WO2023034938A1

WO2023034938A1 - Compositions comprising reducing and / or hydrolyzable sugars for oxygen scavenging and methods of their use in packaging

Info

Publication number: WO2023034938A1
Application number: PCT/US2022/075867
Authority: WO
Inventors: Jason Pratt; Ivy COMER; Megan BRYANT; Justin BOX
Original assignee: Csp Technologies, Inc.
Priority date: 2021-09-01
Filing date: 2022-09-01
Publication date: 2023-03-09

Abstract

Disclosed are sugar-based compositions, materials and their methods of use for oxygen modified packaging of oxygen sensitive products. Reducing and / or hydrolyzable sugars, such as starches, are optionally incorporated into polymer compositions to function as oxygen scavengers. Particular applications in the food and beverage industry are highly desired.

Description

COMPOSITIONS COMPRISING REDUCING AND I OR HYDROLYZABLE SUGARS FOR OXYGEN SCAVENGING AND METHODS OF THEIR USE IN PACKAGING

FIELD OF INVENTION

[0001] The present invention relates to oxygen scavenging compounds and methods of using oxygen scavenging materials to reduce oxygen levels and maintain product properties of packaged oxygen sensitive products. For example, the oxygen scavenging materials and methods of the invention comprise the step of incorporating carbohydrates such as starches and reducing and I or hydrolyzable sugars into a polymer material or container used to package oxygen sensitive objects, such as foods, beverages, cosmetics, pharmaceutical products and others typically in order to increase the shelf life of the product packaged therein.

BACKGROUND OF THE INVENTION

[0002] It is well known that regulating the exposure of oxygen-sensitive products to oxygen maintains and enhances the quality and stability or shelf life of the product. In packaging oxygen sensitive materials such as foodstuffs, herbs, beverages, pharmaceuticals, cosmetics, tobacco, and cannabis, oxygen contamination can be particularly troublesome. Electronic components and military products such as ammunition and other explosives, may also be sensitive to moisture or atmospheric oxygen and require special packaging. Care is generally taken to reduce the detrimental or undesirable effects of oxygen on the product.

[0003] In the food and beverage packaging industry, many food products suffer oxygen- initiated degradation - for example, individual portions of prepared foods are marketed in containers made of plastics, and air entrapped therein, and leaking or transferring into the package after processing, is an acknowledged continuing industry problem. Limiting the exposure of oxygen sensitive food products to oxygen in a packaging system maintains the quality or freshness of the food, reduces spoilage, and extends the food’s shelf life.

[0004] Effective, safe, and environmentally-friendly packaging materials and containers useful for food, pharmaceutical, cosmetics and other industry applications continue to be highly desired in the packaging industry with improved oxygen regulating properties. In the food industry, for example, in order to preserve the color and flavor of certain food products, it is necessary to remove even minimal traces of oxygen from the package and the package must be maintained oxygen-free throughout the desired shelf life of the product. Currently, in this regard, small amounts of oxygen permeate many of the relatively gas-impermeable flexible packaging materials presently available commercially.

[0005] Numerous means for regulating oxygen exposure within packaging containers are used. In the 1960s, packaging containers were developed that envelop a product in an attempt to form a barrier within an oxygen-free package wherein free oxygen is ejected from the product and oxygen external to the package can be precluded. Such containers include modified atmosphere packaging (MAP) and oxygen barrier film packaging. Methods for excluding oxygen involving mechanical means also include vacuum and inert gas packaging. In these procedures, the oxygen is removed by displacement of the entire atmospheric mixture in the package by vacuumizing or flushing the oxygen from the container. In some instances, the package is backfilled with an inert gas. Such systems are used in boiler water treatment, the orange juice and brewing industries, and in modified-atmosphere packaging of food products. This technology, while somewhat equipment intensive, can remove about 90-95% of the oxygen present in air from the product (or its container) prior to or during packaging. However, the removal of the remaining 5-10% of oxygen using this approach requires longer times for vacuum treatment and increasingly larger volumes of higher and higher purity inert gas which must not itself be contaminated with trace levels of oxygen. This makes the removal by such methods of the last traces of oxygen expensive. A further disadvantage of these methods is a tendency to remove volatile product components. This is a particular problem with foods and beverages, wherein such components are often responsible for some or all of the aroma and flavor. These methods do not quantitatively remove all the oxygen from the package because complete evacuation is never achieved and oxygen often remains dissolved or trapped in the packaged product. In addition, when an inert gas backfill is used, the inert gas often brings traces of oxygen back into the package. Such vacuum or flushing methods, especially where inert gas handling is involved, often require machines of considerable cost and sophistication for highspeed packaging. It has proven extremely difficult to remove all traces of oxygen from packages of food products by mechanical means.

[0006] Another method used for regulating oxygen exposure is “active packaging”, whereby the package containing the food product has been modified in some manner to regulate the food’s exposure to oxygen. This concept combines such systems as oxygen regulation (by oxygen scavengers), moisture regulators, carbon dioxide (CCh) emitters, carbon dioxide (CO2) absorbers, ethylene absorbers and many more. [0007] Antioxidants (such as sulfur dioxide, trihydroxy butyrophenone, binylated hydroxy toluene and butylated hydroxy anisole) and oxygen scavengers (such as ascorbic acid, isoascorbic acid and glucose oxidase -catalase) have been used in an attempt to reduce the effects of oxygen contamination. The direct addition of such agents has several disadvantages. Both sulfur dioxide and ascorbates, (when added to beer, for example), can result in production of off-flavors thus negating the intended purpose of the addition.

[0008] One form of active packaging uses oxygen scavenging sachets which contain a composition which scavenges the oxygen through oxidation reactions. One type of sachet contains unsaturated fatty acid salts on a particulate adsorbent. Another type of sachet contains metal/polyamide complexes. Yet another type of sachet contains iron-based compositions which oxidize to their ferric states. A disadvantage arising from the iron-based sachets is that certain atmospheric conditions, for example high humidity or low carbon dioxide levels in the package are sometimes required in order for scavenging to occur at an adequate rate. A further potential problem with sachets containing synthetic chemical materials is that they can present a health hazard to consumers if accidentally ingested.

[0009] According to one embodiment, provided is a method of reducing the amount or oxygen level in a container by providing a sachet comprising the oxygen scavenger. The sachet may be presented in any desirable shape or configuration, for example, the sachet may be in a geometric shape, such as, a circle or an ornamental shape such as a flower. The sachet may have additional parts such as flaps. Typically, in accordance with the present invention, the sachet shall be comprised of an oxygen-permeable envelope used for the body of the sachet. For food applications, the sachet will be of food grade filter paper or gauze material. In an embodiment, the sachet containing the oxygen scavenger is provided and retained directly in a container. In an embodiment, the sachet is placed in direct contact with the packaged product, such as in a vacuum sealed package. In an alternate embodiment, the sachet is retained in the headspace of a package. In an alternate embodiment, the sachet is placed into a separate compartment that adjoins the product retention compartment wherein the oxygen is able to permeate between the two compartments enabling the oxygen scavenger to react and thereby affect the level of oxygen within the entire container.

[0010] Another means for regulating exposure of a packaged product to oxygen involves incorporating an oxygen scavenger into the packaging structure itself. A more uniform scavenging effect through the package is achieved by incorporating the scavenging material in the package instead of adding a separate scavenger structure such as a sachet to the package. Uniformity may be especially important where there is restricted airflow inside the package. In addition, incorporating the oxygen scavenger into the package structure provides a means of intercepting and scavenging oxygen as it permeates the walls of the package (the “active oxygen barrier”), thereby maintaining the lowest possible oxygen level in the package. Limited success has been achieved in incorporating oxygen scavenging material into the walls of packages for various types of foods. Previously developed scavengers include sulfite-based, ascorbate-based and enzymebased systems as well as oxidizable polyamides and ethylenically unsaturated hydrocarbons.

[0011] It is an object of this invention to provide alternative oxygen scavenging compounds, materials and related methods that are safe and effective for use with foods and other objects. It is a further object of this invention to provide packaging and methods for packaging of oxygen sensitive products comprising safe and effective oxygen scavenging materials. It is a further object of the invention to provide a package which will remain oxygen-free or at reduced concentration of oxygen for a desired storage period of the product or packaged therein. A still further object of the invention is to provide an improved method for packaging products wherein the level of oxygen in the package is controlled. Another object of the invention is to provide a sealed package for food products wherein free oxygen is effectively removed. A further object of the invention is to provide a material which is suitable for forming an oxygen-free, substantially oxygen-free or oxygen modified package.

SUMMARY OF THE INVENTION

[0012] For hundreds, even thousands of years, it has been known to use sugars in meats, jams, jellies and myriad of other food and beverage products for preservation of the product. Sugar not only increases flavor but helps formation of a gel that aids in preservation of a product for increased shelf life. When large amounts of sugar are used, the sugar acts as a preservative by inhibiting microbial activity, typically by rupturing the walls of the bacteria through osmotic effect. However, heretofore, sugar in and of itself has not been utilized or known for its oxygen scavenging characteristics in the manner disclosed herein.

[0013] Applicant has discovered that reducing sugars, in the forms of starch and other carbohydrates, can be used for oxygen modification within a closed environment, which functions separately from its antimicrobial activity and can therefore be of great use in oxygen modified packaging and materials. Applicant further notes that certain non-reducing sugars can, upon hydrolysis, yield reducing sugars which themselves can be used for oxygen modification. For this reason, non-reducing sugars can be utilized in the compositions and methods disclosed herein, particularly if methods of hydrolysis are considered.

[0014] Sugars are found in the tissues of most plants. Honey and fruit are abundant natural sources of unbounded simple sugars. Sucrose is especially concentrated in sugarcane and sugar beet, making them ideal for efficient commercial extraction to make refined sugar. It is reported that the world’s sugar production in 2019/2020 was approximately 166 million metric tons. Due to it being a natural and highly abundant ingredient, sugar is an ideal material for use in food packaging applications, and presents obvious benefits over alternative materials discussed above, especially in food and beverage packaging.

[0015] Disclosed herein is a method for reducing the concentration of oxygen in a container, the method including placing into a closable container an effective amount of an oxygen scavenging polymer composition entrained with one or a plurality of reducing and I or hydrolyzable sugars for a time sufficient to reduce the concentration of oxygen in the container when closed. Further disclosed are polymer compositions comprising reducing and I or hydrolyzable sugars and entrained polymer materials for use in packaging of oxygen-sensitive objects. The compositions, materials and packaging methods reduce oxygen concentrations and exposure to oxygen of oxygen-sensitive products thus reducing oxygen-initiated degradation of such products.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The invention will be described in conjunction with the following drawings in which like reference numerals designate like elements and wherein:

[0017] FIG. 1 is a representational graph showing the recorded experimental results of Example la of the oxygen scavenging film incorporating the daucus-based oxygen scavenging composition prepared from fresh carrots according to an optional aspect of the invention.

[0018] FIG. 2 is a representational graph showing the recorded experimental results of Example lb of the oxygen scavenging film incorporating the daucus-based oxygen scavenging composition in the form of dried carrot powder according to an optional aspect of the invention.

[0019] FIG. 3 is a representational graph showing the recorded experimental results of Example 1c of the oxygen scavenging film incorporating the daucus-based oxygen scavenging composition in the form of carrot juice according to an optional aspect of the invention, and showing samples with green tea.

[0020] FIG. 4 is the representational graph of FIG. 1, Example 1c, as further compared to a reference control sample film without the oxygen scavenging composition of the invention.

[0021] FIG. 5 is a cross sectional view of a sheet or film formed of a polymer composition comprising the oxygen scavenging agent according to an optional embodiment of the present invention, adhered to a barrier sheet substrate.

[0022] FIG. 6 is a close-up schematic view of the entrained polymer according to FIG. 5 showing the tea oxygen scavenging agent.

[0023] FIG. 7 is a cross section of a package that may be formed using an entrained polymer comprising the oxygen scavenging agent according to an optional embodiment of the present invention.

[0024] FIG. 8 is a representational graph showing the experimental results of Example 2a of an oxygen scavenging film according to the invention.

[0025] FIG. 9 is a second representational graph showing the experimental results of Example 2b of an oxygen scavenging film according to the invention as compared to an alternate control oxygen scavenging film.

[0026] FIG. 10 is a graph of the experimental results of Example 2c showing the oxygen scavenging capacity of an embodiment of a film according to the invention with and without the presence of water in a sealed container.

[0027] FIG. 11 is a graph of the experimental results of Example 2d showing the performance of an embodiment of the oxygen scavenging agent of the invention comprising black tea.

DETAILED DESCRIPTION OF THE INVENTION

[0028] Herein, the term “oxygen scavenger” means a compound, composition or material which can react with, adsorb or bind oxygen so as to remove oxygen and/or reduce the oxygen level from the interior of a closed or enclosed environment, typically a vessel, such as a package or container. The oxygen scavenger can modify the amount, level or concentration of oxygen within the enclosed space (e.g., in a container or package). The term “oxygen scavenging” refers herein to oxygen regulation, oxygen modification and/or oxygen control. Generally, the oxygen scavenging material of the invention may also function as an “antioxidant”, a substance that inhibits oxidation and refers to a compound, composition or material which slows the rate of oxidation or otherwise reduces the undesirable effects of oxidation upon an oxygen-sensitive object. Specifically, the oxygen scavenger or oxygen scavenging active material used in accordance with the invention herein are reducing and I or hydrolyzable sugars.

[0029] Applicant has tested multitudes of materials, particularly natural source materials that are known to be safe, in an attempt to discover new and useful oxygen scavengers that could optionally be incorporated into polymer compositions for use in oxygen modified packaging. During the studies, it was determined that multiple varieties of materials that function effectively as oxygen scavengers had one common component between them, which was that they contained one or multiple types of reducing and / or hydrolyzable sugars. Consequently, Applicant has developed and discloses herein compositions, materials and methods for use in oxygen modified packaging using reducing and I or hydrolyzable sugars as active agents for oxygen modification.

[0030] As used herein, the term “sugar” refers to and includes disaccharides, oligosaccharides and polysaccharides and any other soluble carbohydrates. Common examples are sucrose, lactose and maltose. Sugar herein also includes starch, which is a glucose polymer found in plants, commonly such as corn, potatoes and yams, and rice, as well as in fruits such as figs, peaches and bananas. The sugar useful herein can be derived from any source and is not limited, such as sugarcane, honey, maple syrup, agave, molasses, fruits, vegetables, tea, coffee, other plants and flowers, dairy products (ex. lactose) and/or is synthesized. Sugar includes both what is commonly known as white sugar and brown sugar and can be course crystals, granulated, or milled for incorporation into polymer compositions herein. The sugars useful herein can be used in their raw form, refined form or in liquid form. Although some monosaccharides may be functional in the compositions and methods herein, monosaccharides are not ideal because they are not easily hydrolyzable. Optionally, the sugar is provided in raw form. Alternatively, the sugar is a natural component of a plant-derived material (e.g., tea, fruit or vegetable) and the plant derived material is used as an oxygen scavenging composition.

[0031] As used herein, the term “reducing sugar” refers to a sugar whose anomeric center is free, i.e., the sugar is an aldose in linear or cyclic form, and therefore contains an aldehyde or an aldehyde equivalent. It will be recognized by persons skilled in the art that ketoses, which contain ketones, may readily interconvert to the aldehyde form upon tautomerization, and therefore are embraced by the term “reducing sugar”. [0032] As used herein, the term “non-reducing sugar” refers to a sugar that is lacking a free anomeric center. Lacking an aldehyde or an aldehyde equivalent, non-reducing sugars do not participate in oxidation I reduction reactions nearly as much as reducing sugars. Examples of nonreducing sugars recognized in the art include sucrose, raffinose, and trehalose. Certain nonreducing sugars, including sucrose, will undergo hydrolysis to yield reducing sugars.

[0033] Optionally, the sugars used herein are hydrolyzable, whereby in their most hydrolyzed state, the carbohydrate molecules are broken down by water molecules to produce their fundamental monosaccharides, meaning that the water molecule is consumed to effect separation of a larger sugar molecule into its component parts, such as glucose, fructose, and galactose. The sugars herein do not require absolute hydrolysis in order to function within the intended scope of the invention for oxygen scavenging.

[0034] In some embodiment, hydrolysis of a non-reducing sugar can produce a reducing sugar. This can occur upon hydrolytic cleavage of a glycosidic bond, which provides a new sugar with a free anomeric center. In some embodiments, the oxygen scavenger comprises a nonreducing sugar which becomes a reducing sugar upon hydrolysis. Use of sugars in this manner can provide a time-release aspect to oxygen scavenging, whereby a certain amount of reducing sugar is released over a period of time.

[0035] According to an optional embodiment, an oxygen scavenging packet comprising sugar is provided to a container or package for oxygen regulation, for example, as a sugar packet commonly available on the general market or oxygen permeable sachet or cannister. Alternatively, sugar or sugar-containing source material may be loosely disposed in a compartment that is open to, or is otherwise configured to enable oxygen transmission between, the compartment and an interior space of a package.

[0036] According to an optional aspect of the invention, sugar or source material containing sugar is combined with a polymer or combination of polymers and/or incorporated into polymer compositions in order to form oxygen scavenging polymer compositions. Suitable polymer compounds useful herein include thermoplastic polymers such as polypropylene, polyethylene, and polyoxmethylene, polyolefins such as polypropylene and polyethylene, olefin copolymers, polyisoprene, polybutadiene, acrylonitrile butadiene styrene (ABS), polybutene, polysiloxane, polycarbonates, polyamides, ethylene-vinyl acetate (EVA), ethylene- methacrylate copolymer, polyvinyl chloride (PVC), polystyrene, polyesters, polyanhydrides, polyacrylianitrile, polysulfones, polyacrylic ester, acrylic, polyurethane and polyacetal, or copolymers or combinations thereof.

[0037] The polymer articles comprising the sugar component according to the invention are preferably produced by extrusion molding, injection molding, blow molding or vacuum molding using standard molding equipment, as will be dictated by the intended particular product application and are generally well known.

[0038] According to another embodiment, sugar-based polymer compositions are further formed into packaging materials, such as food storage trays or boxes, or are incorporated directly into the packaging material or component thereof for packaging applications. Standard materials commonly used in the package production industry are plastics, paper, glass, metals, synthetic resins and combinations thereof.

[0039] The oxygen scavenging property of the sugar group is typically activated for scavenging oxygen by contact with atmospheric moisture, such as water or vapor. When in a container, the moisture is provided by the moisture content in the container or moisture vapor that permeates into or through the package. According to an embodiment, the sugar-based oxygen scavenging entrained polymer compound is retained in the container in a dry state and remains substantially inactive until activated for oxygen scavenging by contact with moisture.

[0040] Once activated, the sugar-based oxygen scavenging compositions of the invention function to control oxygen levels by reducing or maintaining a certain amount of oxygen within an enclosed space, such as in a vessel. Optionally, the amount of oxygen within the vessel will be controlled by the amount of sugar molecules or number of sugar groups that are incorporated into the polymer composition.

[0041] According to an embodiment, the sugar-based polymers herein are formed into films and/or sheets typically made of layers of film. The terms “film” and “sheet” may be used interchangeably or synonymously herein. The sugar-based component that is reactive with oxygen may either be embedded in the matrix of the polymer film or incorporated covalently therein. The sheet of polymer material may be either totally or partially clear, tinted, transparent or opaque, depending on the properties of the polymer and on the desired use of the film.

[0042] In an alternate embodiment, a film composition incorporating the sugar-based component according to the invention can be placed directly or wrapped directly around the entire package or container, be placed on part of the container or be placed on the object or on part of the object requiring oxygen control. For a food product, the item can be wrapped directly with the film product of the invention, that in an embodiment, will typically be provided in the form of polyethylene film commonly known as “cling-wrap”, “shrink wrap” or “saran wrap” (formerly a registered trademark of Johnson Home Storage, Inc., Delaware, USA). Alternatively, a layer or multiple layers of the film of the invention can be placed into any container in order to convey the oxygen-scavenging characteristics of the invention to such container and thereby reduce the level of oxygen within the container. The desired specific oxygen transport rate (OTR) of the wrap will typically depend upon the desired end-use application, such as the type of food, drug or cosmetic to be packaged.

[0043] In an alternate embodiment, the sugar-based oxygen scavenging compound is incorporated into an entrained polymer. As used herein, the term “entrained” as in “entrained polymer” refers to a generally monolithic material having an essentially uniform composition formed of at least a base polymer, an active agent (the sugar component herein) and optionally, a channeling agent that are distributed throughout. The entrained polymer composition is essentially uniform throughout but does not need to be perfectly homogeneous. An entrained polymer thus comprises at least two phases (the base polymer and active agent, without a channeling agent) or at least three phases (base polymer, active agent and a channeling agent). As used herein, the term “three phase” is defined as a monolithic composition or structure comprising three or more phases. An example of a three phase composition is an entrained polymer formed of a base polymer, an active agent (the oxygen scavenging sugar component), and a channeling agent. Optionally, a three phase composition or structure may include an additional phase, such as a colorant or antibacterial agent, but is nonetheless still considered “three phase” on account of the presence of the three primary functional components.

[0044] As disclosed above, the methods of producing entrained polymers according to the present invention are not particularly limited. The entrained polymer may be manufactured, extruded, molded, attached, adhered, placed, or otherwise included in any container or package via conventional methods as discussed above. Preferably, the entrained polymers according to the invention comprising the sugar-based active component(s) are molded by extrusion or injection molding into a variety of desired forms, e.g., containers, molds, container liners, plugs, film sheets, pellets and other such structures. [0045] Typical production of the three phase entrained polymer includes blending a base polymer, the active material and a channeling agent. The active agent is blended into the base polymer either before or after adding the channeling agent. All three components are uniformly distributed within the entrained polymer mixture. The entrained polymer thus prepared contains at least three phases. Entrained polymers are further described, for example, in U.S. Pat. Nos. 5,911,937, 6,080,350, 6,124,006, 6,130,263, 6,194,079, 6,214,255, 6,486,231, 7,005,459, and U.S. Pat. Pub. No. 2016/0039955, each of which is incorporated herein by reference as if fully set forth herein.

[0046] Suitable channeling agents of the entrained polymer operable herein include polyglycol such as polyethylene glycol (PEG), ethylene-vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin poly amine, polyurethane and polycarboxylic acid including poly aery lie acid or polymethacrylic acid. Alternatively, the channeling agent can be, for example, a water insoluble polymer, such as a polypropylene oxide-monobutyl ether, polyethylene glycol, which is commercially available under the trade name Polyglykol B01/240; polypropylene oxide monobutyl ether, which is commercially available under the trade name Polyglykol B01/20; and/or polypropylene oxide, which is commercially available under the trade name Polyglykol DO 1/240, all produced by Clariant Specialty Chemicals Corporation. Other embodiments of channeling agents comprise ethylene vinyl acetate, nylon 6, nylon 66, or any combination of the foregoing. Optionally, the optional channeling agent ranges from 1% to 25%, optionally from 2% to 20%, optionally from 2% to 12%, optionally from 5% to 15%, optionally from 5% to 10%, optionally from 8% to 15%, optionally from 8% to 10%, optionally from 10% to 20%, optionally from 10% to 15%, or optionally from 10% to 12% by weight with respect to the total weight of the entrained polymer.

[0047] FIGS. 5 and 6 are a schematic illustration of an active sheet or film 75 formed of base polymer 25 with channeling agent 35 and the tea oxygen scavenging active agent 30 forming entrained polymer 20. FIG. 5 illustrates film 75 used in combination with a barrier sheet 80 to form a composite, according to an optional aspect of the invention. FIG. 6 is a close-up schematic view of the entrained polymer of FIG. 5. A channeling agent 35 forms interconnecting channels 45 through the entrained polymer 20. At least some of the active agent 30 is contained within these channels 45, such that the channels 45 enable communication between the active agent 30 and the exterior of the entrained polymer 20 via channel openings 48 formed at outer surfaces 25 of the entrained polymer 20. FIG. 6 shows the tea active agent 30 with arrows indicating the path 10 of moisture (not shown) from an exterior of the entrained polymer 20, through the channels 45, to the particles of active agent 30 for initiation of oxygen scavenging activity.

[0048] FIG. 7 illustrates an optional embodiment in which the active sheet or film 75 and the barrier sheet 80 are combined to form a package 85 in the form of a wrap having active characteristics at an interior surface formed by the entrained polymer 20 in the active sheet or film 75, and moisture vapor resistant characteristics at an exterior surface formed by the barrier sheet 80. In this embodiment, the active sheet or film 75 occupies a portion of the barrier sheet 80. The barrier sheet 80 may be a substrate such as foil and/or a polymer with low moisture and/or oxygen permeability. The barrier sheet 80 is compatible with the entrained polymer structure 75 and is thus configured to thermally bond to the active sheet or film 75, when the active sheet or film 75 solidifies after dispensing. As illustrated, the sheets are joined together to form an active package 85. As shown, two laminates or composites are provided, each formed of an active sheet or film 75 joined with a barrier sheet 80. The sheet laminates are stacked, with the active sheet or film 75 facing one another, so as to be disposed on an interior of the package, and are joined at a sealing region 90, formed about a perimeter of the sealed region of the package interior.

[0049] The oxygen scavenging property of the sugar component is typically activated for scavenging oxygen by contact with atmospheric moisture, moisture content in the package or moisture vapor that permeates into or through the package. According to an embodiment, the sugar-based oxygen scavenging compound is retained in the packaging material in a dry state and remains substantially inactive until activated for oxygen scavenging by contact with water or water vapor.

[0050] According to an alternate embodiment, rather than incorporating the sugar-based oxygen scavenging agent into or onto a base polymer, the sugar-based oxygen scavenging agent may also be combined with, suspended in, or otherwise incorporated into an absorbent material directed to and suitable for absorbency of liquids or moisture within the container in order to enhance oxygen scavenging control and regulation within the container. For example, the sugar- based oxygen scavenging agent can be combined directly with an absorbent matrix material.

[0051] An example of such a matrix material is an adsorbent composition of matter as disclosed in U.S. Pat. No. 6,376,034, which is incorporated by reference herein in its entirety. The absorbent composition of matter or “absorbent packet” used interchangeably herein, has an absorbency, the absorbency being defined by weight of liquid absorbed/weight of the absorbent composition of matter. The absorbent composition of matter optionally includes the following: (i) at least one non-crosslinked gel-forming water soluble polymer having a first absorbency, the first absorbency being defined by weight of liquid absorbed/weight of the at least one non-crosslinked gel forming polymer, the at least one non-crosslinked gel forming polymer being food safe; and (ii) at least one mineral composition having a second absorbency, the second absorbency being defined by weight of liquid absorbed/weight of the at least one mineral composition, the at least one mineral composition being food safe, the absorbency of the absorbent composition of matter exceeding a sum of the first absorbency and the second absorbency, the absorbent composition of matter being compatible with food products such that the absorbent composition of matter is food safe when in direct contact with the food products. Optionally, the absorbent composition of matter includes additionally: (iii) at least one soluble salt having at least one trivalent cation, the at least one soluble salt having at least one trivalent cation being food safe.

[0052] The absorbent material contains from about 10 to 90% by weight, preferably from about 50 to about 80% by weight, and most preferably from about 70 to 75% by weight of a non- crosslinked gel forming polymer. The non-crosslinked gel forming polymer can be a cellulose derivative such as carboxymethylcellulose (CMC) and salts thereof, hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose, gelatinized starches, gelatin, dextrose, and other similar components, and may be a combination of the above. Certain types and grades of CMC are approved for use with food items and are preferred when the absorbent is to be so used. The preferred polymer is a CMC, most preferably sodium salt of CMC having a degree of substitution of about 0.7 to 0.9. The degree of substitution refers to the proportion of hydroxyl groups in the cellulose molecule that have their hydrogen substituted by a carboxymethyl group. The viscosity of a 1% solution of CMC at 25° C., read on a Brookfield viscometer, should be in the range of about 2500 to 12,000 mPa.

[0053] The clay ingredient in the matrix material can be any of a variety of materials and is preferably attapulgite, montmorillonite (including bentonite clays such as hectorite), sericite, kaolin, diatomaceous earth, silica, and other similar materials, and combinations thereof. Preferably, bentonite is used. Bentonite is a type of montmorillonite and is principally a colloidal hydrated aluminum silicate and contains varying quantities of iron, alkali, and alkaline earths. The preferred type of bentonite is hectorite which is mined from specific areas, principally in Nevada. Diatomaceous earth is formed from the fossilized remains of diatoms, which are structured somewhat like honeycomb or sponge. Diatomaceous earth absorbs fluids without swelling by accumulating the fluids in the interstices of the structure.

[0054] Optionally, a soluble salt is provided in order to render a trivalent cation. The soluble salt is optionally derived from aluminum sulfate, potassium aluminum sulfate, and other soluble salts of metal ions such as aluminum, chromium, and the like. Preferably, the trivalent cation is present at about 1 to 20%, most preferably at about 1 to 8%. The inorganic buffer is one such as sodium carbonate (soda ash), sodium hexametaphosphate, sodium tripolyphosphate, and other similar materials. If a buffer is used, it is present preferably at about 0.6%, however beneficial results have been achieved with amounts up to about 15% by weight.

[0055] The combination of the non-crosslinked gel forming polymer, trivalent cation, and clay forms an absorbent material which when hydrated has an improved gel strength over the noncrosslinked gel forming polymer alone. Further, the gel exhibits minimal syneresis, which is exudation of the liquid component of a gel. In addition, the combined ingredients form an absorbent which has an absorbent capacity which exceeds the total absorbent capacity of the ingredients individually. The sugar-based oxygen scavenging component may function to further enhance the moisture absorbing characteristics of the absorbent material. The oxygen scavenging absorbent gel compositions according to the invention are typically glass clear, firm gels which may have applications in areas such as for cosmetic materials.

[0056] The resulting absorbent material can be fashioned into a number of different structures or flexible packages, such as pouches, thermoformed packs, lidding materials, or other packages of various sizes and geometric shapes. In an embodiment, for example, a two-ply wall within the package can be made by standard techniques such as a two-wall sheath of material or the flexible packs with two-ply walls, one or both of which may comprise the absorbent material. [0057] The permeable or inner ply of the absorbent wall can have a dual layer structure with two layers of the same fibers. The fibers are packed more closely together on the side which is closer to the absorbent and are packed into a more open network on the side closer to the packaged products. In this way the absorbent ply has smaller pores on the side closer to the absorbent and the absorbent is thus unlikely to migrate through the fabric. On the other hand, the ply next to the liquid typically has larger pores to encourage migration of the liquid throughout. While a specific embodiment of a flexible package is described, other embodiments of flexible packages are envisioned utilizing the sugar-based oxygen scavenging component absorbent composition described herein.

[0058] According to an optional aspect of the invention, liquid or moisture within the container of the invention serves to initiate the oxygen scavenging characteristics of the sugar oxygen scavenging material, causing the modification, specifically, the decrease in the level of oxygen within the container environment or headspace. Without being bound to a mechanism of action, it is thought that the liquid component functions to initiate, further facilitate, hasten, or augment the oxygen scavenging reaction of the sugar component. Thus, in a preferred embodiment of the invention, a liquid such as water is added to a sealable container of the invention. Any liquid or solutions may be utilized and will depend on the compatibility of the liquid component with the object being stored within a container. Other moisture-containing compositions which exude moisture, such as gels, lotions, creams, may be utilized and will also be dictated by the desired use of the container. Alternatively, the stored products themselves (e.g., moisture-rich foods) may exude moisture in an amount sufficient to activate oxygen scavenging material of the present invention. It is a distinct advantage that no metal salts or photoinitiators are required to initiate or cause the oxygen modification within the package.

[0059] Optional embodiments of absorbent materials usable in conjunction with an optional aspect of the invention include potassium aluminum sulfate, bentonite (i.e. hectorite), diatomaceous earth, soda ash (sodium carbonate), and alginate, though the absorbent materials are not limited to only these compounds and other commonly used compounds may be used.

[0060] In certain embodiments, the polymer comprising the sugar-based active agent is activated once a barrier film is removed and the sugar active is exposed to the atmospheric moisture within the container or moisture coming from the object within the container. In certain embodiments, a controlled release or a desired release profile can be achieved by applying a coating to the active agent, such as for example, such as using a spray coater, wherein the coating is configured to expose, and thus render effective, the sugar component within a desired time frame. Different coatings may be applied to achieve different release effects. For example, the film may be coated with extended release coatings of varying thicknesses and/or properties to achieve the desired release profile. For example, some active agent will be coated such that the polymer composition will not begin oxygen scavenging until after a few hours or a few days, while other coating agents will allow oxygen scavenging to begin immediately. Spray coating technology is known in the art. For example, pharmaceutical beads and the like are spray coated to control the release rate of active ingredient, e.g., to create extended or sustained release drugs. Optionally, such technology may be adapted to apply coatings to the active agent to achieve a desired controlled rate of oxygen modification in the container of the invention.

[0061] Optionally, in an embodiment of a container of the invention, the entrained polymer is covered with a barrier film on one or both sides of the surface of the polymer in order to protect the sugar-based oxygen scavenging active agent from potential premature reaction within the container. The barrier film is preferably gas or moisture impermeable. When the entrained polymer is placed in the container, the barrier film is removed, allowing the sugar-based oxygen scavenging agent to perform.

[0062] Optionally, the entrained polymer may also be covered with a backing film on one or both sides. The backing film may be gas or moisture permeable to allow the sugar-based oxygen scavenging component to travel to the surrounding environment. For example, a high-density polyethylene film, such as a nonwoven film (e.g. TYVEK® by DuPont de Nemours, Inc.), may be used as a gas permeable backing film.

[0063] Alternatively, a controlled release and/or desired release profile may be achieved by providing a layer, optionally on both sides of a film according to the invention, of a material configured to control exposure. For example, the film may include a polymer liner, made e.g., from low density polyethylene (LDPE) disposed on either side or both sides thereof. The thickness of the film and liner(s) can vary as disclosed above. The LDPE liners may be coextruded with the film or laminated thereon. Alternatively, a controlled release and/or desired release profile may be achieved by modifying the formulation of an entrained polymer according to the invention. For example, adjusting the type and the concentration of the channeling agent to provide a desired control rate of the oxygen scavenging sugar agent.

[0064] Optionally, an entrained polymer film according to the invention may be used in combination with a barrier sheet to form a composite. The barrier sheet may be a substrate such as foil and/or a polymer with low moisture or oxygen permeability. The barrier sheet is compatible with the entrained polymer structure of the active sheet or film and is thus configured to thermally bond therewith, when the active sheet or film solidifies after dispensing.

[0065] Optionally, the active sheet or film and the barrier sheet are combined to form a packaging wrap having active characteristics at an interior surface formed by the entrained polymer in the active sheet or film, and vapor and oxygen resistant characteristics at an exterior surface formed by the barrier sheet. In this embodiment, the active sheet or film occupies a portion of the barrier sheet.

[0066] In one embodiment, the barrier sheets are joined together to form an active package, as shown in Fig. 7. As shown, two laminates or composites are provided, each formed of an active sheet or film joined with a barrier sheet. The sheet laminates are stacked, with the active sheet or film facing one another, so as to be disposed on an interior of the package, and are joined at a sealing region, formed about a perimeter of the sealed region of the package interior.

[0067] Optionally, within an embodiment of a polymer composition according to the invention, the sugar-based oxygen scavenging active agent loading level (i.e., the sugar itself in raw form or the source material that contains sugar) is in an amount or concentration sufficient to be effective to act as an oxygen scavenger in a given application or environment. Preferably, the concentration of the sugar-based active agent ranges from 0.1% to 70%, optionally from 5% to 60%, optionally from 10% to 50%, optionally from 20% to 40%, optionally from 30% to 35% by weight with respect to the total weight of the polymer composition with the loading of the base polymer, optionally, the channeling agent, and optionally other additives such as colorant, forming the remainder of the polymer composition. The amount of the sugar-based active component is chosen according to the level of oxygen and amount of oxygen control desired in the container depending on the particular product to be contained within.

[0068] Optionally, an entrained polymer may be a two phase formulation including 20% to 70% by weight of the sugar-based oxygen scavenging agent, preferably in powder form, 30% to 80% by weight a base polymer (such as polyethylene, polyethylene-based copolymer, polypropylene, ethylene vinyl acetate (EVA), or a mixture) . The base polymer is not particularly limited. Optionally, an entrained polymer may be a three phase formulation including 20% to 60% by weight of the sugar-based oxygen scavenging agent, preferably in a powder form, 30% to 70% by weight a base polymer (such as polyethylene, polyethylene-based copolymer, polypropylene, ethylene vinyl acetate (EVA), or a mixture) , and 2-15% by weight a channeling agent (such as a PEG). The base polymer and the channeling agent are not particularly limited.

[0069] In optional embodiments, the sugar-based oxygen scavenging active in accordance with the invention may be combined with other oxygen scavenging agents in order to achieve and control desired oxygen levels. Such other oxygen scavenging materials include, but are not limited to, oxidizable polymers, ethylenically unsaturated polymers, benzylic polymers, allylic polymers, polybutadiene, poly[ethylene-methyl-acrylate-cyclohexene acrylate] terpolymers, poly[ethylene- vinylcyclohexene] copolymers, polylimonene resins, poly beta -pinene, poly alpha-pinene and a combination of a polymeric backbone, cyclic olefinic pendent groups and linking groups linking the olefinic pendent groups to the polymeric backbone. Other additional oxygen scavenging agents can include polycarboxylic or salicylic acid chelate or complexes. Furthermore, although no metal salts or photoinitiators are required in order to initiate the sugar-based oxygen scavenging materials of the invention, in optional embodiments, incorporating other oxygen scavenging materials, metals salts and photoinitiators may be may be utilized in order to further catalyze the oxygen scavenging properties of such materials.

[0070] According to yet another embodiment, the sugar-based component may be incorporated into a composite material composed of a plurality of polymer layers joined together. For example, the matrix may be formed from an organic -inorganic hybrid polymer; alternatively it may have a purely organic construction.

[0071] The terms “package,” “packaging” and “container” are used interchangeably herein to indicate a vessel that holds or contains an object. Optionally, a package may include a container with an object (i.e. product) stored therein. “Headspace” refers to any empty space surrounding an object stored within the interior space of the package or container. Non-limiting examples of a package, packaging and container include a tray, box, carton, bottle, jar, pouch, vial, flexible bag, blister pack or any other receptacle or vessel capable of holding an object.

[0072] In certain embodiments of a vessel herein, the sugar entrained oxygen scavenging polymer material component is located in the headspace or other compartment of the container and does not physically contact the oxygen sensitive product, for example, as an insert, plug or film on the walls of a container, or a cap of a bottle. For example, in an optional embodiment of a food package, the sugar entrained polymer film according to the invention is disposed onto or within the walls of a food package. Optionally, the film may be adhered, e.g., using an adhesive, to an inner surface of the package. Alternatively, the film may be heat staked (without an adhesive) to the inner surface of the package. Heat staking allows the film to permanently adhere to the sidewall without use of an adhesive. An adhesive may be problematic in some circumstances because it may release unwanted volatiles in a food-containing headspace. Heat staking, in this instance, refers to heating a sealing layer substrate on the sidewall while exerting sufficient pressure on the film and sealing layer substrate to adhere the film to the container wall. Optionally, the polymer film or layer is deposited and adhered to the package via a direct in-line melt adhesion. [0073] Alternatively, one or multiple strips of film may be placed inside the package for oxygen regulation with or without being adhered or affixed to a surface of the container. The size and thickness of the film can vary. Optionally, the film may range from 0.1 mm to 1.0 mm, more preferably from 0.2 mm to 0.6 mm. In certain embodiments, the film has a thickness of approximately 0.2 mm or 0.3 mm.

[0074] In the preferred embodiment, the package or container is closed or covered in order to optimize oxygen uptake and regulation. It is contemplated and understood that any type of cover may be used which is appropriate with the use of the particular vessel, such as a cover, a cap, a lid, a plug, a stopper, a cork, a gasket, a seal, a washer, a liner, a ring, a disk, or any other closure device. Optionally, the cover or closure device is transparent so that the interior can be viewed. The cover or closure device may optionally be further sealed onto the package using a variety of processes including but not limited to, for example, a lidding sealant, an adhesive, or a heat seal. The container or package of the invention can be used in commerce for any purpose such as food transportation, preservation and/or storage. The shape or geometry of the container or package is not limited. In one optional embodiment, the package or container is composed of a rigid or semirigid polymer, optionally polypropylene or polyethylene, and preferably has sufficient rigidity to retain its shape under gravity.

[0075] The invention is further illustrated in more detail with reference to the following actual and prophetic examples, but it should be understood that the invention is not deemed to be limited thereto.

EXAMPLES

Example 1 - Daucus

[0076] Applicant tested the compositions and methods herein using daucus, commonly known as carrots. Disclosed below are relevant examples demonstrating the invention herein and provides a thorough understanding of the subject invention and its various embodiments. The experimentation is described as relating to the use of carrots as an oxygen scavenging active agent. Without being bound to a mechanism of action, Applicant further determined that the oxygen scavenging capacity of the daucus-based compositions was a result of the reducing and I or hydrolyzable sugars found in the daucus as described in the current specification. The results set forth below demonstrate the oxygen scavenging function of the reducing and I or hydrolyzable sugars derived from carrots (in various forms) when incorporated into entrained polymer compositions. Some of the results set forth below are also contained in the PCT Application No. PCT/US21/70237, filed by Applicant on March 5, 2021, entitled, “Daucus-Based Compositions for Oxygen Modified Packaging,” (and is incorporated by reference herein in its entirety).

Example la - Natural Carrot Powder

[0077] Five samples of film comprising dry carrot (daucus) powder were prepared by Aptar CSP Technologies Inc. by slicing raw fresh carrots, drying the slices in a vacuum oven for 3 days at 60°C, then grinding the dried slices into a powder. 0.25g of the daucus powder was placed into the glass bottles and sealed. The amount of oxygen within the bottles was measured for 135 days. The averaged results of the five sample group are set forth in the representational graph of FIG. 1. The concentration of oxygen within the enclosed bottles was significantly reduced to as low as zero (0%) or essentially zero percent (0%) in all the samples. As used herein, the term “essentially zero” in referring to a concentration of oxygen indicates a concentration that was not detectable by the OXYSENSE® measuring apparatus used herein. The concentration of oxygen continued to remain at low or at essentially zero levels for the duration of the testing period.

Example lb - Dried Carrot Powder

[0078] Fifteen (15) samples of film incorporating freshly dried carrot powder were tested. Three different sample groups of polymer film were extruded incorporating 0.5g of dried carrot powder that was first prepared according to the following methods set forth in Table 1:

Table 1: Preparation of dried carrot powder samples.

[0079] 1 mL of water was added to each container and the containers were sealed. The oxygen level in each container was measured over a duration of 136 days. FIG. 2 illustrates the recorded results. The results were consistent across all three sample preparations. The oxygen concentration within the sealed containers dropped significantly from the normal atmospheric concentration to below 5% in the first 10 days, and to essentially 0% within 20 to 30 days, thereafter remaining at 0% or essentially 0% for the duration of the testing period.

Example 1c - Carrot Juice

[0080] Fifteen (15) samples were prepared of the oxygen scavenging component as set forth in Table 2 and incorporated into polymer film. Five sealed bottles containing 0.425g ground fresh carrot with 1 mL of water were prepared, making a carrot juice (samples 1-5); five bottles were similarly prepared and an additional 0.0425g of ground green tea was added to the bottles and sealed (samples 6-10); five additional samples containing 0.0425g of carrot juice powder, 0.0425g of ground green tea and 1 mL of water were prepared and sealed.

Table 2: Preparation of carrot juice samples.

[0081] The results at of the full test period of 150 days are illustrated in FIG. 3. Samples 1-5 containing ground fresh carrot reduced the oxygen level within the bottles to approximately 7 to 10%. Samples 5-10 incorporating green tea in addition to the carrot juice demonstrated a greater decrease in the oxygen level within the container to essentially 0% as was found in the other Examples above. It was interesting to note that samples 11-15 having a carrot juice made of carrot powder with water instead of fresh ground carrots (also incorporating green tea as in samples 5- 10) showed a reduction level of oxygen to essentially 0%, whereas the carrot juice made from ground carrot (samples 1-5) showed a reduction of oxygen to only approximately 10%.

Example Id - Comparison with Control Oxygen Scavenger

[0082] The oxygen scavenging results of the 15 samples of Example 1c were compared to a control sample. The control sample constituted a reference film that is a commercially available oxygen-absorbing resin film made based on the teachings of U.S. Pat. No. 7,893,145, a known oxygen scavenging material within the industry of packaging materials, without any oxygen scavenging component of the invention. Oxygen concentration was measured over 15 days. FIG. 4 is a representational graph illustrating the 15 samples of Example 1c as compared to the reference control sample. FIG. 4 demonstrates clearly that the oxygen scavenging compositions of the invention operate far more effectively than the reference control sample in reducing the concentration of oxygen in a closed container.

Example le - Moisture Test

[0083] Further samples of film according to the invention comprising carrot juice in powder form, with and without green tea and with and without water (ImL) were studied as set forth above. For all samples, it was observed that water (or moisture) was instrumental in initiating oxygen scavenging by the polymer films of the invention within the sealed containers. With water, the containers of the invention comprising daucus oxygen scavenging material, as well as samples of daucus with green tea, maintained the concentration of oxygen within the sealed container at essentially zero for over 160 days.

Example 2 - Tea

[0084] Applicant tested the compositions and methods herein using tea. As with the daucus example presented above, it is now understood and appreciated that the oxygen scavenging capacity of tea-entrained polymer compositions is due at least in part to hydrolysis of sugars in the tea component. Some of the results set forth below are also contained in the PCT Application No. PCT/US 21/70240 filed by Applicant on March 5, 2021 entitled, “Tea-Based Compositions for Oxygen Modified Packaging” (and is incorporated herein by reference in its entirety)

Example 2a

[0085] Fifteen samples of polymer film were prepared composed of seven different formulations. Samples 1 to 3 contained polymer with green tea leaf and colorant; samples 4 to 6 contained polymer film with green tea incorporated into the polymer in powder form; samples 7 to 9 contained polymer film with pre-ground green tea leaves; samples 10 to 12 contained polymer film with decaffeinated green tea; samples 13 to 15 contained TYVEK® film on both sides (from DuPont de Nemours, Inc. of Wilmington, Delaware, USA), blue colorant, and green tea. Each sample was placed into either a glass 2. IL Mason lar with a strip of filter paper (WhatmanTM 110mm diameter circle paper from GE Healthcare Life Sciences) which was squirted with one ImL drop of water and the sample sealed with an air tight screw top lid. Another set of samples were placed in the same way into a 120 mL serum vial and sealed with a lid crimped onto the vial. The level of oxygen within the containers was measured approximately each day or every few days for a period of 330 days using OXYSENSE® oxygen measuring system and technique of OxySense Inc., Devens, MA, USA, (https://www.oxysense.com/how-oxysense-works.html) consisting of probes glued to the inside of the sample chamber wherein a florescent pen causes the probe to phosphoresce at a varying intensity based upon the oxygen concentration in the chamber. [0086] The oxygen concentrations as measured were recorded. FIG. 8 demonstrates the recorded results for each of the 15 samples up to appx. 2200 hours of the test period. The results clearly show the oxygen scavenging effect of the film of the invention. The concentration of oxygen in the containers was significantly reduced for all of the 15 samples tested. Test results also demonstrated a difference or spread in the concentration, i.e., effectiveness of oxygen scavenging between the seven different formulations, as can be seen on FIG. 8. FIG. 8 shows a general trend of oxygen scavenging across various formulations in varying degree. Without being bound to any mechanism of action, it is thought that the difference in oxygen scavenging effect by the active film was a result of the preparation process of the tea component incorporated into the polymer composition. The test samples that show a lower oxygen scavenging effect, performance could have been affected by prior oxidation of the tea active agent during its processing or longer storage times as compared to freshly ground and used tea leaves.

[0087] As such, specific processing or preparation of the tea component, (in addition to the amount of the tea component and the formulation and concentrations of other components), will be a factor in the design of polymer compositions with specific oxygen scavenging properties.

Example 2b

[0088] Samples of polymer film with a pre-ground green tea component were prepared and were compared to a control sample reference film. The control sample was commercially available oxygen-absorbing resin film made based on the teachings of U.S. Pat. No. 7,893,145, which did not have any tea component. Oxygen scavenging of the test samples was initiated by moisture from the filter paper, whereas oxygen scavenging by the control samples required a photo initiator, which was not needed for the tea- active film test samples. The tests as set forth in Example 2a were performed and analyzed to measure the concentration of oxygen in Mason jars or vials. Measurements were recorded and represented in FIG. 9. The results showed that the films prepared according to the invention with a tea component incorporated into the polymer in ground form functioned as well, or better, than the control sample oxygen scavenging resin film. Example 2c

[0089] Ten samples of entrained three phase polymer film were prepared according to the invention consisting of polypropylene and polyethylene and 30% green tea by total weight of the composition. The green tea was ground to powder by a coffee grinder. The film was extruded by a typical extrusion process. Each sample of 2g of film was placed into a 150mL sealed Mason jar. The level of oxygen in the container was measured for approximately 330 days utilizing the OXYSENSE® oxygen measuring system of OxySense Inc., Devens, MA, USA. Samples 1 through 5 measured the oxygen scavenging properties of the film only. For samples 6 through 10, ImL of water was added to the container and the oxygen scavenging properties measured. The initial level of oxygen in the container was that of the typical or standard concentration of oxygen known in the atmosphere, to be between 20% to 22%, and is indicated as measured for each sample on day one. The level of oxygen in the container for each sample was measured approximately every day or every few days for approximately 330 days.

[0090] FIG. 10 demonstrates the results achieved. The recorded results indicate a clear decrease in the level of oxygen in the container. The concentrations of oxygen in the containers was maintained consistently at the decreased level, continuing to decrease slightly over the measured period of time.

[0091] The results also showed that the oxygen scavenging property of the tea active component was greatly enhanced within the container by the addition of water. This demonstrated that the moisture level in the container was instrumental in initiating the oxygen scavenging property of the tea to a greater or to its more complete capacity. As such, it is believed that the oxygen scavenging materials of the invention will be most useful for packaging and storage of products that contain some level of moisture in order to achieve the greatest oxygen scavenging effect within the container, or in packages where moisture is released or exuded by a product stored therein, or alternatively, where moisture may be added to the container from an alternate source or mechanism.

Example 2d

[0092] Samples of raw black tea were tested for their oxygen scavenging properties without incorporation into a polymer composition. Fresh black tea was prepared into black tea powder. Five samples were scattered into Mason jars in dry form; another 5 samples were scattered into Mason jars in a one to one ratio with water, 1g of tea to 1 mL of water spritzed into the container. Oxygen concentration was measured in the Mason jars. After approximately 2 to 3 days, the initiation of formation of mold was observed in three of the samples. The remaining samples did not develop mold. The average calculated results for each group are presented on FIG. 11. It is theorized that with the three samples with mold, the mold may have played some part in oxygen uptake. Mold formation may present a problem with products used in accordance with the invention in this manner for oxygen control. Further investigation and development is needed to resolve this issue.

[0093] However, regardless of the samples with mold formation, the results of the remaining samples clearly demonstrate the oxygen scavenging activity of black tea initiated with the addition of water to the system for oxygen modification in a container.

Example 3 - Table Sugar

[0094] Sugar entrained three phase polymer is prepared according to the invention consisting of polypropylene and polyethylene and 30% sugar by total weight of the composition. The sugar source utilized for the experiment is regular white table sugar purchased from a grocery store. The sugar is added and extruded by a typical extrusion molding process into appx. 0.2 mm to 0.3 mm thick film. The film is cut into strips of appx. 1.0 mm x 1.0 mm, weighing appx. 2g. Each sample strip is placed into a 150mL Mason Jar and the jar sealed. The level of oxygen in the container is measured for approximately 160 days utilizing the OXYSENSE® oxygen measuring system of OxySense Inc., Devens, MA, USA. The initial level of oxygen in the container is that of the typical or standard level of oxygen known in the atmosphere, to be between 20% to 22%, and is indicated as measured for each sample on day one. The film is activated by dipping into water for 1 to 2 seconds. The level of oxygen in the container for each sample is measured approximately every day over the duration of the experiment. The oxygen level drops to nearly zero by day 30 and is maintained at that level thereafter.

Example 4 - Alternative Sugar-Containing Source Materials

[0095] The experiment of Example 3 is repeated with various source materials that contain a sugar component. This includes the following non-limiting materials as potential oxygen scavengers: rice flower, potato starch, fresh beets, blueberries, bananas, honey, and celery. It is found that each of the aforementioned materials provide some level of oxygen scavenging effect.

[0096] The innovation is further defined by the appended claims. It is to be understood that the examples set forth are also intended to cover modifications and equivalent arrangements that are within the spirit and scope of the appended claims. In the claims, the word “comprising” does not exclude the presence of elements or steps other than those listed in a claim. The word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements. The mere fact that claim elements are recited in mutually different dependent claims does not indicate that these elements cannot be used in combination.

Claims

CLAIMS What is claimed is:

1. An oxygen scavenging polymer composition comprising: (a) a base polymer, (b) a sugar or a sugar-containing foodstuff, and (c) optionally, a channeling agent.

2. The oxygen scavenging polymer composition of claim 1, wherein the sugar or sugar-containing foodstuff is added to the base polymer in an amount sufficient to function as an effective oxygen scavenger.

3. The oxygen scavenging polymer composition of either one of claims 1 and 2, comprising a sugar.

4. The oxygen scavenging polymer composition of claim 3, wherein the amount of sugar is in a range from 20% to 80%, optionally from 40% to 70%, optionally from 45% to 65%, optionally from 55% to 65% by weight with respect to the total weight of the oxygen scavenging polymer composition.

5. The oxygen scavenging polymer composition of claims 3 and 4, wherein the oxygen scavenging polymer composition comprises a hydrolyzable or reducing sugar.

6. The oxygen scavenging polymer composition of claim 5, wherein the hydrolyzable or reducing sugar is a disaccharide, oligosaccharide, polysaccharide or a combination thereof.

7. The oxygen scavenging polymer composition of claim 6, wherein the hydrolyzable or reducing sugar is selected from sucrose, lactose, maltose or combination thereof.

8. The oxygen scavenging polymer composition of claim 5, wherein the hydrolyzable or reducing sugar is a carbohydrate, a starch or a combination thereof.

9. The oxygen scavenging polymer composition of claim 5, wherein the hydrolyzable or reducing sugar is a reducing sugar.

10. The oxygen scavenging polymer composition of claim 9, wherein the reducing sugar is chosen from a monosaccharide and a disaccharide. The oxygen scavenging polymer composition of claim 10, wherein the reducing sugar is a monosaccharide. The oxygen scavenging polymer composition of claim 11, wherein the reducing sugar is chosen from glucose, galactose, and fructose. The oxygen scavenging polymer composition of claim 10, wherein the reducing sugar is a disaccharide. The oxygen scavenging polymer composition of claim 13, wherein the reducing sugar is chosen from lactose and maltose. The oxygen scavenging polymer composition of claim 5, wherein the hydrolyzable or reducing sugar is a hydrolyzable sugar. The oxygen scavenging polymer composition of claim 15, wherein the hydrolyzable sugar is chosen from a disaccharide and an oligosaccharide. The oxygen scavenging polymer composition of claim 15, wherein the hydrolyzable sugar is not a reducing sugar. The oxygen scavenging polymer composition of claim 17, wherein hydrolysis of the hydrolyzable sugar produces a reducing sugar. The oxygen scavenging polymer composition of either one of claims 3 and 4, wherein the sugar is provided by or derived from sugarcane, sugar beet, honey, maple syrup, agave, molasses, fruits, vegetables, tea, coffee, plants, flowers, dairy products or is synthesized. The oxygen scavenging polymer composition of either one of claims 1 and 2, wherein the oxygen scavenging polymer composition comprises a sugar-containing foodstuff. The oxygen scavenging polymer composition of claim 20, wherein the sugar-containing foodstuff contains at least about 5% sugar, optionally at least about 10% sugar, optionally at least about 15% sugar, optionally at least about 20% sugar, optionally at least about 25% sugar, optionally at least about 30% sugar. The oxygen scavenging polymer composition of either one of claims 20 and 21, wherein the amount of the sugar-containing foodstuff is in a range from 20% to 80%, optionally from 40% to 70%, optionally from 45% to 65%, optionally from 55% to 65% by weight with respect to the total weight of the oxygen scavenging polymer composition. The oxygen scavenging polymer composition of any one of claims 20 - 22, wherein the sugar-containing foodstuff is derived from a plant. The oxygen scavenging polymer composition of claim 23, wherein the sugar-containing foodstuff is derived from a fruit or vegetable. The oxygen scavenging polymer composition of claim 24, wherein the sugar-containing foodstuff is derived from a vegetable. The oxygen scavenging polymer composition of claim 25, wherein the sugar-containing foodstuff is derived from a root vegetable. The oxygen scavenging polymer composition of claim 26, wherein the sugar-containing foodstuff is derived from a root vegetable chosen from beet, parsnip, turnip, rutabaga, carrot, yuca, kohlrabi, celery root, daikon, radish, potato, yam, and sweet potato. The oxygen scavenging polymer composition of claim 27, wherein the sugar-containing foodstuff is derived from carrot. The oxygen scavenging polymer composition of claim 28, wherein the sugar-containing foodstuff is derived from a leafy plant. The oxygen scavenging polymer composition of claim 29, wherein the sugar-containing foodstuff is derived from the Camellia sinensis tea plant. The oxygen scavenging composition of claim 30, wherein the sugar-containing foodstuff is selected from the leaves, buds, stems or combinations thereof, of the Camellia sinensis tea plant. The oxygen scavenging composition of either one of claims 30 and 31, wherein the oxygen scavenging agent comprises at least one tea component selected from white tea, black tea, yellow tea, green tea, red tea, oolong tea and post-fermented tea. The oxygen scavenging polymer composition of either one of claims 30 and 31, wherein the tea is selected from white tea, black tea, yellow tea, green tea, red tea, oolong tea and post-fermented tea. The oxygen scavenging composition of claim 33, wherein the oxygen scavenging agent comprises green tea. The oxygen scavenging composition of claim 33, wherein the oxygen scavenging agent comprises black tea. The oxygen scavenging polymer composition of any one of claims 1 - 35, wherein the composition is produced by extrusion molding, injection molding, blow molding or vacuum molding. The oxygen scavenging polymer composition of any one of claims 1 - 36, wherein the base polymer is selected from polypropylene, polyethylene, polyisoprene, polyhexene, polybutadiene, polybutene, polysiloxane, polycarbonate, polyamide, ethylene-vinyl acetate copolymer, ethylene-methacrylate copolymer, polyvinyl chloride, polystyrene, polyester, polyanhydride, polyacrylianitrile, polysulfone, polyacrylic ester, acrylic, polyurethane, polyacetal, a copolymer, or a combination thereof. The oxygen scavenging polymer composition of any one of claims 1 - 37, comprising a channeling agent. The oxygen scavenging polymer composition of claim 38, wherein the channeling agent is selected from polyethylene glycol (PEG), ethylene-vinyl alcohol (EVOH), polyvinyl alcohol (PVOH), glycerin polyamine, polyurethane, polycarboxylic acid, propylene oxide polymerisate-monobutyl ether, propylene oxide polymerisate, ethylene vinyl acetate, nylon 6, nylon 66, or a combination thereof. The oxygen scavenging polymer composition of either one of claims 38 and 39, wherein the amount of the channeling agent is in a range from 1% to 25%, optionally from 2% to 15%, optionally from 5% to 20%, optionally from 8% to 15%, optionally from 10% to 20%, optionally from 10% to 15%, or optionally from 10% to 12% by weight with respect to the total weight of the oxygen scavenging polymer composition. The oxygen scavenging polymer composition of any one of claims 1 - 40, wherein the composition is formed into a film, a sheet, a disk, a pellet, a package, a container, a cover, a plug, a cap, a lid, a stopper, a cork, a gasket, a seal, a washer, or a liner. A composite material comprising the polymer compositions of any of claims 1 - 41. A packaging material comprising the oxygen scavenging polymer composition of any of claims 1 - 41. The packaging material of claim 43, wherein the packaging material is selected from plastic, paper, glass, metal, ceramic, synthetic resin and a combination thereof. An oxygen modified sealable container for regulating the amount of oxygen inside the container, the container comprising the oxygen scavenging polymer composition of any one of claims 1 - 41. The oxygen modified sealable container of claim 45, configured to store a food item. The oxygen modified sealable container of claim 45, chosen from a refrigerator, a display case, a drawer, a tray, a box, a bin, a carton, a bottle, a blister pack, a vial, a vessel, a pouch, a flexible bag, or a package. The oxygen modified sealable container of claim 45, wherein the oxygen scavenging polymer composition is provided to the sealed container in the form of a mold, a liner, a plug, a film, a sheet, a pellet or a closure device. The oxygen modified sealable container of claim 45 used for retaining a food, herb, beverage, cosmetic, pharmaceutical, tobacco, cannabis, or electronic component. A method of reducing the concentration of oxygen in a container, the method comprising placing into a sealable container an effective amount of the oxygen scavenging polymer composition of any one of claims 1 - 41 for a time sufficient to reduce the concentration of oxygen in the container when sealed. The method of claim 50, wherein the sealable container is configured to store a food item. The method of claim 50, wherein the sealable container is chosen from a refrigerator, a display case, a drawer, a tray, a box, a bin, a carton, a bottle, a blister pack, a vial, a vessel, a pouch, a flexible bag, or a package. The method of claim 50, wherein the oxygen scavenging polymer composition is provided to the sealable container in the form of a mold, a liner, a plug, a film, a sheet, a pellet or a closure device. A method of reducing oxygen-initiated degradation in a container of an oxygen sensitive product, the method comprising the steps of (a) placing the oxygen sensitive product into the oxygen modified sealabale container of any one of claims 45 - 49, and (b) sealing the container, wherein the oxygen scavenging polymer composition reduces the concentration of oxygen in the sealed container. The method of claim 54, wherein oxygen-initiated degradation of the oxygen sensitive product is reduced while the object is in the container. The method of claim 54, wherein the method extends the shelf life of the oxygen sensitive product as compared to the object being stored in a non-oxygen modified container. The method of claim 54, wherein the oxygen scavenging polymer composition is provided within the headspace of the sealed container such that the composition does not physically contact the oxygen sensitive product. The method of claim 54, further comprising the step of providing an amount of liquid or moisture to the sealed container sufficient to cause the oxygen scavenging composition to scavenge oxygen.