Methods of using an oxygen scavenger

Information

  • Patent Grant
  • 6666988
  • Patent Number
    6,666,988
  • Date Filed
    Monday, November 4, 2002
    21 years ago
  • Date Issued
    Tuesday, December 23, 2003
    20 years ago
Abstract
An oxygen scavenging packet containing an iron-based oxygen scavenger and an electrolyte is set forth in which the rate of uptake of oxygen is increased by virtue of the introduction into the packet of an oxygen uptake accelerator containing water. Methods of increasing the rate of oxygen absorption by use of the iron-based oxygen scavenging packet are also set forth.
Description




FIELD OF THE INVENTION




The present invention relates generally to a device and method for maximizing the rate of oxygen uptake of an oxygen absorber. More particularly, the invention relates to an iron based oxygen scavenging packet having an improved composition for accelerating the rate of oxygen absorption wherein the packet is specifically designed to be used in a packaging system designed to keep meat fresh.




BACKGROUND OF THE INVENTION




Perishable foods, such as meats, fruits, and vegetables are typically placed into packaging systems after harvesting in order to preserve these foods for as long as possible. Maximizing the time in which the food remains preserved, especially the time between initial packaging at the plant and delivery at the retail grocery store, increases the profitability of all entities in the chain of distribution by minimizing the amount of spoilage.




The environment in which the food is preserved is a critical factor in the preservation process. Not only is maintaining an adequate temperature important, but the molecular and chemical content of the gases surrounding the food is important as well. By providing an appropriate gas content to the environment surrounding the food, the food can be better preserved when maintained at the proper temperature or even when it is exposed to variations in temperature. This gives the food producer some assurance that after the food leaves his or her control, the food will be in an acceptable condition when it reaches the retail grocery store and ultimately, the consumer.




In meat packaging, in particular, packaging systems which provide extremely low levels of oxygen are desirable because it is well known that the fresh quality of meat can be preserved longer under anaerobic conditions than under aerobic conditions. Maintaining low levels of oxygen minimizes the growth and multiplication of aerobic bacteria.




One way to insure a minimal level of oxygen in a meat package is to subject the package or rigid gas barrier materials to a vacuum in order to remove as much of the gas in the package as possible prior to sealing the package. The package can then be sealed and the meat maintained in a “zero” atmosphere environment (commonly referred to as vacuum packaging). Under vacuum packaging conditions, red meat turns purple. Consumers, however, prefer to see their meat bright red. As a result, vacuum packaging has not been well accepted for consumer cuts of meat.




Another means of insuring a minimal level of oxygen in a meat package is to seal the meat in a refill modified atmosphere packaging system. This kind of modified atmosphere packaging technology (MAP) is so successful that meat can be cut and packaged several weeks before purchase and still remain fresh. Such systems typically utilize multiple layers of packaging. The outside layer of packaging is generally a rigid container with good barrier properties. The inner layer of packaging is an oxygen permeable film. To provide a modified atmosphere environment, the air-evacuated package is typically filled with a mixture of gases consisting of about 30 percent carbon dioxide (CO


2


) and 70 percent nitrogen (N


2


). Refilling the air-evacuated package with such a mixture of gases is believed to suppress the growth of anaerobic bacteria. The outer layer is peeled off just prior to presenting the consumer cut for sale at the supermarket. This allows the meat to rebloom to a bright red color. An excellent example of such an evacuation and refill MAP process is described in U.S. Pat. No. 5,115,624 to Garwood. Vacuum packaging and refill MAP is very expensive for three reasons. First, the rigid part of the package is expensive. Second, processing speeds are slow due to the vacuum and refill steps. And third, the equipment to do these procedures is very complicated and expensive.




Another less expensive means of insuring a minimal level of oxygen in a meat package is to use a gas flush MAP process. The complicated steps of evacuating the package and refilling with the desired gas mixture are eliminated. The outer bag (a barrier layer), is simply flushed with the proper gas mixture as it is formed around the inner container. The flush process reduces the oxygen content of the package to about two percent. An oxygen scavenger is placed in the package to absorb additional oxygen just prior to or simultaneously with forming and flushing the outer bag. An excellent example of such a MAP system is described in the patent application entitled “Modified Atmosphere Package” filed on Apr. 3, 1996, and given Ser. No. 08/627,137.




A critical feature of a gas flush MAP packaging system is the ability to keep meat looking fresh and palatable. Oxidized meat turns an undesirable brown color. Accordingly, as discussed, an oxygen scavenger is typically placed inside the meat package in order to absorb any residual oxygen within the package after gas flushing and sealing the package. It is critically important to quickly remove the oxygen from meat to prevent it from turning brown. Especially important in preventing the irreversible change from red to brown is the rate at which oxygen is scavenged. If oxygen is removed quickly, the packaged meat turns a purple red color. This purple red color quickly “blooms” to a bright red color upon removal of the outer layer of packaging.




Oxygen scavengers are increasingly being used in packaging systems in order to protect various products from the detrimental effects of oxygen exposure. Several oxygen scavengers utilize the oxidation of particulate iron as a method to absorb oxygen. A small amount of water is essential for this reaction. In some instances, a water attracting agent such as silica gel can be used to attract water and at times to supply water in the packet initially. A major drawback to this technology is, however, the limited amount of water that can be supplied. Typically, a major portion of the water needed for the oxidation of particulate iron is provided by the product and/or packaging environment being protected. This is oftentimes an inadequate amount to promote the efficient and expedient oxidation of iron. And as mentioned, the slower the rate of oxygen reduction, the more likely meat will turn irreversibly brown.




A need thus exists to accelerate the rate of oxygen scavengers, particularly in the confines of a modified atmosphere packaging system. Optimally, it would be desirable to lower the oxygen level to about 0.04 percent (400 PPM) within 90 minutes and to about zero within 24 hours. This need will be addressed by the present invention.




SUMMARY OF THE INVENTION




The present invention provides an iron-based oxygen scavenging packet which exhibits an increased rate of oxygen absorption especially in the confines of a concomitant meat packaging system. The invention specifically provides an oxygen scavenging packet that comprises an iron-based oxygen absorber and an oxygen uptake accelerator comprising water. The oxygen uptake accelerator accelerates the rate of oxygen uptake of the iron-based absorber. In a preferred embodiment, the invention provides an oxygen scavenging packet where a ratio of between 0.2 ml and 0.8 ml of oxygen uptake accelerator to about 2.5 grams of iron is present in the packet. Plain water makes an excellent accelerator, but the addition of an electrolyte, either dissolved in the water or added as a solid in the oxygen scavenger packet, will further increase the rate of oxygen uptake. Examples of electrolytes that may be used are acids such as acetic acid and citric acid and salts such as metal (e.g., copper) salts and NaCl, CaCl


2


, and MgCl


2


. Optimally, approximately 0.6 ml of oxygen uptake accelerator per 2.5 grams of iron is present in the packet.











BRIEF DESCRIPTION OF THE DRAWINGS




Other objects and advantages of the invention will become apparent upon reading the following detailed description and upon reference to the drawings in which:





FIG. 1

illustrates an oxygen scavenging packet in which the oxygen uptake accelerator is being introduced into the packet via a syringe.





FIGS. 2



a


and


2




b


, respectively, illustrate an oxygen scavenging packet containing a capsule which can be ruptured at an appropriate time to release the oxygen uptake accelerator and a packet containing a capsule being ruptured.





FIGS. 3



a


and


3




b


, respectively, illustrate an oxygen scavenging packet including a protruding wick for absorption of the oxygen uptake accelerator into the packet and an oxygen scavenging packet in which the wick is being dipped into the oxygen scavenger accelerator.





FIG. 4

is an isometric view of the oxygen scavenging packet of the instant invention inside a modified atmosphere packaging system.





FIG. 5

is a graph illustrating the rate of oxygen absorption when a dry oxygen scavenging packet is introduced into a quart sized container which also includes 0.5 ml of water.





FIG. 6

is a graph illustrating the rate of oxygen absorption when an oxygen scavenging packet having 0.5 ml of water injected into the packet is introduced into a quart sized container.





FIG. 7

is a graph illustrating the rate of oxygen absorption as a function of the amount of water injected into oxygen scavenging packets.





FIG. 8

illustrates the rate of oxygen absorption in the presence of varying amounts of CO


2


utilizing an oxygen scavenging packet which has been injected with 0.6 ml of water.





FIG. 9

is a graph illustrating the rate of oxygen absorption as a function of the number of oxygen scavenging packets introduced into a one quart jar.





FIG. 10

is a graph showing the percent oxygen after 1 hour as a function of the amount of acetic acid (vinegar) injected into each of two oxygen scavenging packets.





FIG. 11

is a graph showing the percent oxygen as a function of time and as a function of the material injected into the oxygen scavenging packets.





FIG. 12

is a graph illustrating the rate of oxygen absorption as a function of the amount of acetic acid injected into an iron containing packet and further as a function of whether or not the packet contains impregnated silica gel.





FIG. 13

is a graph illustrating the rate of oxygen absorption as a function of time and the concentration of acetic acid in water.











While the invention is susceptible to various modifications and alternative forms, certain specific embodiments thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the invention to the particular forms described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.




DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT




Turning now to the drawings, FIGS.


1


through


3


(


a


and


b


) depict an oxygen scavenging packet having a liquid oxygen uptake accelerator present in some form within the packet.




Specifically,

FIG. 1

depicts an oxygen scavenging packet


10


containing elemental iron


12


and in which an oxygen uptake accelerator


14


is introduced into the packet utilizing a syringe


16


. Injection can be performed manually with a syringe and hand placement of the packet inside the package. Alternatively, the injection process can be automated by using a commercially available metering and dispensing pump such as the Luft Systematic model 45/50 and appropriate conveying equipment to position the packets for injection and then subsequently to place the packets into a package.





FIG. 2



a


depicts an oxygen scavenging packet


20


containing elemental iron


22


and in which an oxygen uptake accelerator


24


is present inside a capsule


26


. As

FIG. 2



b


shows, the capsule


26


may be ruptured by mechanical force at an appropriate time in order to release the oxygen uptake accelerator


24


. Optimally, the capsule should be ruptured immediately prior to or immediately after the sealing of the package in order to properly activate the iron-based scavenger for accelerated oxygen uptake.





FIG. 3



a


depicts an iron-based oxygen scavenging packet


30


containing elemental iron (not specifically shown) and in which an oxygen uptake accelerator


32


can be introduced into the packet by absorption onto a wick


34


which protrudes from the packet. As

FIG. 3



b


shows, the wick


34


dipped into the oxygen uptake accelerator


32


. An appropriate amount of oxygen uptake accelerator


32


is absorbed through the wick


34


into the packet


30


. Optimally, the dipping occurs immediately prior to the sealing of the package in order to properly activate the iron based scavenger for accelerated oxygen uptake.




Further information concerning the construction of the oxygen absorber packet preferred for use in the instant invention may be obtained from U.S. Pat. No. 5,262,375 to McKedy, entitled “Oxygen Absorber.” The preferred oxygen absorber packets are manufactured by Multiform Desiccants Incorporated. However, other iron-based oxygen absorbers will work comparably well in the instant invention.




The instant invention particularly concerns an iron-based oxygen scavenging packet which contains an oxygen uptake accelerator consisting of water or an aqueous solution of some other substance dissolved in or mixed with water. The oxygen uptake accelerator accelerates the rate of oxygen uptake of the oxygen absorber. Water alone will activate and accelerate iron-based oxygen absorbers via the presence of hydronium ions in the water. However, solutions prepared with electrolytes, such as dilute acid solutions, are preferred oxygen uptake accelerators. The electrolyte may be present as part of the oxygen uptake accelerator or it may be added in a dry form as part of the oxygen absorbing packet.




Acids provide increased numbers of hydronium ions which increase the oxidation rate of iron by acting as electron acceptors. These electron acceptors facilitate the ionization of neutral iron. Once ionized, the iron readily reacts with the available oxygen and water to form a hydrated iron oxide. Other electron acceptors such as the positively charged ions making up salt solutions or metals such as copper also facilitate the ionization of neutral iron.




The preferred aqueous solution of the instant invention is an aqueous solution which contains approximately five percent acetic acid.




The introduction of the oxygen uptake accelerator (comprising water or an aqueous solution of an electrolyte) into the oxygen absorber packet (comprising iron-based oxygen absorber, and optionally dry electrolytes) serves to activate and dramatically increase the rate of oxygen uptake of the iron inside the packet. The particulate iron in the packet, in effect, turns to rust as oxygen is absorbed from the atmosphere surrounding the packaged meat or other packaged food product. As discussed, the water or aqueous solution enhances oxygen absorption by the iron by acting as an electron acceptor. A proposed mechanism for rust formation is as follows:






Fe(


s


)→Fe


2+


+2


e







  (1)










e







+H


3


O


+


→H+H


2


O  (2)








4H+O


2


→2H


2


O  (3)








4Fe


2+


+O


2


(


g


)+(12+2


x


)H


2


O→2(Fe


2


O


3




.x


H


2


O))


s


)+8H


3


O


+


  (4)






In step (1) ferrous ions are produced by loss of electrons from the elemental particulate iron in the packet. However, this process cannot go very far unless there is some way to get rid of the electrons which accumulate on the residual Fe. One way to do this is by step (2) in which H


3


O


+


ions either from the water or from acid substances in the water, pick up the electrons to form neutral H atoms. Since Fe is known to be a good catalyst for hydrogenation reactions in general, it is believed that step (3) now occurs to use up the H atoms. In the meantime, the ferrous ion reacts with O


2


gas by step (4) to form the rust and restore H


3


O


+


required for step (2). The net reaction, obtained by adding all four steps is




 4Fe(


s


)+3O


2


(


g


)+2


x


H


2


O→2(Fe


2


O


3




.x


H


2


O)(


s


).




Acid accelerates the reaction by providing excess hydronium ions (H


3


O


+


) and driving step 2. Therefore, the preferred embodiment of the present invention utilizes a dilute aqueous solution of acid. Such acid solutions should, of course, be compatible with food products and include, for instance, acetic acid and/or citric acid.




Salt solutions also drive step (2) of the aforementioned reaction by providing an electron acceptor, thus they are suitable for use in the aqueous solution of the instant invention. Additionally, it has been found that adding copper to water and/or dilute aqueous solution of acid speeds the rate of oxygen absorption by the iron. It is believed that the copper induces a phenomena called electrolytic corrosion. Electrons flow from the iron to the copper, where their energy is lower. This removes the excess negative charge from the iron. In addition H atoms, which now form on the negative copper surface instead of the iron, detach themselves more readily from copper than from iron, thus accelerating step (3) of the aforementioned reaction.




As shown in FIGS.


1


-


3


(


a


and


b


), the aqueous solution can be introduced into the packet utilizing an injection type process. Alternatively, the solution can be included in the absorber packet in a separate capsule or compartment which can be ruptured at the time of sealing the meat package. Also, a wick could be included in, and protrude from, the packet such that the wick could be dipped in liquid just prior to sealing the meat package.




A preferred embodiment of the present invention involves the injection of an oxygen uptake accelerator comprising water into the MRM absorbers manufactured by Multiform Desiccants Incorporated. This is done just prior to the placement of the absorber into a package. This can be done manually with a syringe and hand placement or the process can be automated by using a commercially available metering and dispensing pump such as the Luft Systematic model 45/50 and appropriate conveying equipment to position the packets for injection and then subsequently to place the packets into a package.




The following data, depicted in

FIGS. 5-13

and in Table 1 is specific to Multiform's MRM 100 scavenger packets. All of these experiments involve using these scavengers. The MRM 100 oxygen scavengers are specifically formulated to work in the presence of CO


2


and refrigeration. MRM 100 oxygen scavengers contain approximately 2.5 grams of iron and silica gel impregnated with a carbon dioxide generator, NaHCO


3


. A carbon dioxide generator is utilized to replace gas volume in the sealed meat package as O


2


is absorbed. The iron in MRM absorbers is electrolytically reduced and annealed which means that the iron is reduced by the passage of electric current through a solution of the iron which is in the form of a molten salt. As one skilled in the art will appreciate, while MRM 100 scavenger packets were used in the following described experiments, similarly constituted scavenger packets would be expected to have comparably enhanced oxygen scavenging activities with the addition of water and other accelerators.





FIGS. 5 and 6

illustrate that the oxygen uptake accelerator, in this case water, must be contained within the oxygen scavenging packet in order to increase the rate of oxygen absorption. Specifically,

FIG. 5

shows the decrease in percent oxygen as a function of time when 0.5 ml of water is merely present in a quart-sized jar along with an oxygen scavenging packet. As shown in

FIG. 5

, at 40° F. it takes approximately 30 hours for the percent oxygen to be reduced to approximately 0.5% (5,000 PPM) and more than 40 hours for the percent oxygen to be reduced to near 0.0% oxygen. By contrast,

FIG. 6

shows the decrease in percent oxygen as a function of time when 0.5 ml of water is injected into an oxygen scavenging packet which is then placed in a quart-sized jar. At 40° F., it takes approximately 15 hours for the percent oxygen to be reduced to approximately 0.5% and about 20 hours for the percent oxygen to be reduced to near 0.0% oxygen. At 70° F., oxygen is scavenged much more quickly.





FIG. 7

shows that the oxygen scavenging rate is maximized when 0.6 ml of water is present in the oxygen scavenging packet.





FIG. 8

shows that oxygen absorption appears to be independent of the amount of carbon dioxide in the container.





FIG. 9

shows that two oxygen scavenging packets absorb oxygen at nearly twice the rate of one packet.




As shown in

FIG. 10

, acetic acid, commonly known as vinegar acid, works particularly well in accelerating the rate of oxygen absorption of an MRM oxygen scavenger packet. Specifically, the injection of 0.5 ml. of acetic acid into each of two absorber packets reduces the amount of oxygen in a quart jar to approximately 0.1% O


2


(1000 PPM) in one hour. As shown in

FIG. 11

, the percent O


2


is reduced to approximately 0.04% O


2


(400 PPM) in about ninety minutes when 0.5 ml. of acetic acid is injected into each of two MRM 100 scavenger packets. Two conclusions can be drawn from the data in

FIGS. 10 and 11

. First, injected acetic acid seems to work better than plain water in increasing the rate of oxygen absorption of an absorber packet. Second, from

FIG. 10

, 0.5 ml. acetic acid appears to work particularly well in increasing the rate and total amount of oxygen absorption. In the experiments resulting in the data in

FIGS. 10 and 11

, the starting level of oxygen in the jars was 2.0%, simulating the amount of oxygen which would be present after the gas flush step of a gas flush MAP process. Also, the experiments were performed under refrigeration.




Below is a table which shows the results of an experiment designed to determine the range of amounts of water needed to be introduced into an oxygen scavenging packet containing approximately 2.5 grams of iron in order to satisfactorily activate the packets in a gas flush MAP packaging process for red meat.

















TABLE 1













Color











Rating -







Water






1.5 hrs.






Sample




Injec-




Initial




Final




Of Bloom




Color Rating - 24 hrs.






No.




tion




Oxygen




Oxygen




(Day 8)




Of Bloom (Day 9)





























1




.8




ml




1.9%




0.00%




Dark Red




Some Browning






2




.6




ml




1.24%




0.00%




Dark Red




Bright Red






3




1.0




ml




2.30%




0.26%




Major




Major Browning











Browning






4




.4




ml




2.20%




0.00%




Dark Red




Bright Red






5




.2




ml




1.70%




0.00%




Dark Red




Dark Red






6




.4




ml




1.50%




14.9%




Excluded




Excluded











(Leaked)






7




.8




ml




1.70%




0.00%




Dark Red




Dark Red






8




.6




ml




1.55%




0.00%




Dark Red




Bright Red






9




1.0




ml




2.20%




0.00%




Dark Red




Some Browning






10




.2




ml




2.40%




0.00%




Major




Major Browning











Browning














The results show that water injections greater than 0.2 ml but less than 0.8 ml per 2.5 grams of iron (approximately 100 cc of absorber capacity) are required. For adequate oxygen scavenging, water injections must be within this range, preferably at 0.6 milliliters. Water injections outside of this range will result in a high risk of metmyoglobin formation (browning) due to initial oxygen exposure. This experiment was performed utilizing Multiform's MRM oxygen scavengers but other similar iron-based absorbers are believed to work comparably.




EXAMPLE 1




Determination of Range of Water Volume Necessary for Optimal Oxygen Scavenging of an Iron Based Oxygen Scavenging Packet




A ten pound chunk of fresh boneless beef (five days post mortem) was cut into ten pieces and individually placed on meat trays or a soaker pad. The meat trays had one and one half inch tall side walls. The meat and trays were then stretch wrapped with a standard PVC film on a Hobart machine. After wrapping, a half inch diameter hole was created through the PVC in one corner of the tray to allow free flow of gases in and out of this “inner package.” Next, two MRM 100 scavengers were injected with a precisely measured amount of water and attached to one of the inner packages containing the beef. The water injections were varied from 0.2 to 1.0 mils per scavenger. The inner package, with the oxygen absorbers attached, was then immediately run through a Fuji/Foremost form fill and seal machine and packaged in a flushed outer bag made from Print Pack 861D 2.5 mil barrier film. The flush gas was approximately 80% nitrogen and 20% carbon dioxide. The initial O


2


level in the barrier bag was measured through a rubber septum with a Dansensor oxygen analyzer and recorded. The completed packages were then placed in a refrigerator and stored at 34° F. for eight days. On the eight day the final oxygen level was measured and the barrier bag and oxygen absorbers removed. The meat was allowed to rebloom in the inner package for one and a half hours in the refrigerator. At that time the packages were removed from the refrigerator and the meat visually rated for color acceptability. The packages were then returned to the refrigerator for another 24 hours after which the meat was again rated for color acceptability.




The tray that was used for the experiment detailed in Example 1 and the data detailed in Table 1 left a significant amount of air space surrounding the meat, necessitating the use of two MRM 100 scavengers. However, beef has been successfully packaged on shallow wall meat trays using only one MRM 100 scavenger with a 0.5 ml injection of acetic acid.





FIG. 12

shows that maximum oxygen absorption occurs at an amount of vinegar between about 0.4 and 0.6 ml acetic acid.

FIG. 12

also illustrates that maximum oxygen absorption occurs when the oxygen scavenging packet contains silica gel impregnated with NaHCO


3


in addition to iron. MRM-100 absorbers and other similarly formulated absorbers employ silica gel to absorb and release atmospheric H


2


O. As discussed previously, silica gel will not by itself absorb enough water to satisfactorily accelerate the oxygen scavenging ability of the iron to allow for the preservation of meats for longer than a few days at a time. For this reason, the present inventors have affirmatively added concrete amounts of water to the oxygen scavenging packets of the instant invention.





FIG. 13

shows the rate of oxygen absorption as a function of time and the concentration of acetic acid in water. As can be seen, 5% acetic acid performs very well at accelerating the rate of oxygen absorption at 30, 60 and 90 minutes. Furthermore, 5% acetic acid is very easy to obtain, being common table vinegar.




The present invention is particularly useful when used in a modified atmosphere packaging (MAP) process for fresh meats. The MAP process is a gas flush process that initially flushes the package to an oxygen atmosphere of about two percent or less. The oxygen scavenging packet of the instant invention is utilized to additionally reduce the oxygen level of the package to 400 PPM (0.04%) or less within ninety minutes.




A brief description of the typical modified atmosphere package will follow. This description is not meant to be limiting, but instead is provided merely to elucidate one particular use for the instant invention.





FIG. 4

depicts a modified atmosphere package


40


including an outer container


42


and an inner container


44


. The inner container


44


includes a conventional semi-rigid plastic tray


46


thermoformed from a sheet of polymeric material which is substantially permeable to oxygen. Exemplary polymers which may be used to form the non-barrier tray


46


include polystyrene foam, cellulose pulp, polyethylene, polypropylene, etc. In a preferred embodiment, the polymeric sheet used to form the tray


46


is substantially composed of polystyrene foam and has a thickness ranging from about 100 mils to about 300 mils. The use of a common polystyrene foam tray


46


is desirable because it has a high consumer acceptance. The inner container


44


further includes a stretch film wrapping or cover


48


substantially composed of a polymeric material, such as polyvinyl chloride (PVC), which is substantially permeable to oxygen. In a preferred embodiment, the stretch film used to form the cover


48


contains additives which allow the film to cling to itself and has a thickness ranging from about 0.5 mil to about 1.5 mils. One preferred stretch film is Resinite™ meat film commercially available from Borden Packaging and Industrial Products of North Andover, Mass.




A food item such as a retail cut of raw meat


50


is located inside the inner container


44


. Prior to fully wrapping the tray


46


with the cover


48


, the partially formed inner container


44


may be flushed with an appropriate mixture of gases, typically a mixture of about 30 percent carbon dioxide and about 70 percent nitrogen, to lower the oxygen level in the inner container


44


to about 1.5 to 5.0 percent. The foregoing mixture of gases displaces the oxygen within the inner container


44


during the flushing operation. After flushing the inner container


44


, the tray


46


is manually or automatically wrapped with the cover


48


. The cover


48


is wrapped over the retail cut of raw meat


50


and about the bottom of the tray


46


. The free ends of the cover


48


are overlapped along the underside of the bottom wall of the tray


46


, and, due to the cling characteristic inherent in the cover


48


, these overlapping free ends cling to one another to hold the cover


48


in place. If desired, the overwrapped tray


46


, i.e., the inner container


44


, may be run over a hot plate to thermally fuse the free ends of the cover


48


to one another and thereby prevent these free ends from potentially unraveling.




The outer container


42


is preferably a flexible polymeric bag composed of a single or multilayer plastics material which is substantially impermeable to oxygen. The outer container


42


may, for example, include an oriented polypropylene (OPP) core coated with an oxygen barrier coating such as polyvinylidene chloride and further laminated with a layer of sealant material such as polyethylene to facilitate heat sealing. In a preferred embodiment, the outer container


42


is composed of a multilayer barrier film commercially available as product no. 325C44-0EX861D from PrintPack, Inc. of Atlanta, Ga. The co-extruded film has a thickness ranging from about 2 mils to about 6 mils. Prior to sealing the peripheral edges of the outer container


42


, the inner container


44


is placed within the outer container


42


. Also, the outer container


42


is flushed with an appropriate mixture of gases, typically about 30 percent carbon dioxide and about 70 percent nitrogen, to lower the oxygen level in the outer container


42


to about 0.05 to 5.0 percent or 500 to 50,000 parts per million (PPM). Prior to or simultaneously with flushing the outer container


42


, but still prior to sealing the outer container


42


, the oxygen scavenging packet


52


is placed in the outer container


42


external to the sealed inner container


44


. The outer container


42


is then sealed.




After a time period of about ninety minutes, the oxygen scavenging packet


52


lowers the oxygen level in the bag from its initial level of oxygen to less than about 0.04 percent or 400 PPM and most preferably to about zero percent. The oxygen uptake accelerator contained within the oxygen scavenging packet


52


is responsible for this fast rate of oxygen absorption. The oxygen scavenger


52


also absorbs any oxygen which might permeate into the outer container


42


from the ambient environment. In

FIGS. 1 through 4

, the oxygen scavenger


10


,


20


,


30


, and


52


respectively, is illustrated as a packet or label which is inserted into the outer container


42


prior to sealing the outer container


42


. Alternatively, an oxygen scavenging material may be added to the polymer or polymers used to form the outer container


42


so that the oxygen scavenging material is integrated into the outer container


42


itself.




The retail cut of raw meat


50


within the package


40


takes on a purple-red color when the oxygen is removed from the interior of the package


40


. The meat-filled modified atmosphere package


40


may now be stored in a refrigeration unit for several weeks prior to being offered for sale at a grocery store. A short time (e.g., less than one hour) prior to being displayed at the grocery store, the inner container


44


is removed from the outer container


42


to allow oxygen from the ambient environment to permeate the non-barrier tray


46


and non-barrier cover


48


. The purple-red color of the raw meat


50


quickly changes or “blooms” to a generally acceptable bright red color when the raw meat


50


is oxygenated by exposure to air.




While the present invention has been described with reference to one or more particular embodiments, those skilled in the art will recognize that many changes may be made thereto without departing from the spirit and scope of the present invention. Each of these embodiments and obvious variations thereof is contemplated as falling within the spirit and scope of the claimed invention, which is set forth in the following claims.



Claims
  • 1. A method for reducing the oxygen concentration in a modified atmosphere package, comprising:(a) placing an oxygen scavenging packet in the package, said oxygen scavenging packet comprising: (i) a plurality of side walls defining an enclosed space; and (ii) an oxygen absorber within the enclosed space, said oxygen absorber comprising iron, silica gel, a carbon dioxide generator, and an electrolyte; (b) introducing a liquid oxygen uptake accelerator comprising water directly onto said oxygen absorber; and (c) immediately sealing the modified atmosphere package; wherein the amount of liquid oxygen uptake accelerator which is introduced into said packet is from about 0.2 mL to about 0.8 mL for each 2.5 grams of iron.
  • 2. The method of claim 1, wherein said iron is electrolytically annealed and reduced.
  • 3. The method of claim 1, wherein said oxygen uptake accelerator is contained within a frangible capsule and further including rupturing said tangible capsule such that the oxygen uptake accelerator is introduced directly onto said oxygen absorber.
  • 4. The method of claim 1, wherein said oxygen uptake accelerator is contained within a bibulous wick, wherein said wick extends from the exterior of said packet, through at least one of said plurality of side walls and into said enclosed space.
  • 5. The method of claim 1, wherein said oxygen uptake accelerator further comprises an acid.
  • 6. The method of claim 1, wherein said silica gel is impregnated with said carbon dioxide generator.
  • 7. The method of claim 1, wherein said packet further comprises means for introducing said liquid oxygen uptake accelerator directly onto the oxygen absorber.
  • 8. The method of claim 1, wherein said oxygen uptake accelerator is present in said packet in an amount from about 0.3 ml to about 0.7 ml per approximately 2.5 grams of said iron.
  • 9. The method of claim 8, wherein approximately 0.4 to about 0.6 ml of said oxygen uptake accelerator is present in said packet per approximately 2.5 grams of said iron.
  • 10. The method of claim 9, wherein approximately 0.6 ml of said oxygen uptake accelerator is present in said packet per approximately 2.5 grams of said iron.
  • 11. The method of claim 1, wherein said electrolyte is chosen from the group consisting of acids and salts.
  • 12. The method of claim 11, wherein said acid is acetic acid or citric acid.
  • 13. The method of claim 11, wherein said salt is a metal salt.
  • 14. The method of claim 13, wherein said salt is a copper salt.
  • 15. The method of claim 11, wherein said salt is selected from the group consisting of NaCl, CaCl2, and MgCl2.
  • 16. The method of claim 1, wherein introducing said oxygen uptake accelerator directly onto said oxygen absorber includes injecting said oxygen uptake accelerator onto said oxygen absorber.
  • 17. The method of claim 16, wherein introducing said oxygen uptake accelerator directly onto said oxygen absorber is carried out using a syringe.
  • 18. The method of claim 16, wherein introducing said oxygen uptake accelerator directly onto said oxygen absorber includes placing into said packet a frangible capsule containing the oxygen uptake accelerator, and further including rupturing the frangible capsule such that the oxygen uptake accelerator is introduced directly onto the oxygen absorber.
  • 19. A method for minimizing metmyoglobin formation in fresh meat which is contained within a modified atmosphere package, comprising:(a) placing an oxygen scavenging packet in the package, said oxygen scavenging packet comprising: (i) a plurality of side walls defining an enclosed space; and (ii) an oxygen absorber within the enclosed space, said oxygen absorber comprising iron, silica gel, a carbon dioxide generator, and an electrolyte; (b) introducing a liquid oxygen uptake accelerator comprising water directly onto said oxygen absorber; and (c) immediately sealing the modified atmosphere package; wherein the amount of liquid oxygen uptake accelerator which is introduced into said packet is from about 0.2 mL to about 0.8 mL for each 2.5 grams of iron.
  • 20. The method of claim 19, wherein said iron is electrolytically annealed and reduced.
  • 21. The method of claim 19, wherein said oxygen uptake accelerator is contained within a frangible capsule and further including rupturing said frangible capsule such that the oxygen uptake accelerator is introduced directly onto said oxygen absorber.
  • 22. The method of claim 19, wherein said oxygen uptake accelerator is contained within a bibulous wick, wherein said wick extends from the exterior of said packet, through at least one of said plurality of side walls and into said enclosed space.
  • 23. The method of claim 19, wherein said oxygen uptake accelerator further comprises an acid.
  • 24. The method of claim 19, wherein said silica gel is impregnated with said carbon dioxide generator.
  • 25. The method of claim 19, wherein said oxygen uptake accelerator is present in said packet in an amount from about 0.3 ml to about 0.7 ml per approximately 2.5 grams of said iron.
  • 26. The method of claim 25, wherein approximately 0.4 to about 0.6 ml of said oxygen uptake accelerator is present in said packet per approximately 2.5 grams of said iron.
  • 27. The method of claim 26, wherein approximately 0.6 ml of said oxygen uptake accelerator is present in said packet per approximately 2.5 grams of said iron.
  • 28. The method of claim 19, wherein said electrolyte is chosen from the group consisting of acids and salts.
  • 29. The method of claim 28, wherein said acid is acetic acid or citric acid.
  • 30. The method of claim 28, wherein said salt is selected from the group consisting of NaCl, CaCl2, and MgCl2.
  • 31. The method of claim 28, wherein said salt is a metal salt.
  • 32. The method of claim 31, wherein said salt is a copper salt.
  • 33. The method of claim 19, wherein said packet further comprises means for introducing said liquid oxygen uptake accelerator directly onto the oxygen absorber.
  • 34. The method of claim 33, wherein said step of introducing said oxygen uptake accelerator directly onto said oxygen absorber includes placing into said packet a frangible capsule containing the oxygen uptake accelerator, and further including rupturing the frangible capsule such that the oxygen uptake accelerator is introduced directly onto the oxygen absorber.
  • 35. The method of claim 19, wherein introducing said oxygen uptake accelerator directly onto said oxygen absorber includes injecting said oxygen uptake accelerator onto said oxygen absorber.
  • 36. The method of claim 35, wherein introducing said oxygen uptake accelerator directly onto said oxygen absorber is carried out using a syringe.
RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No. 09/439,615, filed Nov. 13, 1999 now U.S. Pat. No. 6,508,955, which has been allowed and is incorporated by reference in its entirety. The present application claims priority to provisional U.S. Patent Application Serial No. 60/108,315, filed Nov. 13, 1998, which is a continuation-in-part of U.S. application Ser. No. 08/856,448 filed on May 14, 1997 and now U.S. Pat. No. 5,928,560, issued on Jul. 27, 1999, which is a continuation-in-part of U.S. patent application Ser. No. 08/700,644, filed Aug. 8, 1996, now abandoned.

US Referenced Citations (195)
Number Name Date Kind
1475396 Kestner Nov 1923 A
1679543 Rector Aug 1928 A
2825651 Loo et al. Mar 1958 A
3363395 King Jan 1968 A
3419400 Hayhurst et al. Dec 1968 A
3467244 Mahaffy et al. Sep 1969 A
3481100 Bergstrom Dec 1969 A
3545163 Mahaffy et al. Dec 1970 A
3574642 Weinke Apr 1971 A
3634993 Pasco et al. Jan 1972 A
3650775 Simon et al. Mar 1972 A
3679093 Chang Jul 1972 A
3686822 Wolfelsperger Aug 1972 A
3750362 Kishpaugh et al. Aug 1973 A
3788369 Killinger Jan 1974 A
3792181 Mahaffy et al. Feb 1974 A
3843806 Kishpaugh et al. Oct 1974 A
3851441 Marchand Dec 1974 A
3903309 Mahaffy et al. Sep 1975 A
4083372 Boden Apr 1978 A
4127503 Yoshikawa et al. Nov 1978 A
4166807 Komatsu et al. Sep 1979 A
4192773 Yoshikawa et al. Mar 1980 A
4201030 Mahaffy et al. May 1980 A
4230595 Yamaji et al. Oct 1980 A
4242659 Baxter et al. Dec 1980 A
4299719 Aoki et al. Nov 1981 A
4308711 Mahaffy et al. Jan 1982 A
4317742 Yamaji et al. Mar 1982 A
4337276 Nakamura et al. Jun 1982 A
4340138 Bernhardt Jul 1982 A
4349999 Mahaffy et al. Sep 1982 A
4366179 Nawata et al. Dec 1982 A
4379453 Baron Apr 1983 A
4384972 Nakamura May 1983 A
4406813 Fujishima et al. Sep 1983 A
4411122 Cornish et al. Oct 1983 A
4411918 Cimino et al. Oct 1983 A
4424659 Perigo et al. Jan 1984 A
4454945 Jabarin et al. Jun 1984 A
4510162 Nezat Apr 1985 A
4517206 Murphy et al. May 1985 A
4524015 Takahashi et al. Jun 1985 A
4536409 Farrell et al. Aug 1985 A
4543770 Walter et al. Oct 1985 A
4564054 Gustavsson Jan 1986 A
4574174 McGonigle Mar 1986 A
4579223 Otsuka et al. Apr 1986 A
4581764 Plock et al. Apr 1986 A
4622229 Toshitsugu Nov 1986 A
4622239 Schoenthaler et al. Nov 1986 A
4642239 Ferrar et al. Feb 1987 A
4645073 Homan Feb 1987 A
4657610 Komatsu et al. Apr 1987 A
4683139 Cheng Jul 1987 A
4683702 Vis Aug 1987 A
4711741 Fujishima et al. Dec 1987 A
4737389 Hartsing, Jr. et al. Apr 1988 A
4740402 Maeda et al. Apr 1988 A
4756436 Morita et al. Jul 1988 A
4769175 Inoue Sep 1988 A
4820442 Motoyama et al. Apr 1989 A
4830855 Stewart May 1989 A
4830863 Jones May 1989 A
4836952 Nasu et al. Jun 1989 A
4840271 Garwood Jun 1989 A
4842875 Anderson Jun 1989 A
4876146 Isaka et al. Oct 1989 A
4877664 Maeda et al. Oct 1989 A
4897274 Candida et al. Jan 1990 A
4908151 Inoue et al. Mar 1990 A
4910032 Antoon, Jr. Mar 1990 A
4923703 Antoon, Jr. May 1990 A
4928474 Schirmer May 1990 A
4942048 Nasu et al. Jul 1990 A
4943440 Armstrong Jul 1990 A
4949847 Nagata Aug 1990 A
4952451 Mueller Aug 1990 A
4956209 Isaka et al. Sep 1990 A
4992410 Cullen et al. Feb 1991 A
4996068 Hatakeyama et al. Feb 1991 A
5019212 Morita et al. May 1991 A
5021515 Cochran et al. Jun 1991 A
5045331 Antoon, Jr. Sep 1991 A
5049624 Adams et al. Sep 1991 A
5064698 Courtright et al. Nov 1991 A
5085878 Hatakeyama et al. Feb 1992 A
5096724 Zenner et al. Mar 1992 A
5101611 Biskup et al. Apr 1992 A
5103618 Garwood Apr 1992 A
5108649 Matsumoto et al. Apr 1992 A
5110677 Barmore et al. May 1992 A
5112674 German et al. May 1992 A
5115624 Garwood May 1992 A
5116660 Komatsu et al. May 1992 A
5120349 Stewart et al. Jun 1992 A
5120585 Sutter et al. Jun 1992 A
5124164 Matsumoto et al. Jun 1992 A
5128060 Ueno et al. Jul 1992 A
5129512 Garwood Jul 1992 A
5132151 Graney Jul 1992 A
5135787 Bair Aug 1992 A
5139702 Carter et al. Aug 1992 A
5143763 Yamada et al. Sep 1992 A
5143769 Moriya et al. Sep 1992 A
5145950 Funaki et al. Sep 1992 A
5151331 Beeson et al. Sep 1992 A
5153038 Koyama et al. Oct 1992 A
5155974 Garwood Oct 1992 A
5158537 Haak et al. Oct 1992 A
5171593 Doyle Dec 1992 A
5176849 Hwa et al. Jan 1993 A
5176930 Kannankeril et al. Jan 1993 A
5183573 Kreh et al. Feb 1993 A
5183574 Hwa et al. Feb 1993 A
5183848 Samuel et al. Feb 1993 A
5186991 Samuel et al. Feb 1993 A
5194315 Itoh Mar 1993 A
5202052 Zenner et al. Apr 1993 A
5204289 Moh Apr 1993 A
5204389 Hofeldt et al. Apr 1993 A
5211875 Speer et al. May 1993 A
5223146 Kreh Jun 1993 A
5226531 Garwood Jul 1993 A
5226735 Beliveau Jul 1993 A
5227411 Hofeldt et al. Jul 1993 A
5239016 Cochran et al. Aug 1993 A
5241149 Watanabe et al. Aug 1993 A
5242111 Nakoneczny et al. Sep 1993 A
5244600 Cuisia et al. Sep 1993 A
5247746 Johnson et al. Sep 1993 A
5250310 Fujino et al. Oct 1993 A
5254354 Stewart Oct 1993 A
5258537 Takeuchi et al. Nov 1993 A
5270337 Graf Dec 1993 A
5284871 Graf Feb 1994 A
5286407 Inoue et al. Feb 1994 A
5288907 Sherwin et al. Feb 1994 A
5290268 Oliver et al. Mar 1994 A
5296291 Muller Mar 1994 A
5310497 Ve Speer et al. May 1994 A
5320598 Haak et al. Jun 1994 A
5322701 Cullen et al. Jun 1994 A
5323590 Garwood Jun 1994 A
5332590 McKedy Jul 1994 A
5334405 Gorlich Aug 1994 A
5346312 Mabry et al. Sep 1994 A
5346644 Speer et al. Sep 1994 A
5348752 Gorlich Sep 1994 A
5350622 Speer et al. Sep 1994 A
5362531 Samuel et al. Nov 1994 A
5364555 Zenner et al. Nov 1994 A
5364669 Sumida et al. Nov 1994 A
5378428 Inoue et al. Jan 1995 A
5390475 Iwauchi et al. Feb 1995 A
5399289 Speer et al. Mar 1995 A
5418112 Mirle et al. May 1995 A
5422366 Mintzis et al. Jun 1995 A
5425896 Speer et al. Jun 1995 A
5430098 Samuel et al. Jul 1995 A
5443727 Gagnon Aug 1995 A
5445607 Venkateshwaran et al. Aug 1995 A
5491019 Kuo Feb 1996 A
5492705 Porchia et al. Feb 1996 A
5492742 Zenner et al. Feb 1996 A
5498364 Speer et al. Mar 1996 A
5510166 Inoue et al. Apr 1996 A
5529833 Speer et al. Jun 1996 A
5580573 Kydonieus et al. Dec 1996 A
5585129 Geddes et al. Dec 1996 A
5631036 Davis May 1997 A
5638660 Kuo Jun 1997 A
5639815 Cochran et al. Jun 1997 A
5643625 Perry et al. Jul 1997 A
5648020 Speer et al. Jul 1997 A
5660761 Katsumoto et al. Aug 1997 A
5665822 Bitler et al. Sep 1997 A
5667863 Cullen et al. Sep 1997 A
5672406 Challis et al. Sep 1997 A
5686126 Noel et al. Nov 1997 A
5686127 Stockley, III et al. Nov 1997 A
5698250 DelDuca et al. Dec 1997 A
5700554 Speer et al. Dec 1997 A
5811142 DelDuca et al. Sep 1998 A
5928560 DelDuca et al. Jul 1999 A
5948457 DelDuca et al. Sep 1999 A
6054153 Carr et al. Apr 2000 A
6132781 Carr et al. Oct 2000 A
6183790 DelDuca et al. Feb 2001 B1
6231905 DelDuca et al. May 2001 B1
6315921 DelDuca et al. Nov 2001 B1
6321509 DelDuca et al. Nov 2001 B1
6395195 Evans et al. May 2002 B1
6494023 DelDuca et al. Dec 2002 B2
6508955 DelDuca et al. Jan 2003 B1
Foreign Referenced Citations (5)
Number Date Country
924298 Jun 1992 EP
0 547 761 Jun 1993 EP
1556853 Nov 1979 GB
06278774 Oct 1994 JP
06278774 Dec 1994 JP
Non-Patent Literature Citations (155)
Entry
US 6,103,281, 8/2000, DelDuca et al. (withdrawn)
Fran Labell, “Controlled & Modified Atmosphere Packating—Methods for Extending Shelf Life of a Variety of Food Products,” Food Processing, (Jan., 1995), 125-54.
Patent Abstracts of Japan 03202150 (1991).
Multiform Desiccants Inc. Product brochure, (1994).
Principles of Modified-Atmosphere and Sous Vide Product Packaging; J. Barber and K. Dodds, Ed. “Modified Atmosphere Packaging-Present and Future Uses of Gas Absorbents and Generators”, by J. Smith et al., p. 287-292 (1995).
Conference Publication Modified Atmosphere Packaging (MPAP) and Related Technologies. Chipping Camden UK. Presentation—“Active Packaging with Oxygen Absorbers in the Food Industry”, by Jonathan Hurst., Sep. 6-7, 1995.
T. Labuza and W. Breene, “Applications of ‘Active Packaging’ for Improvement of Shelf-Life and Nutritional. Qual.ity of Fresh and Extended Shelf-Life Foods”, p. 36-37 (1989).
Principles of Modified Atmosphere of Modified Atmosphere Packaging of Foods by R. T. Parry, Ed., “Meat Products” by P.N. Church, p. 244-245 (1993).
Active Food Packaging, M. L. Rooney, Ed., “Interactive Packaging Involving Sachet Technology” by J. Smith et al. P. 143-152, p. 82-85 (1995).
Leward, D.A., “Metmyoglobin Formation in Beef Stored in Carbon Dioxide Enriched and Oxygen Depleted Atmospheres,” Journal. of Food Science vol. 35 pp. 33-37 (1970).
Gill, C. O., et al., “The Use of Oxygen Scavengers to Prevent Transcient Discolouration of Ground Beef Packaged Under Controlled, Oxygen-depleted Atmospheres,” Meat Science, vol. 41, No. 1, pp. 19-27, (1995).
Gill, C. O., “Extending the Storage Life of Raw Chilled Meats,” Elsevier Science Ltd., S99-S109 (1990).
Abstract No. 84:72833 CA.
Abstract No. 86:87906 CA.
Abstract No. 86:187942 CA.
Abstract No. 90:202465 CA.
Abstract No. 94:177380 CA.
Abstract No. 82:137914 CA.
Abstract No. 99:120969 CA.
Abstract No. 98:73550 CA.
Abstract No. 119:272963 CA.
Abstract No. 113:232991 CA.
Abstract No. 113:189998 CA.
Abstract No. 121:150818 CA.
Abstract No. 115:234163 CA.
Abstract No. 97:125982 CA.
Abstract No. 90:202475 CA.
Abstract No. 90:202474 CA.
Abstract No. 92:162415 CA.
Abstract No. 92:162419 CA.
Abstract No. 88:36115 CA.
Abstract No. 88:20812 CA.
Abstract No. 88:20813 CA.
Abstract No. 88:20814 CA.
Abstract No. 88:20807 CA.
Abstract No. 88:20808 CA.
Abstract No. 93:44408 CA.
Abstract No. 92:162423 CA.
Abstract No. 92:162424 CA.
Abstract No. 92:162422 CA.
Abstract No. 92:162421 CA.
Abstract No. 92:162420 CA.
Abstract No. 88:135035 CA.
Abstract No. 88:135039 CA.
Abstract No. 120:162007 CA.
Abstract No. 95:40919 CA.
Abstract No. 96:102621 CA.
Abstract No. 101:37293 CA.
Abstract No. 97:24981 CA.
Abstract No. 103:70144 CA.
Abstract No. 114:159181 CA.
Abstract No. 121:106915 CA.
Abstract No. 122:8480 CA.
Abstract No. 94:31753 CA.
Abstract No. 109:229141 CA.
Abstract No. 121:302240 CA.
Abstract No. 116:135950 CA.
Abstract No. 116:213870 CA.
Abstract No. 119:93984 CA.
Abstract No. 114:37856 CA.
Abstract No. 116:82513 CA.
Abstract No. 88:36119 CA.
Abstract No. 115:10409 CA.
Abstract No. 117:252831 CA.
Abstract No. 92:56886 CA.
Abstract No. 90:101969 CA.
Abstract No. 122:54216 CA.
Abstract No. 106:48956 CA.
Abstract No. 89:128079 CA.
Abstract No. 90:202468 CA.
Abstract No. 98:162097 CA.
Abstract No. 106:83270 CA.
Abstract No. 114:60693 CA.
Abstract No. 88:36110 CA.
Abstract No. 88:36112 CA.
Abstract No. 87:199474 CA.
Abstract No. 89:89110 CA.
Abstract No. 91:18612 CA.
Abstract No. 89:145374 CA.
Abstract No. 90:37838 CA.
Abstract No. 91: 37778 CA.
Abstract No. 91:18615 CA.
Abstract No. 91:156319 CA.
Abstract No. 93:24803 CA.
Abstract No. 93:44367 CA.
Abstract No. 93:93837 CA.
Abstract No. 97:71152 CA.
Abstract No. 102:114740 CA.
Abstract No. 113:4951 CA.
Abstract No. 117:149868 CA.
Abstract No. 114:120487 CA.
Abstract No. 123:117300 CA.
Abstract No. 120:132783 CA.
Abstract No. 96:161139 CA.
Abstract No. 88:35888 CA.
Abstract No. 121:11294 CA.
Abstract No. 119:206378 CA.
Abstract No. 104:150081 CA.
Abstract No. 111:231023 CA.
Abstract No. 112:200253 CA.
Abstract No. 119:195629 CA.
Abstract No. 119:199523 CA.
Abstract No. 118:19132 CA.
Abstract No. 102:74246 CA.
Abstract No. 119:208661 CA.
Abstract No. 115:70144 CA.
Abstract No. 88:138618 CA.
Abstract No. 102:50897 CA.
Abstract No. 104:184989 CA.
Abstract No. 92:162414 CA.
Abstract No. 92:162418 CA.
Abstract No. 93:24783 CA.
Abstract No. 92:179358 CA.
Abstract No. 113:130909 CA.
Abstract No. 114:205791 CA.
Abstract No. 122:159237 CA.
Abstract No. 122:217607 CA.
Abstract No. 122:216062 CA.
Abstract No. 114:162789 CA.
Abstract No. 117:250329 CA.
Abstract No. 95:202299 CA.
Abstract No. 95:131188 CA.
Abstract No. 93:44362 CA.
Abstract No. 91:209670 CA.
Abstract No. 91:54914 CA.
Abstract No. 91:37783 CA.
Abstract No. 91:92660 CA.
Abstract No. 90:37839 CA.
Abstract No. 98:15724 CA.
Abstract No. 98:15725 CA.
Abstract No. 97:71153 CA.
Abstract No. 93:112563 CA.
Abstract No. 121:81494 CA.
Abstract No. 2681558 IFIPAT.
Abstract No. 122:11836 CA.
Abstract No. 118:214320 CA.
Abstract No. 118:170560 CA.
Abstract No. 105:189533 CA.
Abstract No. 116:85409 CA.
Abstract No. 88:168561 CA.
Abstract No. 117:51733 CA.
Abstract No. 118:16068 CA.
Abstract No. 121:117332 CA.
Abstract No. 93:237305 CA.
Abstract No. 93:237306 CA.
Abstract No. 122:104527 CA.
Abstract No. 117:51734 CA.
Abstract No. 116:195864 CA.
Abstract No. 98:124507 CA.
Abstract No. 122:79435 CA.
Abstract No. 95:95814 CA.
Abstract No. 91:139162 CA.
Abstract No. 90:202476 CA.
Abstract No. 120:109182 CA.
Abstract No. 119:205054 CA.
Provisional Applications (1)
Number Date Country
60/108315 Nov 1998 US
Continuation in Parts (2)
Number Date Country
Parent 08/856448 May 1997 US
Child 09/439615 US
Parent 08/700644 Aug 1996 US
Child 08/856448 US