KR20000064394A - Oxygen Scavenging Metal-Added Ion Exchange Compositions - Google Patents

Abstract

The present invention relates to an oxygen scavenging composition consisting of a carrier material and a metal-added cation exchange material in which the metal is zero. This composition is contained in the interior cavity of the container to eliminate oxygen inside. The composition may form at least a portion of the interior surface of the container or be present in the container in the form of a film, mat, sachet or ceramic.

Description

Metal-Added Ion Exchange Compositions for Oxygen Scavenging

This application is the part-continuation of US patent application Ser. No. 08 / 573,337, filed December 15, 1995, co-pending, the disclosure of which is incorporated herein by reference.

This composition consists of a carrier material mixed with a metal-added ion exchange material for oxygen scavenging, each of which is fully described later. In particular, the composition uses ion exchange materials doped with a zero-valent metal atom selected from magnesium, calcium, tin, transition metals (from scandium to zinc) or mixtures thereof. The oxygen scavenging composition of the present invention effectively absorbs oxygen from the inside of the container without negatively affecting the color, taste or smell of the packaged material contained in the container. In addition, the resulting composition is thermally stable and does not release volatile byproducts that contaminate the packaged material.

The oxygen scavenging composition has the ability to effectively chemically bond with oxygen without excessively moving the oxygen scavenging catalyst out of the matrix when in contact with the interior of the vessel or the like. Stability against catalyst movement is particularly advantageous in that the catalyst can significantly reduce or eliminate the negative effects on the color, taste or odor of the product when in contact with the matrix composition.

In order to enhance the preservation effect, it is standard practice to pack food and other materials in laminated packaging that generally includes a barrier layer with low oxygen permeability. The sheet material may be thin to wrap the material to be packaged, or may be thick enough to form a container equipped with a lid or other separate closure device. The polymeric sheet material may constitute most or all of the interior exposed surface area of the container.

It is known to include oxygen scavengers in sheet materials. Oxygen scavenger reacts with oxygen trapped in the package or penetrated into the package. This is described, for example, in US Pat. No. 4,536,409, US Pat. No. 4,702,966 and the prior art discussed in these documents. For example, US Pat. No. 4,536,409 describes a cylindrical container formed of such sheet material and equipped with a metal lid.

If the vessel is formed of glass or metal bodies and equipped with a sealed metal closure device, it is theoretically impossible for oxygen to penetrate through the body and the closure device due to the oxygen impermeability of the body and the material forming the closure device. In practical cases, the metal can reliably suppress the penetration of oxygen. However, some oxygen may penetrate by diffusion through a gasket or the like located between the container body and its lid. When conventional containers of this type are used for the storage of oxygen sensitive materials, it has long been known that the shelf life of stored materials is very limited. The quality of the packaged material tends to deteriorate over time, partly due to the presence of dissolved oxygen from the time the material is filled in the package, and partly due to the penetration of oxygen generated during storage.

When the container is in the form of a can, in many cases the end or other closure device of the can is a pressing component or a pulled configuration that is pressed to allow removal of the fluid or other material in the container without removing the entire closure device from the container. Contains an element. Such push or pull components are often defined by discontinuities or weakening lines in the panel of the closure device. Problems caused by these weakening or discontinuous lines include the risk of oxygen permeation into the vessel and the risk of corrosion of metals in which normal protective lacquer coatings rupture in the weakening or discontinuous lines.

It would be highly desirable to be able to significantly increase the shelf life while continuing to use conventional materials to form the vessel body, the closure device of the vessel and the gasket (if applicable) between the body and the closure device.

Various kinds of oxygen scavengers have been proposed for this purpose. For example, it is known to contain iron powder in a sachet for use with dry foods (Mitsubishi Gas Chemical Company Inc., Ageless-A New Age). in Food Preservation]. However, these materials require the addition of water soluble salts to improve the rate of oxygen scavenging, and when water is present the salts and iron tend to migrate into the liquid, producing off-flavor. Similarly, US Pat. No. 4,536,409 to Farrell et al. Recommends potassium sulfite as an scavenger, but shows similar results. U. S. Patent No. 5,211, 875 to Sper et al. Discloses the use of unsaturated hydrocarbons as oxygen scavenger in packaging films.

Because ascorbate compounds (ascorbic acid, salts thereof, optical isomers and derivatives thereof) are oxidized by oxygen molecules, they can act as components of oxygen scavenging formulations, for example, as components of hermetic device compounds. Known in For example, US Pat. No. 5,075,362 to Hofeldt et al. Discloses the use of ascorbate in container closure devices as oxygen scavenger.

US Pat. No. 5,284,871 to Graf relates to the use of oxygen scavenging compositions consisting of a reducing agent and a solution of dissolved copper species mixed in food, cosmetics and pharmaceuticals. This document teaches that most reducing agents require transition metals that catalyze oxygen uptake at usable rates (columns 3, lines 32-38). However, it is pointed out that a relatively large amount of Cu ²⁺ (5 ppm or less) is required for food for effective scavenging, but a small amount of Cu ²⁺ and oxygen in the food damage the food. To avoid damage, it is necessary to reduce the O ₂ in the upper void space or partially flush the vessel with an inert gas (columns 5, lines 32-39).

Paper by E. Graf, "Copper (II) Ascorbate: A Novel Food Preservation System", Journal of Agricultural Food Chemistry, Vol. 42, p. 1616-1619 (1994), shows gluconate copper as a preferred raw material.

In addition, International Patent Publication No. 91/17044, "Polymer Compositions Containing Oxygen Scavenging Compounds", such as Teumac, FN, filed May 1, 1991 and published November 4, 1991. It is also known that the catalyst can be used to significantly increase the rate of oxidation of ascorbate compounds. Typical oxidation catalysts for ascorbic acid and derivatives thereof are water soluble transition metal salts. When these catalysts are mixed with ascorbate compounds in a polymeric matrix (such as a PVC enclosure formulation), they effectively promote the oxidation of ascorbate compounds and increase the oxygen scavenging rate of ascorbate.

In each of the above documents, as an activator of the oxygen scavenging system, organic substances which produce by-products of oxidation processes (for example, aldehydes, acids, ketones) are used, and these by-products tend to have a negative effect on the packaged substances.

Tubular reactors containing copper zeolite powder as particulate filler have been used to remove small amounts of oxygen contained in air streams at relatively high temperature conditions (eg 140 ° C. or higher) (Sharma and Secham, et al., " Activation of Copper Dispersed on a Zeolite for Oxygen Absorption ", Chem. Modif. Surf., 3 (Chem Modif Oxide Surf), 65-80). Since foods are typically stored at low temperatures and are not exposed to temperatures above about 120 ° C. for any extended period of time, reagents operating at high temperatures such as 140 ° C. or higher are not considered suitable for use in food or food container applications. .

It would be desirable to provide an effective oxygen scavenging system suitable for packaging applications that is excellent in the oxygen absorbing capacity of the oxygen scavenging system and does not spill materials that may adversely affect the color, taste or smell of the packaged material.

It would also be desirable to provide an effective oxygen scavenging system that contains an active scavenging reagent in a carrier while the reagent still provides an effective scavenging ability.

It is also desirable to provide a thermally stable and effective system for oxygen scavenging.

Summary of the Invention

The present invention relates to an oxygen scavenging composition capable of providing excellent oxygen absorption capacity without adversely affecting the color, taste or smell of a material packaged in a container containing the oxygen scavenging composition as part of the container. The oxygen scavenging composition of the present invention consists of a carrier having a metal-added cation exchange material in which the metal is substantially zero.

The invention also relates to shaped structures containing or derived from the compositions of the invention.

The present invention relates to polymeric compositions that can be used to maintain product quality and increase the shelf life of oxygen sensitive materials, intermediate molding structures containing such compositions (eg films, coatings, three-dimensional solids, fibers, webs, etc.). And molded articles incorporated or applied to become part of or attached to the container structure.

1 is a graph of the test results of Example 1 using an inorganic cation exchange material with 3% by weight copper added.

FIG. 2 is a graph of the test results of Example 2 using an inorganic cation exchange material with iron addition amount of 3.8% by weight.

FIG. 3 is a graph of the test results of Example 3 showing an inorganic cation exchange material with 8.8 wt% copper addition. 10% by weight of the ion exchanged zeolite material was blended into low density polyethylene and ethylene / vinyl acetate blended into the polymeric matrix.

4 is a graph of the results of Example 6, showing that the composition is stably stored in the dry state and active in the wet state.

5 is a graph of the results of Example 7, showing that the composition is stably stored in the dry state and active in the wet state.

The present invention relates to an oxygen scavenging composition consisting of a carrier having a metal-added cation exchange material in which the added metal is substantially zero. The carrier may comprise a polymer matrix in which the metal-added cation exchange material of the present invention is substantially uniformly distributed; Films or mats (fabric or nonwoven) in which the metal-added cation exchange material of the present invention is deposited on or within a film or mat (eg, the pores of the mat); Moisture permeable pouches or sachets containing the metal-added cation exchange material of the present invention; Or a porous inorganic matrix in which the metal-added cation exchange material is distributed.

The present invention also provides an improved container for packaging materials such as food, beverages, etc., which are susceptible to oxidation and deterioration. The improved container of the present invention enables the oxygen scavenging composition of the present invention to maintain product quality and improve shelf life of the packaged material without negatively affecting the color, taste or smell of the packaged material. .

In one embodiment of the invention, the carrier of the composition of the invention comprises a polymeric matrix material which is a polymeric material that forms a matrix of solidified deposits in which a metal-added cation exchange material is distributed. The polymeric matrix material will be selected in consideration of the properties of the composition (eg, dispersions, latexes, plastisols, dry blends, solutions or melts) and use thereof as part of the container in conventional manner.

The polymeric matrix material is selected from one or more polymeric materials that can form a solid or semisolid matrix. The polymeric matrix material can be derived from various polymers available from various bulk physical structures, such as dispersions, latexes, plastisols, dry blends, solutions or melts (eg, meltable thermoplastic polymers). The particular physical structure of the polymer selected in admixture with the oxygen scavenging composition depends on the final structure in which the composition of the present invention is eventually molded or incorporated. The polymeric matrix is derived from a polymer type that may be thermoplastic or thermoset.

The primary function of the polymer matrix for the purposes of the present invention is to act as a carrier compatible with the oxygen scavenging composition (a material that is stable under normal packaging temperature conditions and does not inactivate the oxygen scavenging ability of the active material). Thus, the range of polymers can generally be very broad. However, the polymer matrix may be selected to perform additional functions depending on the physical structure provided in the final structure to be shaped or incorporated. Thus, the particular polymer or polymer mixture selected will ultimately depend on the end use that exerts the oxygen scavenging effect.

Thus, suitable polymers from which the polymeric matrix can be derived include vinyl polymers, polyethers, polyesters, polyamides, phenolformaldehyde condensation polymers, polysiloxanes, ionic polymers, polyurethanes and natural polymers such as celluloses, tannins. , Polysaccharides and starches).

For example, suitable materials for use as polymeric matrix components of latex compositions for can ends are described in US Pat. No. 4,360,120, US Pat. No. 4,368,828, and European Patent 0182674. Suitable polymeric materials for use when the composition is an organic solution or an aqueous dispersion are described in US Pat. No. 4,360,120, US Pat. No. 4,368,828 and UK Pat. No. 2,084,601. Suitable materials for use in thermoplastic compositions include U.S. Patent 4,619,848, U.S. Patent 4,529,740, U.S. Patent 5,014,447, U.S. Patent 4,698,469, U.S. Patent 1,112,023, U.S. Patent 1,112,024, U.S. Patent 1,112,025 And materials proposed in European Patent No. 129309. The teachings of the references cited herein are hereby incorporated by reference.

In particular, polymeric materials are generally polyolefins such as polyethylene, polypropylene, ethylene / propylene copolymers, acid modified ethylene / propylene copolymers, polybutadiene, butyl rubber, styrene / butadiene rubber, carboxylated styrene / Butadiene, polyisoprene, styrene / isoprene / styrene block copolymer, styrene / butadiene / styrene block copolymer, styrene / ethylene / butylene / styrene block copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylate and ethylene / metha Acrylate copolymers such as ethylene / butyl acrylate or ethylene / butyl methacrylate copolymers, ethylene / vinyl alcohol copolymers, vinyl chloride homopolymers and copolymers, styrene / acrylic polymers, polyamides and vinyl acetate polymers, And blends of one or more of these. Polyethylenes found to be useful in forming the compositions of the present invention include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), and the like, and one or more other lower alkenes such as octene. ) And a copolymer formed from ethylene.

In this embodiment, particularly preferred compositions according to the invention are polyethylene, copolymers of polyethylene (eg ethylene / vinyl acetate, etc.) or polyethylene blends (eg blends of HDPE and butyl rubber, blends of polyethylene and ethylene / vinyl acetate copolymers) And blends of polyethylene and styrene / butadiene / styrene block polymers, and the like. Polyethylene (if used) is preferably low density polyethylene, but may be very low density or ultra low density polyethylene, which may be branched or linear. The ethylene / vinyl acetate copolymer (if used) has a melt index of 3 to 15, preferably 5 to 10, and generally a content of vinyl acetate of 5 to 40%, preferably 5 to 30%.

It is also possible to use plastisols or dry blends of polymers with plasticizers to form polymer matrices. When the composition is a plastisol, suitable materials for use include vinyl chloride homopolymers and copolymers. Instead of preparing such compositions as pure plastisols, they may be provided as a dry blend of polymer and plasticizer. The proportion of plasticizer present in the vinyl resin plastisol may be a conventional ratio, typically from 30 to 150 parts by weight of plasticizer per 100 parts by weight of vinyl resin.

The polymeric matrix of the composition may further contain conventional plasticizers, including phthalates, adipates, glycols, citrate and epoxidized oils and the like. Examples include dioctyl phthalate, diisooctyl phthalate or diisodecyl phthalate, which are readily available. Other plasticizers that can be used are butyl benzyl phthalate, acetyl tributyl citrate, ethyl diphenyl phosphate and diisobutyl phthalate. One particularly useful plasticizer mixture for use with vinyl chloride / vinyl acetate copolymer resins is a mixture of diisodecyl phthalate and diisooctyl phthalate with a weight ratio of about 7: 1 to 8: 1.

The polymeric matrix of the composition of the present invention typically contains fillers, slip aids, processing aids, pigments, stabilizers, antioxidants, tackifying resins, foaming agents, and other conventional additives, depending on the composition and the end use. It may also be contained in an amount of. If the composition is a thermoplastic composition, the total amount of such additives is generally less than 10%, most preferably less than 3%, based on the total amount of the composition, and if the composition is a plastisol, dispersion, organic solution or latex, the polymer The amount of additives based on the substance may be higher. For example, large amounts of filler may be incorporated. If an antioxidant is incorporated, the antioxidant must be present in an amount capable of stabilizing the polymeric composition against alteration due to free radicals formed during processing. However, the amount of antioxidant should be small enough to allow the oxidizer component of the composition to react effectively with oxygen molecules. The specific amount depends on the antioxidant used and can be determined by side experiments.

The compositions of the present invention may be formulated in any convenient form, such as melts, plastisols, organic solutions, dry blends, latexes or dispersions. The main components of the composition other than the oxygen scavenger are typically the typical components that are typically present for the intended purpose. It is preferred that the entire composition is non-aqueous (ie, anhydrous solution, plastisol or thermoplastic melt) to prevent initiation of the reaction of the scavenger in the composition. Optionally, the scavenger may be encapsulated or otherwise prevented from contacting the water used to form the composition of the present invention.

The polymer matrix of the composition of the present invention may be selected from those used to form a coating on at least a portion of the inner surface of a packaging (eg, a rigid container such as a can, can lid, box, etc.). Polymer matrices may be selected from a class of polymers commonly referred to as epoxides, phenols (e.g. phenol-formaldehyde condensation polymers), lacquers (e.g. cellulose esters or ethers, shellac, alkyl resins, etc.), polyurethanes, and the like. have.

The compositions of the present invention are particularly suitable for use with carrier materials commonly used to coat the interior surfaces of containers (eg cans), the coating process being heated to remove solvents and / or to cure the carrier material. need. For example, lacquer, epoxy resin, or the like may be coated on the inner surface of the metal can as a protective coating. To cure the coating, the treated can is subjected to high temperatures for a short time to remove solvent and cure the coating before filling the can and sealing it. Conventional oxygen scavengers composed of oxidizable organic compounds are not suitable as part of such curable coatings because they are known to deteriorate at the high temperatures generally required in this curing step. The composition of the present invention is particularly suitable for applications in which the scavenger must be stable at high curing temperatures. For example, the carrier may be an alcohol (eg C ₁ -C ₃ alkyl alcohol), ketone (eg methyl ethyl ketone), acetate (eg butyl acetate) or aromatic (eg toluene, xylene) or mixtures thereof. It may be a polymer matrix consisting of organic lacquers composed of cellulose ethers or esters in solvents, alkyl resins or mixtures thereof. The metal-added zeolites or other cation exchange materials of the present invention that are stable (applied to the high temperatures expected during the curing process do not degrade or lose oxygen scavenging activity) can be used as the oxygen scavenger component.

In a second aspect, the composition of the present invention uses a film or fiber mat (woven or nonwoven) containing the oxygen scavenger of the present invention described below. The carrier may be formed from a polymeric material as described above, which may form a film and deposit the oxygen scavenger of the present invention on its surface. The surface of the film can be coated with an oxidizing scavenger of the present invention by forming an emulsion or dispersion of oxygen scavenger powder in the polymer and depositing directly on the surface of the carrier film by conventional methods (e.g., by spraying or knife coating, etc.). Can be. The particular nature of the carrier film will depend on its use and the ability of the carrier formed to attach the oxygen scavenger to its surface and will substantially remain intact during use.

Optionally, the carrier may be in the form of a fibrous (woven or nonwoven) mat. An oxygen scavenger is contained in the gap of the mat structure. The fibers forming the mat may be any suitable material or synthetic fiber (e.g., cotton, glass, nylon, polyethylene and copolymers of ethylene with one or more ethylenically unsaturated monomers, polypropylene and one or more ethylenically unsaturated monomers with propylene Copolymers, etc.). The particular nature of the carrier mat will depend on its use and the ability of the mat to retain oxygen scavenger material in the gaps of the mat structure during use. The scavenger may be deposited on the mat structure by any method such as dipping the mat into a dispersion or emulsion of scavenger and then removing the liquid from the mat.

In a third aspect, the oxygen scavenger of the present invention described below may be retained in the carrier in the form of a pouch or sac of a size suitable for insertion into a container comprising an oxygen sensitive material. The pouch or sachet must be sufficiently porous to allow moisture and oxygen to permeate through the material forming the pouch or sachet at ambient temperature conditions. The oxygen scavenger material of the present invention is preferably in the form of particles having a particle size (eg, pore size diameter, pore structure) sufficient to allow the sasei structure to retain the oxygen scavenger therein. Pouches or sachets may be formed from natural or synthetic materials (eg, paper, cotton garments, polymer films, etc.) in a manner known in the packaging art.

A fourth aspect is the use of a carrier in the form of a porous inorganic material, such as a ceramic, in which the oxygen scavenger described below is distributed. The ceramic may be molded to any desired shape (spherical, cube, etc.) and of a size suitable for insertion into a container having an oxygen sensitive material. Useful ceramics include clays such as kaolinite, montmorillonite or illite with diaspore, gibbsite and bauxite. Ceramics also include quartz, tridymite, cristabalite, diatomite and the like.

An essential feature of the present invention is that the composition of the present invention contains an oxygen scavenger, ie a reagent capable of reacting with oxygen gas. The oxygen scavenger is preferably a reducing agent capable of reacting with oxygen gas in an ionic reaction that can occur in the presence of moisture.

It has been found that metal-added cation exchange materials with metals in the zero-valent state as part of the exchange material structure when present in the carrier can be used as the oxygen scavenger composition. Finely divided cation exchange materials include, for example, inorganic aluminosilicates. The resulting composition can be used for the preservation of oxygen sensitive foods stored at ambient conditions. Such compositions have advantages over compositions containing organic oxygen scavengers such as ascorbates and unsaturated hydrocarbons because they do not produce organic oxidation byproducts that may contaminate food materials. In addition, there is no need for a water soluble salt generally used with an oxygen scavenger to increase the scavenging rate. The compositions of the present invention also minimize the migration of metal ions to aqueous solutions. Accordingly, oxygen scavenger compositions have been found that do not discolor or impair the taste of food products packaged by the present invention.

Oxygen scavengers of the invention are cation exchange materials to which substantially zero-valent metals are added. It has been found that a feature of this system is that the metal is supported by a cation exchange material so that the metal can react sufficiently with molecular oxygen. Scavenging activity is initiated by the presence of moisture, providing effective scavenging at ambient conditions. Preferred exchange materials are a class of materials known as inorganic zeolites. Such materials are generally hydrated alumina silicates comprising sodium and / or calcium. Such materials may be formed naturally or synthetically. For the purposes of this patent, zeolites are aluminosilicates that have a skeleton structure surrounding a cavity that can be occupied by large ions and water molecules, and because the large ions and water molecules move fairly freely, ion exchange and reversible dehydration It is possible. A typical naturally occurring zeolites are the general formula _{Na 13 Ca 11 Mg 9 K 2} Al 55 Si 137 O 384 · mineral faujasite (faujasite) having 235H ₂ 0. Ammonium and alkylammonium cations such as NH ₄ , CH ₃ NH ₃ , (CH ₃ ) ₂ NH ₂ , (CH ₃ ) ₃ NH, and (CH ₃ ) ₄ N) may be incorporated into the synthetic zeolites. Zeolite A, Zeolite X, Zeolite Y, Zeolite ZK-5, Faujasite and Laulingite are linked cut-off octahedrons (beta-cage) that are characteristic of sodalite structures Has a skeleton consisting of. Some synthetic zeolites are structurally related to minerals and are included in this class, but for most synthetic zeolites no structures are known. Many synthetic zeolites are also useful and are preferred for the purposes of the present invention.

To prepare the scavenger of the present invention, zeolites or other exchange materials are ion exchanged with a solution of the desired metal salt. It is believed that zeolites trap metal ions. The metal ions are chemically reduced to zero by any suitable means. One way to reduce is to apply the added material to hydrogen gas under high pressure and high temperature. The resulting scavenger is then dried and ready to be incorporated into the carrier.

Any metal capable of substantially reducing O to a state capable of reacting with molecular oxygen is suitable for the present invention. In practice, metals are chosen that do not react too quickly with oxygen because handling the scavenger is difficult if they react too quickly with oxygen. In addition, in view of food safety, metals with low toxicity are preferred. In general, it is preferred to use a zero-valent reduced metal selected from calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and tin. Preferred metals are transition metals of the periodic table from scandium to zinc (ie Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn), with iron and copper being more preferred. Copper is particularly preferred for use in the present invention.

Metal-added cation exchange materials are particularly suitable to replace some or all of the fillers generally found in sealant compositions, which are the uses expected as a finely divided solid. As mentioned, the composition is preferably anhydrous throughout. Thus, if a polymeric matrix is used, it is preferred to be anhydrous. In general, the polymeric matrix protects the scavenger from moisture under conditions of substantially normal atmospheric pressure, so the scavenger remains substantially inert to the scavenging activity until high moisture is present. The polymer matrix should be porous enough to allow moisture to pass through the formed composition.

A preferred aspect of the present invention is that the scavenger remains substantially inert in the composition and in gaskets or other solid deposits molded into the composition of the invention until the composition of the invention is on or in the sealed container. Exposing the composition to high humidity, which may generally be present in a sealed container, will allow moisture to fully penetrate into the composition, thereby causing the oxygen scavenger of the present invention to begin scavenging to a satisfactory level and to increase the shelf life of the packaged material. However, the scavenging reaction in a closed vessel that increases the penetration of moisture can be promoted by heating the composition sufficiently. Thus, until the scavenging reaction is promoted by heating in the presence of moisture, the scavenger is preferably a substance that remains substantially inert in the carrier.

Preferably, the scavenging reaction of the present composition is facilitated by filling the vessel with an aqueous content, sealing it and then pasteurizing the vessel (typically at 50 ° C to 110 ° C) or sterilizing (typically at 100 ° C to 150 ° C). This stimulus appears to be the effect of the composition which, when heated, permeates moisture into the composition and the scavenger of the present invention. When moisture is trapped in the composition, the scavenger comes into contact with sufficient water and reacts with oxygen. Oxygen trapped in the vessel when the vessel is filled or oxygen that has subsequently entered the vessel from the ambient atmosphere may penetrate through the composition.

The composition may preferably comprise a substance which increases the permeability of the composition to water, for example a surfactant such as sodium dodecylbenzene sulfonate, with a suitable amount of such surfactant being 0.1 to 1.0% by weight. .

The amount of scavenger depends on the application form. When the scavenger is incorporated into the gasket, the amount is generally at least 0.5% by weight, generally at least 1% by weight, preferably at least 2% by weight, based on the polymeric matrix material. Generally an amount of at least 20% by weight is not necessary and a convenient maximum amount is from 4% by weight to 10% by weight. In other words, the amount of scavenger is typically from 0.01 to 2 g, often from 0.02 to 1 g per container.

In the case of plastisols, lacquers or hot melts applied to the central panel of the closure device, in which the matrix does not act as a gasket, the amount of scavenger addition may be greater. For example, the addition amount is 20% to 60% by weight, in some cases up to 90% by weight is feasible.

If the composition is in the form of a film, mat, pouch or sachet, the oxygen scavenger should be present in an amount effective to scaveng oxygen during the expected shelf life of the container for the proper contents. This amount is generally from 0.01 to 2 g per container of normal size.

By the present invention, it is possible to significantly increase the shelf life of oxygen sensitive foods or other contents of the sealed container by reducing the degree of alteration by oxygen.

The compositions of the present invention can be used as part of a packaging container that can provide storage stability to the material packaged therein without altering the taste, aroma or odor of the material. The composition of the present invention may be produced in any form, such as a coating on all or a portion of the interior of a container body or sealing means (eg lid, can end), or an insert in the form of a film, mat, pouch, sasei or ceramic structure. The interior atmosphere of the sealed closure container.

The invention formed of a polymer matrix or film can be applied as a central panel lining on a container closure device. The closure device may be a cap, can end, lidstock or film. The invention also includes a container closure device that contains a solid deposit formed from a polymer matrix or film composition on the closure device and is disposed to seal around or above the weakening line in the closure device. The solid deposit may be a gasket deposited around the closure device and formed from the composition. Instead of or with deposits, such as gaskets, the composition may be deposited on the inner surface of the closure device in a location where there are discontinuities or weakening lines around the press or pull component for opening the container sealed by the closure device. Typically, the closure device occupies only a small portion of the exposed surface area of a closed container, often less than 25% of the surface area. Thus, the area of the solid deposit can be very small relative to the container area. Nevertheless, the present invention can provide a greatly improved storage capacity for the contents.

The invention also includes a filled container sealed with such a closure device. The sealed container includes a container body, a sealing device fitted to the body, and a filler contained in the container body. Preferably, the container body is glass or metal. Preferably, the closure device is a metal.

The filling may be a beverage, food or other substance which should be stored in the container, but the invention is particularly useful when the filling is a substance in which the shelf life of the contents or the quality of the product is generally limited due to contamination during oxygen penetration or storage. It is important. The container body may generally be a metal can, in which case the closure device may be the can end. In general, the entire closure device may be made of a metal or polymeric material, while the panel of the closure device may be a removable component of the metal or polymeric material.

Instead of the can body, the container body may be a bottle or jar in which the closure device is a cap. The bottles or jars are preferably made of glass, but can be made of polymeric materials with very low oxygen permeability. The cap may be a polymeric material, such as polypropylene, which may include a barrier layer. In general, the cap consists of a metal and may include a pressing or pulling component of a metal or polymeric material. Caps can be crown caps (e.g., pry-off or twist-off crowns), twist-on caps, lug caps, press-on -on / twist-off or press-on / fry-off caps, screw-on caps, roll-on metal caps, continuous thread caps, or bottles or jars It may also be any other conventional form of metal cap or polymeric cap suitable for sealing.

In general, a gasket is provided between the container body and the closure device. This gasket can be used to contain the composition of the invention (particularly as a polymer matrix containing the composition) as a blend in the gasket composition or as a separate component applied on or around the gasket, but the composition of the invention is hermetically sealed. It is possible to be used elsewhere in the apparatus or container. In that case, the gasket forming composition may be any unmodified conventional composition suitable for forming a gasket.

When the closure device is a cap, the scavenger composition of the present invention may form the entire gasket or part of the entire gasket. This is typically the case for small diameter caps of less than 50 mm in diameter. For large diameter caps, the gasket is an annular gasket and may be deposited by conventional methods from the gasket-forming composition. For example, the annular gasket can be formed on the cap by applying it like a ring in liquid form, and then dried, heated to cure, or cooled to cure the thermoplastic to be converted into a solid form if necessary. have. The composition for oxygen scavenging may be applied to areas of the cap (center panel) that are blended into, deposited on, or covered by the gasket material. The gasket-forming composition may be a dispersion, latex, plastisol, dry blend, suitable thermoplastic composition or organic solution for this purpose. The cap with the gasket is then pressed against the appropriate sealing face around the open end of the filled container body and sealed in a conventional manner.

When the composition is molded with a thermoplastic polymer matrix, the composition is applied as a low viscosity melt during spinning of the cap to make the composition annular, or later to a disc with a desired shape, often a thickened annular portion. It can also be applied as a melt to be molded. The gasket may also be in the form of a pre-formed ring or disc that is held in the cap (eg, by mechanical or adhesive means).

When the closure device is can end, oxygen scavenger is typically not used in the gasket composition because under typical can sealing conditions the gasket is not substantially exposed to oxygen in the package. In addition, the suture is not particularly easy to penetrate oxygen. Oxygen scavenging materials are typically applied to the center panel or other inner surface of the can, such as applied to the can's coating.

The gasket or coating on the vessel closure device is preferably formed by applying the fluid or melt composition of the invention formed of a polymer matrix and solidifying it on the closure device. Application and solidification methods are generally common. Since the use of a limited composition to form a gasket appears to produce particularly beneficial results, it is preferred that the container and can ends are both metal, or the container body is glass and the closure device is metal or plastic. In particular, good results can be obtained when the container body is a glass bottle and the closure device is a metal cap.

Instead of or using the fluid or meltable polymer matrix composition of the present invention to form a gasket, it is possible to deposit the composition elsewhere on the inner surface of the closure device. It may be applied as the entire coating of the inner surface of the closure device panel or may be applied to only a portion of the inner surface. In particular, where the panel comprises one or more push or pull components defined by discontinuities or weakening lines within the panel, the composition may first be applied to just cover the discontinuous or weakening lines.

For example, one type of closure device, typically a can end, includes one or more, often two pressing components, defined by partial notches across the metal panel, so that the finger holds the circular area of the panel. Press inward to access the contents of the container. Thus, there may be a small press component for releasing pressure and a larger press component for pouring liquid from the vessel. Such a system is described, for example, in German Patent No. 3,639,426. In particular, the composition of the first aspect of the invention may be deposited as an annulus (or disc) covering the weakening line. The weakening line may be only a weakened line in the metal panel, but may be cut all around the pressing component, for example in German Patent No. 3,639,426, in which case the pressing component is generally defined by the cutting line. With an area slightly larger than the opening in the panel to be made, the compositions of the present invention can form a seal between the pressing component and the remaining panels of the closure device.

In all cases of forming the press or pull component in the metal panel, forming the press or pull component may damage the polymeric lacquer film that is generally present on the inner surface of the metal panel. This can expose the metal and cause corrosion. Application of the composition of the present invention to the container as described above can not only inhibit corrosion of the metal container but also improve the storage stability of the content of the container, in particular the content containing water (eg beer).

In addition to use in metal, glass and plastic containers, the compositions can be used in cardboard or laminated containers such as juice boxes. This container is a cardboard box or tube with an inner liner. The composition may be placed on or laminated to the inner liner of the cardboard wrapper along the weakening line at the packaging closure device or at any other convenient location in the package. Alternatively, the compositions of the present invention may be placed in a container as a film, mat or assay.

In addition, when the polymer matrix is a thermoplastic resin, the composition of the first aspect may be blended and extruded into the desired shape. For example, the composition of the present invention may be molded into the film itself or molded into the constituents of the film composition used to make the flexible packaging (such as a bag), or the film may later be used for cans and closure devices. It can be laminated to a metal material capable of forming. The composition may also be included in a flexible packaging (eg, multilayer film or laminate) or as a ribbon, patch, label or film over a thermoplastic bag or lidstock. If the composition of the invention is part of a multilayer film, the layer made of the composition is a surface layer exposed to the inner surface of the resulting flexible packaging material or is very porous so that O ₂ and moisture are layers containing the composition of the invention. It may also be an inner layer covered by a surface layer that penetrates and contacts with it. Thus, as used herein and in the appended claims, the term "internally exposed" means that the composition of the present invention is exposed, directly or indirectly, to the interior atmosphere of the containment vessel containing the substance.

The compositions may also be used in conjunction with or as part of a membrane for use in pharmaceuticals and foods, where the traces are revealed when opened.

The following examples are provided merely for the purpose of illustration and are not intended to limit the claims appended hereto. All parts and percentages are by weight unless otherwise indicated.

Example 1

A solution of 11.14 g CuSO ₄ 5 H ₂ O in about 500 mL deionized water was prepared. Approximately 21 g of zeolite Y (USY zeolite, steam-treated zeolite showing improved stability, Davidson Division, WR Grace & Co.-Conn., Baltimore, MD) Available from) and slurried with CuSO ₄ overnight. The zeolite was isolated by filtration, washed several times with deionized water and dried to give a light blue powder. Inductively coupled plasma (ICP) analysis showed a copper addition of about 3%.

Cu ²⁺ exchanged zeolite powder was reduced by hydrogenation at 300 ° C. in the presence of about 100 psi of H ₂ . After 24 hours, a dark purple Cu ⁰ exchanged zeolite powder was obtained.

Oxygen scavenging properties of the upper void space of the Cu ⁰ exchanged zeolite powder were determined in a plastic pouch (oxygen barrier bag BDF 2001, oxygen permeability of about 5 cc O ₂ / m 2 film / d / atm O ₂ , Duncan, SC, USA The powder samples were tested by heat-sealing in the W. R. Grace &Company's Cryoback Division (available from Cryovac division). The gas sample in the upper void space was periodically withdrawn through a syringe through a septum with adhesive contact, attached to the pouch. Oxygen concentration in the upper void sample was measured by injecting the sample into a Mocon LC-700F oxygen analyzer (available from Modern Controls, Inc., Minneapolis, Minn.). Cu ⁰ exchanged zeolite samples were tested in the presence of ambient air and 1 ml of water. The results are shown in FIG.

FIG. 1 shows that Cu ⁰ exchanged zeolites oxidize rapidly at room temperature and that oxidation of copper is enhanced at higher humidity.

Example 2

An iron-exchanged zeolite was prepared in the same manner as in Example 1 except that 9.6 g of FeCl ₃ · 6H ₂ O was replaced with CuSO ₄ · 5H ₂ O and dissolved in about 400 mL of deionized water. The pH of the solution was adjusted to 5 using KOH. About 32 g of zeolite Y (USY zeolite, Davidson) was added and slurried in Fe ³⁺ solution for 2 days. A tan Fe ³⁺ exchanged zeolite was isolated as in Example 1. As a result of analysis of ICP, the amount of iron added was 3.8%.

The Fe ³⁺ exchanged zeolite powder was reduced by hydrogenation at 300 ° C. in the presence of 800 psi of H ₂ for 3 weeks. Silver gray powder was obtained.

Oxygen scavenging properties of the upper void of the Fe ⁰ exchanged zeolite powder were tested as in Example 1. The results are shown in FIG.

The results indicate that the Fe ⁰ exchanged zeolite clears quickly at room temperature but not as fast as copper exchanged zeolites.

Example 3

Cu ²⁺ exchanged zeolite was prepared as in Example 1 except that about 100 g of CuSO ₄ H ₂ O was dissolved in 400 mL of deionized water. About 25 g of zeolite Y (USY zeolite, Davidson) was added to form a slurry. After the slurry was stirred for 3 hours, it was washed as in Example 1 and the Cu ²⁺ added zeolite powder was isolated. The Cu ²⁺ exchanged zeolite powder was then reduced by hydrogenation as described in Example 1. The resulting dark purple copper exchanged zeolite contained 8.8% copper by ICP analysis.

The Cu ⁰ exchanged zeolite powder was then melt blended into a blend of low density polyethylene (LDPE) and ethylene / vinyl acetate (EVA) using a Brabender® mixing chamber at the following ratios:

10% Cu ⁰ Exchanged Zeolite Powder,

54% LDPE,

36% EVA (28% vinyl acetate).

A film of this material was made using a heated hydraulic press. The pouch was then composed of an oxygen barrier film, FS 6055b (available from the Cryoback Division of W. R. Grace and Campani-Con, Duncan, SC, USA) (instead of BDX 2001) and weighing approximately 90 ml. The oxygen scavenging properties of the upper void of the film were tested using the test method of Example 1, except that it contained 3% alcohol carbonized. After the pouch was inflated with 150 ml of air (20.6% oxygen), the pouch was heated to 65 ° C. for 50 minutes in a convection oven. The results are shown in FIG.

The results show that when Cu ⁰ exchanged zeolites are blended into the simulated crown liner formulation, they quickly deoxygenate at room temperature.

Example 4

1.00 g of Cu ⁰ exchanged zeolite sample (containing 8.8% Cu ⁰ ) was added to 250 mL deionized water. In addition, a copper powder sample containing the same amount of copper metal (0.0871 g) as contained in Cu ⁰ exchanged zeolite was added to 250 mL of deionized water. The dissolved oxygen content and conductivity of the two solutions were observed over time. It was observed as follows and recorded in Table 1.

Hour Oxygen scavenging amount Concentration of copper ions In case of Cu ⁰ exchanged zeolite Copper metal case In case of Cu ⁰ exchanged zeolite Copper metal case Concentration of O ₂ (ppm) Concentration of O ₂ (ppm) Cu ²⁺ concentration (ppm) Cu ²⁺ concentration (ppm) Reference 0 8 8 - - Only water 0 8 8 0 0 Cu or Cu ⁰ exchanged zeolite is added 0.5 0.5 8 0 0 3 0.18 8 0 0 22.5 0.14 7 39 0.3

The water containing Cu ⁰ exchanged zeolite was rapidly deoxygenated by its fast oxygen scavenging properties, indicating that the Cu ⁰ exchanged zeolite was rapidly oxidized. However, as can be seen from the oxygen content of the water, which is relatively unchanged, the copper powder does not quickly deplete oxygen. The oxidized Cu ⁰ exchange zeolite only released a small amount of Cu ²⁺ (11% of the available Cu ²⁺ ), indicating that copper ions are substantially bonded to the zeolite structure.

Example 6

Mg ²⁺ exchanged zeolite powder was prepared as in Example 1 except that about 147 g of MgSO ₄ was added to 200 mL of deionized water to form a saturated solution. About 25 g of zeolite Y (USY zeolite, Davidson) was added to form a slurry. The slurry was stirred for about 18 hours, then washed as in Example 1 and the Mg ²⁺ exchanged zeolite powder was isolated. Then, hydrogenation as described in Example 1 reduced the Mg ²⁺ exchanged zeolite powder. The resulting magnesium exchanged zeolite contained 1.38% magnesium as a result of ICP analysis.

Then, 10 wt% of the Mg ⁰ exchanged zeolite powder was added to the PVC plastisol composition (Darex® CR 3692M, W. R. Grace & Company-Con, Lexington, Mass.). Mixed to Container Container Products division. The resulting composition was coated on aluminum foil and solidified by heating to 160 ° C. for 45 seconds on a hot plate. Except for the pouch containing dry air or about 40 ml of water (100% relative humidity), the test method of Example 3 was used to provide Mg ⁰ exchanged zeolites for oxygen scavenging properties of the upper void. The containing PVC film was tested. After the pouch was inflated with 150 ml of air (20.6% oxygen), the pouch was heated to 65 ° C. for 50 minutes in a convection oven. The results are shown in FIG.

The results indicate that the Mg ⁰ exchanged zeolite, when formulated in the simulated crown liner formulation, quickly depletes oxygen at room temperature and is activated by the presence of moisture.

Example 7

Zn ²⁺ exchanged zeolite powder was prepared as in Example 1, except that about 150 g of ZnSO ₄ H ₇ O was added to 200 mL of deionized water to prepare a saturated solution. About 25 g of zeolite Y (USY zeolite, Davidson) was added to form a slurry. The slurry was stirred for about 18 hours and then washed as in Example 1 to isolate Zn ²⁺ exchanged zeolite powder. The Zn ²⁺ exchanged zeolite powder was then reduced by hydrogenation as described in Example 1. The resulting zinc exchanged zeolite contained 3.84% zinc as a result of ICP analysis.

The Zn ⁰ exchanged zeolite powder was then mixed into the PVC plastisol composition (Darex CR 3692M, Grace Container Products) at 10% by weight. The resulting composition was coated on aluminum foil and solidified by heating at 160 ° C. for 45 seconds on a hot plate. The PVC film containing the Zn ⁰ exchanged zeolite was tested for oxygen scavenging properties of the upper void using the test method of Example 5. The results are shown in FIG.

The results indicate that Zn ⁰ exchanged zeolites quickly deplete oxygen at room temperature when formulated in a simulated crown liner formulation and are activated by the presence of moisture.

Example 8

Ni ²⁺ exchanged zeolite powder was prepared as in Example 1 except that about 140 g of NiSO ₄ was added to 200 mL of deionized water to prepare a saturated solution. About 25 g of zeolite Y (USY zeolite, W. R Grace and Company) was added to form a slurry. The slurry was stirred for about 18 hours and then washed as in Example 1 to isolate Ni ²⁺ exchanged zeolite. The Ni ²⁺ exchanged zeolite powder was then reduced by hydrogenation as described in Example 1. The resulting nickel exchanged zeolite contained 2.70% nickel as a result of ICP analysis.

Example 9

Sn ²⁺ exchanged zeolite powder was prepared as in Example 1 except about 150 g of SnSO ₄ was added to 200 mL of deionized water. About 25 g of zeolite Y (USY zeolite, W. R Grace and Company) was added to form a slurry. The slurry was stirred for about 18 hours and then washed as in Example 1 to isolate Sn ²⁺ exchanged zeolite powder. The Sn ²⁺ exchanged zeolite powder was then reduced by hydrogenation as described in Example 1. The resulting tin exchanged zeolite contained 10.3% tin as a result of ICP analysis.

Claims (50)

A composition comprising a carrier containing a metal-added cation exchange material, wherein the added metal is reduced to a substantially zero state. The method of claim 1, Wherein the cation exchange material of the metal-added cation exchange material is selected from the group consisting of zeolite, clay and silica. The method of claim 1, The metal-added cation exchange material is an inorganic cation exchange material, the added metal is a group consisting of calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin and mixtures thereof Composition selected from. The method of claim 1, The metal-added cation exchange material is a zeolite to which iron, copper, zinc, magnesium, tin, nickel or a mixture thereof is added. The method of claim 4, wherein Wherein the metal is copper. The method according to any one of claims 1 to 5, Wherein the carrier comprises a polymer matrix having at least about 0.1 weight percent of a cation exchange material distributed based on the weight of the polymer matrix. The method of claim 6, Wherein the polymer matrix is a thermoplastic resin having from about 0.1 to 20 parts by weight of the cation exchange material based on the weight of the polymer matrix. The method of claim 7, wherein Wherein the thermoplastic resin is selected from the group consisting of polyethylene, ethylene / vinyl acetate copolymers, vinyl chloride homopolymers, vinyl chloride copolymers and blends thereof. The method of claim 7, wherein And wherein the polymer matrix comprises polyethylene selected from the group consisting of high density polyethylene, low density polyethylene, very low density polyethylene, ultra low density polyethylene, linear low density polyethylene, blends thereof, and blends of these polyethylenes with other polymers. The method of claim 7, wherein Wherein the polymer matrix comprises a mixture of at least one polyethylene and at least one ethylene / vinyl acetate copolymer. The method of claim 7, wherein Polymer matrix is polyolefin, ethylene / vinyl acetate copolymer, butyl rubber, styrene / butadiene rubber, styrene / butadiene / styrene block copolymer, isoprene, styrene / isoprene / styrene block copolymer, styrene / ethylene / butylene / styrene block air A composition comprising a polymer selected from the group consisting of coalescing and mixtures thereof. The method of claim 6, A composition wherein the polymer matrix comprises at least one vinyl chloride resin. The method according to any one of claims 1 to 5, A composition comprising a film in which the carrier contains a metal-added cation exchange material to the film surface. The method according to any one of claims 1 to 5, Wherein the carrier comprises a mat containing a metal-added cation exchange material in the voids. The method according to any one of claims 1 to 5, Wherein the carrier comprises a porous pouch or sachet containing a metal-added cation exchange material. The method according to any one of claims 1 to 5, Wherein the carrier comprises a porous inorganic ceramic material in which a metal-added cation exchange material is distributed. The method of claim 6, Wherein the polymer matrix consists of a plastisol, dry blend or lacquer composition. At least one polymeric material dispersed in the liquid medium, and an oxygen scavenger, which is a metal-added cation exchange material, the metal is substantially reduced to zero, and the amount of the oxygen scavenger is at least one At least about 0.1 part by weight per 100 parts by weight of elastomeric material. The method of claim 18, Wherein the polymeric material is selected from epoxides, phenols, polyurethanes, polyvinyl chloride homopolymers, polyvinyl chloride copolymers, and mixtures thereof. The method of claim 18, The metal-added cation exchange material is a zeolite to which iron, copper, zinc, magnesium, tin or a blend thereof is added. The method of claim 18, Wherein the metal is copper. The method of claim 18, And a second oxygen scavenger selected from the group consisting of ascorbate, isoascorbate, tannin, sulfite, oxidizable polymers and blends thereof. Containing an oxygen sensitive material having a solid oxygen scavenging composition comprising as a part of the container a solid oxygen scavenging composition comprising a carrier having a metal-added cation exchange material wherein the added metal is substantially reduced to zero A product having a container having an internal cavity suitable for the. The method of claim 23, wherein A product wherein the cation exchange material of the metal-added cation exchange material is selected from the group consisting of zeolite, clay and silica. The method of claim 23, wherein The metal-added cation exchange material is an inorganic cation exchange material, the added metal is a group consisting of calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin and mixtures thereof Product selected from. The method of claim 23, wherein The metal-added cation exchange material is a zeolite to which iron, copper, zinc, magnesium, tin, nickel or a mixture thereof is added. The method of claim 25, Products whose metal is copper. The method according to any one of claims 23 to 27, Wherein the carrier comprises a polymer matrix having at least about 0.1 weight percent of a cation exchange material distributed based on the weight of the polymer matrix. The method of claim 28, A product of which the polymer matrix consists of a thermoplastic resin selected from the group consisting of polyethylene, ethylene / vinyl acetate copolymers, vinyl chloride homopolymers and copolymers, and blends thereof. The method of claim 28, Polymer matrix is polyolefin, ethylene / vinyl acetate copolymer, butyl rubber, styrene / butadiene rubber, styrene / butadiene / styrene block copolymer, isoprene, styrene / isoprene / styrene block copolymer, styrene / ethylene / butylene / styrene block air An article comprising a polymer selected from the group consisting of coalescing and mixtures thereof. The method of claim 28, Wherein the polymer matrix is at least one vinyl chloride resin. The method of claim 28, The polymer matrix is an elastomeric material selected from the group consisting of organic solvents and organic dispersions, and the at least one elastomeric material is polyolefin, butyl rubber, styrene / butadiene rubber, carboxylated styrene / butadiene, polyisoprene, styrene / isoprene A product selected from the group consisting of styrene block copolymers, styrene / butadiene / styrene block copolymers, styrene / ethylene / butylene / styrene block copolymers and mixtures thereof. The method of claim 28, Wherein the container consists of a container body and a container closure device, wherein the solid oxygen scavenging composition is on the interior surface of the container body, or on the interior surface of the closure device, or a gasket between the container body and the container closure device. The method according to any one of claims 23 to 27, An inner cavity of the container contains a solid oxygen scavenger composition, and wherein the carrier comprises a film containing a metal-added cation exchange material to the film surface. The method according to any one of claims 23 to 27, An interior cavity of the vessel contains a solid oxygen scavenger composition, and wherein the carrier comprises a mat containing a metal-added cation exchange material in the voids. The method according to any one of claims 23 to 27, An article comprising a porous pouch or sachet in which the interior cavity of the vessel contains a solid oxygen scavenger composition and wherein the carrier contains a metal-added cation exchange material. The method according to any one of claims 23 to 27, An interior cavity of the vessel contains a solid oxygen scavenger composition and the carrier comprises a porous inorganic ceramic material in which the metal-added cation exchange material is distributed. Eliminating the oxygen contained in the sealed inner cavity of the container, including exposing the inner cavity of the container to a composition comprising a carrier containing a metal-added cation exchange material in which the metal is substantially reduced to zero How to. The method of claim 38, Wherein the cation exchange material of the metal-added cation exchange material is selected from the group consisting of zeolite, clay and silica. The method of claim 38, The metal-added cation exchange material is an inorganic cation exchange material, the added metal is a group consisting of calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin and mixtures thereof The method chosen from. The method of claim 38, The metal-added cation exchange material is a zeolite to which iron, copper, zinc, magnesium, tin, nickel or a mixture thereof is added. 42. The method of claim 41 wherein The metal is copper. 43. The method of any of claims 38-42, Wherein the carrier comprises a polymer matrix having at least about 0.1% by weight distribution of cation exchange material based on the weight of the polymer matrix. The method of claim 43, Wherein the vessel consists of a vessel body and a vessel closure device, and the composition for solid oxygen scavenging is on the interior surface of the vessel body, or on the interior surface of the closure device, or a gasket between the vessel body and the vessel closure device. The method of claim 43, Wherein the composition is deposited in at least a portion of the container as a plastisol, dry blend or lacquer composition. The method of claim 43, The polymer matrix is a thermoplastic resin selected from the group consisting of polyethylene, ethylene / vinyl acetate copolymers, vinyl chloride homopolymers, vinyl chloride copolymers and blends thereof. 43. The method of any of claims 38-42, Wherein the carrier comprises a film containing a metal-added cation exchange material on the film surface, the film being received in an interior cavity of the vessel. 43. The method of any of claims 38-42, And the carrier comprises a woven or nonwoven mat containing a metal-added cation exchange material in the voids, wherein the woven or nonwoven mat is received in an interior cavity of the container. 43. The method of any of claims 38-42, And the carrier comprises a porous pouch or assay containing a metal-added cation exchange material, the pouch or assay being received in an interior cavity of the container. 43. The method of any of claims 38-42, Wherein the carrier comprises a porous inorganic ceramic material in which a metal-added cation exchange material is distributed, the porous inorganic ceramic material being received in an interior cavity of the vessel.