
structure.
Example 3
Oxygen Scavenging Sachet Packaged with Coffee
[0100] Packets with an approximate size of 1''.times.0.5'' made of
a polyolefin film containing iron-based oxygen scavenging
formulation and moisture regulator were used for the test. The
packets contained iron-based scavenger and a moisture retaining
material patented by Multisorb Technologies. The packet consists by
weight of approximately 40% iron, 10% NaCl, 50% silica gel and some
moisture. The packets had a water activity in the range of 0.4-0.8.
The packets were stored with coffee in 150 cc barrier bag and
tested as described in Example 1. The oxygen absorption property
was measured by using MOCON PacCheck Model 450 Head Space Analyzer.
FIG. 25 shows the oxygen scavenging result that demonstrated that
the oxygen concentration decreased rapidly with time. The
scavenging rate is much faster than the oxygen absorption rate of
the coffee and the background material as shown in Example 1.
Example 4
Oxygen Scavenging Acrylic Coating Preparation
[0101] An acrylic emulsion was made using Neocryl A-5117 from
Zeneca Resins. A formulation comprising 50 weight percent of this
acrylic emulsion and 50 weight percent of a 200 mesh electrolytic
iron reduced iron containing 2 weight percent sodium chloride was
coated on eight square inches of a polypropylene substrate and
dried with heat. The coat weight was 0.0135 grams per square inch.
This oxygen absorbing coating was then placed inside of a test
vessel with 500 cc of air or 100 cc of oxygen along with 2 square
inches of a moisture saturated blotter paper. Three samples were
tested.
TABLE-US-00002 Sample 1 Sample 2 Sample 3 Composition weight 1.47
grams 1.71 grams 1.51 grams CC of oxygen absorbed 13. 16. 15. after
48 hours CC of oxygen absorbed 13. 18. 15. after 114 hours
Example 5
Oxygen Scavenging Polyvinyl Acetate Coating Preparation
[0102] A polyvinyl acetate in water emulsion was made using Vinac
XX-210 from Air Products. Forty three weight percent of this
polyvinyl emulsion was combined with 57 weight percent iron blend
containing 200 mesh electrolytic reduced iron powder containing 2
weight percent of sodium chloride. This formulation was then coated
on to eight square inches of a polypropylene substrate with a coat
weight of 0.026 grams per square inch. The resulting coating was
then placed inside of a test vessel with 500 cc of air or 100 cc of
oxygen. A moisture source was also placed inside of the test vessel
along with the sample. Three samples were tested.
TABLE-US-00003 Sample 1 Sample 2 Sample 3 Composition weight 1.47
grams 1.71 grams 1.51 grams CC of oxygen absorbed 22. 22. 22. after
48 hours CC of oxygen absorbed 25. 25. 25. after 114 hours
Example 6
Extruded Carbon Dioxide Scavenging Sheets
[0103] VitaCal-H calcium hydroxide (Ca(OH).sub.2) powder was
obtained from Mississippi Lime Company. The as received powder was
mixed with ground silica gel (SG) powder that had a mean particle
size of approximately 6 micron with a by weight mixture ratio of
VitaCal-H/SG=75/25. The mixture was then blended with Petrothene
GA502024 low density polyethylene resin obtained from
LynodellBasell Industries to achieve the following blend weight
ratios: Ca(OH).sub.2/SG/LDPE=30/10/60 and 40/10/50
[0104] The blends were extruded in a single screw extruder with a
flat sheet die attached to the extruder to make sheet materials.
SAFOAM FPN3-40 obtained from Reedy International Co. was added in
some runs to make samples that contained some voids or porosity.
The extruder was set at 160-220.degree. C. temperature range and
the die was at 220.degree. C. The extruded sheets, approximately
30-40 mil thick, were air cooled and winded on a roll.
[0105] Samples, approximately 0.4-0.7 grams were cut from the
extruded sheets and used for carbon dioxide scavenging test. The
samples were pre-hydrated with water to obtain approximately 1 to
5% water content determined by weight gain. The samples were then
sealed in foil pouches filled with 600 cc gas that contained
approximately 25-20% carbon dioxide balanced with nitrogen. The
concentration of carbon dioxide was measured using a MOCON model
333 Pac-Check analyzer for various periods of time. The scavenging
test data in terms of cc of CO.sub.2 absorbed is shown in Table-1.
The formulations listed are weight ratios of Ca(OH).sub.2/SG/LDPE.
Safoam was added as additional percentage. The data showed that
carbon dioxide was absorbed effectively with the increase of time
from 24-72 hrs.
TABLE-US-00004 TABLE 1 CO.sub.2 absorption of extruded sheets
Formu- Safoam+, Weight, 0 hrs 24 hrs 48 hrs 72 hrs ID lation* %**
gm CO.sub.2 absorbed, cc 1 30/10/60 5 0.69 0 6.82 12.7 17.2 2
30/10/60 2 0.66 0 6.94 12.8 20.1 3 40/10/50 0 0.57 0 7.7 12.9 20.6
4 40/10/50 5 0.48 0 9.96 11.2 17.8 *Formulation ratio =
Ca(OH).sub.2/SG/LDPE by weight **Percent by weight of formulation
+safoam FPN 3-40 at hydrofluocarbon
Example 7
Injection Molded Carbon Dioxide Scavenging Discs
[0106] Ca(OH).sub.2 and silica gel used were the same as that of
Example 7. Solka-floc wood fiber was obtained from International
Fiber Company. Polypropylene was Sunoco CP360H resin, an elastomer
Kraton G1657 was obtained from Kraton Polymers. These materials
were blended to form the following material weight ratios:
Ca(OH).sub.2/SG/Solka-floc/PP/Kraton 1657=48/6/6/36/4
[0107] The materials were compounded in a twin screw compounding
machine at 200-250 C temperature and extruded into strands, cooled
in water and pelletized. The compounded pellets were injection
molded in a single shot injection molding machine to form 1.3''
diameter discs. The discs were tested for carbon dioxide scavenging
performance following the procedure described above. The test data
showed that the discs gradually absorbed carbon dioxide with the
test time. The absorbing rate was found increased when the disc
surfaces were roughened with a sand paper prior to hydration.
Table-2 shows the data of an injection molded disc, sanded and
hydrated with 1% water prior to test.
TABLE-US-00005 TABLE 2 CO.sub.2 absorption of injection molded
discs Disc weight, 0 hrs 96 hrs 120 hrs 144 hrs ID gm % hydration
CO.sub.2 absorbed, cc Sanded disc 1.2 1.0 0 25.7 27.5 29.9
Example 8
Coated Carbon Dioxide Scavenging Paperboard
[0108] Coating formulations were prepared by using the same sorbent
ingredients as described above. Luvitec K30 (BASF)
polyvinylpyrrolidone (PVP) and polyethylene glycol 6000 (Aldrich
Chemical) were used to make the coating solutions. PVP was
dissolved in water to form a 17 wt % solution. PEG was dissolved in
water to form a 48 wt % solution. Both solutions were clear and
without residues. A mixture of the PEG and PVP solutions was made
with 90/10 ratio to achieve a resin content of approximately 45% in
water. The solutions were used to mix with Ca(OH).sub.2 and SG to
form a coating solution that has the following coating formulation:
Ca(OH).sub.2/SG/(PEG/PVP)=40/10/50
[0109] The solutions were coated on an 20 mil paperboard substrate
and dried in oven at 115 C for more than 2 hours to remove the
water. The coated samples were cut and hydrated with wet sponge to
be used for carbon dioxide scavenging test by using the same test
method described above. The test data is shown in Table-3. It is
seen that carbon dioxide was absorbed rapidly over the test time
period.
TABLE-US-00006 TABLE 3 CO.sub.2 absorption of Ca(OH).sub.2-coated
paperboard coupons Coating weight, % 0 hrs 24 hrs 96 hrs ID gm
hydration CO.sub.2 absorbed, cc 100710-1 1.21 1.2 0 4.8 27.1
100710-2 1.44 4.0 0 15.8 50.5
[0110] Another coating solution was prepared by dissolving
hydroxypropylcellulose resin (Hercules Klucel EF) in water to form
a uniform solution. Ca(OH).sub.2 and SG were mixed with the
solution to form a paste formulation approximately
Ca(OH).sub.2/SG/Klucel=70/10/20 weight ratios. Klucel served as a
binder for the solid formulation. The paste formulation was pressed
on the same paperboard and dried to form a porous coating. The
pressed-coating, although brittle, maintained integrity for test.
It was hydrated with wet sponge and the weight gain was recorded.
This high solid loading sample was tested for CO.sub.2 scavenging
performance. The data in Table-4 showed that CO.sub.2 was absorbed
rapidly over the test time period with high absorption
capacity.
TABLE-US-00007 TABLE 4 CO.sub.2 absorption of Ca(OH).sub.2-coated
paperboard with high solid loading Coating weight, % 0 hrs 24 hrs
336 hrs ID gm hydration CO.sub.2 absorbed, cc 093010-1 0.52 5 0
67.3 86.8
Example 9
Capsule Filled with Carbon Dioxide Absorber Blend
[0111] Plastic capsules were hand filled with Multisorb
Technologies CO.sub.2 absorbing formula (semi-dry flow able
granules) to achieve a CO.sub.2 free environment. The capsules are
breathable, semi-rigid, and are partially resistant to hot water.
The device (capsule) provides for a timed absorption of CO.sub.2
from coffee filled pods stored at various temperatures. The
CO.sub.2 capsule limits the expansion of a non-breathable cup (from
CO.sub.2 emissions from coffee) and also enhances or maintains the
aromas and oils of the freshly roasted coffee powders and granules.
The formulation enclosed in the capsules were Ca(OH).sub.2/SG=67/33
ratio with the silica gel containing water. The net formulation was
Ca(OH).sub.2/SG/H2O=67/20/13 weight ratio. The blend was in loose
powder format contained in the capsule. The CO.sub.2 scavenging
data is shown in Table-5.
TABLE-US-00008 TABLE 5 CO.sub.2 absorption of Ca(OH).sub.2 filled
capsule Coating weight, % 0 hrs 72 hrs 240 hrs ID gm hydration
CO.sub.2 absorbed, cc Caplug 0.65 30 0 32.6 36.4
Example 10
Tablets Made of CO.sub.2 Scavengers
[0112] The formulation used in Example 10 was compressed into
tablets in a mold on a conventional cold or hot pressing machine.
The tablets were then coated with polyethylene powders on the
surface. The coated tablets were heated in a heating chamber at a
temperature below the melting point of polyethylene but hot enough
to fuse the coated powder particles. The coated tablets were
conditioned at room temperature in 80% relative humidity
environment for 16 hrs. The tablets showed CO.sub.2 scavenging
properties as listed in Table-6.
TABLE-US-00009 TABLE 6 CO.sub.2 absorption of Ca(OH).sub.2 filled
tablets Coating 0 hrs 24 hrs 48 hrs 72 hrs ID weight, gm %
hydration CO.sub.2 absorbed, cc 5%-S2 0.85 5 0 11.3 14.9 17.3
Example 11
Sintered Structure Carbon Dioxide Scavenging Disc/Component
[0113] Ca(OH).sub.2 and silica gel used were the same as that of
Example 7. Solka-floc wood fiber was obtained from International
Fiber Company. Polypropylene was Sunoco CP360H resin, an elastomer
Kraton G1657 was obtained from Kraton Polymers. These materials
were blended to form the following material weight ratios:
Ca(OH).sub.2/SG/Solka-floc/PP/Kraton 1657=48/6/6/36/4
[0114] The materials were compounded in a twin screw compounding
machine at 200-250 C temperature, cooled in water and pelletized.
The pellets will then be ground to relatively small particle size
which will then expose portions of the active ingredients. This
exposure will increase the adsorption rate. The ground active
material is then fused together under heat and pressure which is
applied to the material in a mold. The results are a porous
sintered structure that increased active surface area.
Example 12
[0115] A gas permeable polyethylene film sachet container is filled
with 1.1 g of calcium hydroxide of 200 mesh and 1.1 g of silica gel
in a 2:1 blend with water. The sachet is sealed and placed into a
shrink wrap package of 4 ounce of Swiss cheese using conventional
grocery cheese wrap packaging techniques. After four months storage
at about 40.degree. F. the cheese exhibits good color and taste.
Further, the package is not expanded.
Example 13
[0116] This example illustrates the rapid acting of the calcium
hydroxide in absorption of carbon dioxide.
[0117] As a control sachets containing calcium oxide an amount of
1.1 g and 0.9 g of white porous silica gel and water in a 2:1 ratio
are formed. The sachets are each placed into an impermeable bag
that is filled with 300 cm.sup.3 of a bout a 30% by weight carbon
dioxide and oxygen gas mix. The three samples are sampled at two
hours, four hours, six hours, 24 hours, 48 hours and 72 hours. The
results are illustrated in Table 1 below
TABLE-US-00010 TABLE 1 Initial CO.sub.2 % 2 hrs 4 hrs 6 hrs 24 hrs
48 hrs 72 hrs S1 27.5 28.4 27.2 27.2 27.0 26.6 26.2 S2 26.5 26.4
26.3 26.1 26.0 25.7 25.5 S3 26.9 26.7 26.2 26.6 25.8 Flat 25.6
25.8
[0118] Three sachets containing 1.1 g of calcium hydroxide (200
mesh) and 1.1 g of a mixture of water and silica gel in a 2:1 ratio
are formed. The sachets are placed in a bag containing carbon
dioxide as indicated above for the calcium oxide test and are
sampled two hours and 24 hours. The results are illustrated in
Table 2 below:
TABLE-US-00011 TABLE 2 Ca(OH.sub.2).sub.2 Calcium Hydroxide (Lab),
HWPSG Initial 2 hrs 24 hrs S1 25.5 21.6 19.3 S2 25.7 22.1 18.0 S3
25.8 22.1 19.9
[0119] As may be seen from the comparison of Table 1 and Table 2
there is a much faster pickup of the carbon dioxide by the calcium
hydroxide. This is shown by the rapid decrease in carbon dioxide
left in the bag.
[0120] The materials of the above Examples 1-13 may be utilized in
the invention as scavengers or absorbents. Water vapor absorbers
could be made by similar techniques using silica gel and molecular
sieve materials.
[0121] The invention has been described in detail with particular
reference to a presently preferred embodiment, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention. The presently disclosed
embodiments are therefore considered in all respects to be
illustrative and not restrictive. The scope of the invention is
indicated by the appended claims, and all changes that come within
the meaning and range of equivalents thereof are intended to be
embraced therein.
* * * * *