MXPA97001835A

MXPA97001835A - Oxygen elimination structures that have organic elimination material of oxygen and that have a polymeric select barrier

Info

Publication number: MXPA97001835A
Application number: MXPA/A/1997/001835A
Authority: MX
Inventors: Yen Ching Ta; Katsumoto Kiyoshi; L Goodrich Joseph; Diores Gallet J
Original assignee: Chevron Chemical Company
Priority date: 1994-09-12
Filing date: 1997-03-11
Publication date: 1997-06-01

Abstract

The present invention relates to a method for making a package, characterized in that it comprises: (i) identifying the proposed use temperature of the package, and (ii) forming a package comprising a layer having an organic oxygen scavenging material and a polymeric selective barrier layer, wherein the polymeric selective barrier layer is located between the container volume and the layer having an organic oxygen scavenger material, the polymeric selective barrier layer has a glass transition temperature of at least 5% C above the use temperature, the polymeric selective barrier layer has an oxygen transition rate of at least 1 cc O2 / 645 cm2 (100 in2) of polymeric selective barrier layer / day / a

Description

OXYGEN ELIMINATION STRUCTURES THAT HAVE ORGANIC MATERIAL FOR THE ELIMINATION OF OXYGEN AND THAT THEY HAVE A POL RANGE, IMERIC, SELECTIVE BACKGROUND AND BRIEF DESCRIPTION OF THE INVENTION Organic oxygen scavenging materials have been developed partially in response to the food industry's goal of having a longer shelf life for packaged food. These oxygen scavenging materials constitute at least a portion of the food package, and these materials remove oxygen from the volume of the closed package, which surrounds the food product, thereby inhibiting spoilage of the food. The organic oxygen scavenging materials can be low molecular weight oligomers that are typically incorporated in polymers or can be organic oxygen scavenging polymers in which either the skeleton is designed to separate when the polymer reacts with oxygen, or in the which, initially at least, the side chains react with oxygen. They produce a wide REF: 24278 variety of organic compounds due to the oxidation of the organic material of elimination of oxygen. Many of these oxidation products can migrate from the layer that has an organic oxygen removal material and enter the air surrounding the food, or even enter the food itself. Oxidation products may have offensive odors or may even be compounds that are generally considered unsafe for human consumption. Therefore, it is highly desirable to provide a way to prevent odorous oxidation products and / or oxidation products that are not to be consumed from entering a packaged volume containing food. One way to solve the problem of migration of the oxidation products is to form a composition comprising two layers, where one layer has or includes an organic oxygen removal material and one layer is a barrier located between the packaged volume and the layer that has an organic oxygen removal material. The problem with this approach is that many of the barriers that are effective in preventing the oxidation products from migrating in the packaged volume of the package also prevent oxygen from migrating from the packaged volume to the organic oxygen scavenging material. This invention provides compositions that overcome these problems. In one embodiment, the invention is a composition comprising at least two layers: a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, wherein the selective polymer barrier layer has a temperature of vitreous transition of at least about 5 ° C above the use temperature, and the selective, polymeric barrier layer has an oxygen transmission rate of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) of the polymer barrier, selective / guide / atm. The layers may be in the form of a film or films. In another embodiment, the invention is a composition comprising at least two layers: a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, wherein the selective polymeric barrier layer has a transition temperature vitreous at least about 5 ° C above the use temperature, and the composition has an effective oxygen removal rate of at least about 0.5 ce of 02 / gm of organic oxygen removal material / day / atm. In a further embodiment, the invention is a composition comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, wherein the selective polymeric barrier layer has a glass transition temperature of at least about 40 ° C and the selective polymeric barrier layer has an oxygen transition speed of at least about 1 centimeter of 2 / 645.16 cm2 (100 inches2) of the polymer barrier layer, selective / day / atm. In another embodiment, the invention is a composition comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, wherein the selective polymeric barrier layer has a vitreous transition temperature of at least about 40_ ° C and the composition has an effective oxygen removal rate of at least about 0.5 ce of 02 / gm of organic oxygen removal material / day / atm. In additional embodiments, the layer having an organic oxygen scavenging material is a polymer having oxidizable sites and having a transition metal salt catalyst that accelerates the oxidation of oxidizable sites. A particularly useful layer is a copolymer of ethylene-methyl acrylate-benzyl acrylate having a cobalt salt mixed therein. In other embodiments, the selective polymeric barrier layer is a polymer that has been oriented in at least the direction of the machine, such as oriented poly (ethylene terephthalate) or nylon 6 oriented biaxially. Among other factors, this invention is based on the discovery that the two-layer composition, one of which has a polymeric oxygen scavenging material and one in which a polymer selectively blocks or prevents the migration of the oxidation products, but easily transmits oxygen, provides compositions that can reduce food spoilage or otherwise extend the shelf life of oxygen sensitive products and can greatly reduce the amount and type of oxidation products that enter the packaged volume of the container in the which layers are incorporated. Also, this invention is based on the discovery that the vitreous transition temperature of the polymeric barrier layer, selective and its oxygen transmission rate helps determine whether the combination of this layer with a layer having a polymeric material for elimination of Oxygen will effectively reduce the deterioration of the food and will reduce the amount of oxidation products that enter the packaged volume. Furthermore, this invention is based on the discovery that when a polymer barrier layer is oriented, selective in at least one direction, and particularly when the layer is oriented in the directions of the cross machine, the two layers as described above will work for to eliminate oxygen quickly and to control that the oxidation products enter the closed volume of the container in which the two layers are incorporated. These and other advantages are apparent from the subsequent description.

DESCRIPTION OF THE FIGURES Figures 1 and 2 each contain two traces of the gas chromatograph showing the boiling point of the organic compounds in the space of the top above the two layers of the compositions of Examples 1 and 2, respectively. Figure 3 contains two traces of the gas chromatograph showing the boiling point of the organic compounds in the space of the upper part above the two layers of the composition of Comparative Example A.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The composition of this invention comprises a layer having an organic oxygen scavenging material and a polymeric layer which functions as a selective barrier for certain oxidation products, oxidation products which are in general those which are odorous and / or non-consumable, but not oxygen. A layer may be, for example, a rigid or semi-rigid sheet, or a flexible film, or a layer may be, for example, at least a portion of a manufacturing article, such as a bottle wall or the added piece of The bottle cap.

Layer that has the organic oxygen removal material The layer that has an organic oxygen removal material is any layer that has enough of an organic oxygen removal material, that the layer is able to remove at least 0.5 ce of 02 / grams of organic oxygen removal material / day / atm. Preferably, the layer is capable of removing at least about 1, and more preferably at least about 5 ce of 02 / gram of organic oxygen scavenging material / day / atm. The organic oxygen scavenging material may be mixed in the layer or laminar or sprayed in the layer, and / or may be a layer itself. For example, the organic oxygen scavenging material may be an organic compound such as triterpene with six double bonds but which is a mixture of double bond isomers or dehydrated castor oil as described in EP 0 507 207, which is incorporated in the present by reference in its entirety. This organic compound can be mixed with a polymeric carrier, which itself can or can not remove oxygen, or can be coated in a material such as aluminum foil or even incorporated into a material such as paper. The organic oxygen scavenging material may be in areas located in a layer, for example, the organic oxygen scavenging material may be in a patch that is laminated to a layer such as the polymer barrier layer, in which case the Polymer barrier layer is also the layer that has the organic oxygen removal material. The organic oxygen scavenging material can be coated in a polymeric layer or in a multilayer structure, in which case the organic oxygen scavenging material normally forms its own layer. The organic oxygen scavenging material can also be carried or carried as a layer, or in a layer within a multilayer structure. As noted above, the organic material for disposal can be a layer itself. The organic scavenging material is typically a polymer having oxidizable sites in the polymer and containing a catalyst such as a transition metal salt that aids in the initiation of oxidation of the oxidizable sites. Examples of polymers having oxidizable sites include polybutadiene, described in U.S. Patent No. 5,211,875; poly (raeta-xylenediamine-adipic acid) (also known as MXD-6), described in U.S. Patent Nos. 5,021,515 and 5,049,624 and EP 0 519 616; and poly (ethylene, methyl acrylate, benzyl acrylate), described in the North American application Serial No. 08 / 091,120, filed August 12, 1993, inventors T. Ching, K. Katsumoto, S. Current and L. Theard, each of which is incorporated by reference in the present in its entirety. The poly (ethylene), alkyl acrylate, benzyl acrylate) can be made by transesterification in solution. An ethylene-alkyl acrylate copolymer such as ethylene-methyl acrylate copolymer is dissolved in an appropriate solvent such as decalin, and heated and refluxed in the presence of an effective amount and a transesterification catalyst, such as tetraethyl or dibutyltin laurate titanate and an alcohol containing a benzyl radical, such as benzyl alcohol. The solution is then cooled, and the polymer is precipitated in methanol and dried in a vacuum oven. An effective amount of a transition metal salt catalyst such as cobalt neodecanoate is incorporated into the polymer precipitated upon melting the polymer, in, for example, an extruder, and mixing the salt dissolved in a solvent such as hexane in the mass polymer melt. The above transesterification can also occur using a molten copolymer of ethylene-alkyl acrylate in a reactive extruder maintained at transesterification conditions in the presence of an effective amount of a transesterification catalyst and an alcohol containing a benzyl radical.

Layer that functions as a selective barrier for certain oxidation products. The composition of this invention also comprises a polymeric layer that functions as a selective barrier to certain oxidation products but not to oxygen (also referred to herein as a selective, polymeric barrier layer). Oxidation products are often odorous and / or are generally considered unrecognized as safe food additives (GRAS) by the FDA. These oxidation products result from the oxidation of the particular organic material, oxygen removal, used. Examples of these oxidation products include carboxylic acids, such as acetic, propionic, butyric, varlicic and benzoic acids; aldehydes such as heptanal and benzaldehyde ?; ketones, such as acetone and methyl ethyl ketone; esters, such as methyl formate; and other compounds such as benzene. In a preferred embodiment, a polymeric layer functions as a barrier when it completely blocks an oxidation product or when it prevents the migration of an oxidation product to a degree that the amount of the oxidation product found in the volume enclosed after five days at 50 ° C produces a slight or no odor in the case of odorous compounds, or is within the guidance of the US Food and Drug Administration guideline for extractables in the case of compounds that are not generally considered as insurance. See 21 C.F.R. §§ 170-199 and Recommendations for Chemistry Data for Indirect Food Additive Petitions, published by the U.S. Food and Drug Administration, September 1988, Version 1.2, March 1993, each of which is incorporated herein in its entirety. The selective polymeric barrier layer does not necessarily prevent the migration of all oxidation products. For example, it is not necessary for the selective polymeric barrier layer to prevent migration of the oxidation products such as carbon dioxide, water or compounds declared as GRAS. Therefore, these oxidation products can migrate through the polymeric barrier layer, selective to the degree recognized as safe by the FDA. Also, the selective polymeric barrier layer can prevent the migration of many, but not all, oxidation products whose migration must be prevented. In a preferred embodiment, a layer is considered to be a polymer barrier layer, selective when it prevents at least half the number and / or number of oxidation products, which have a boiling point of at least about 75 ° C, pass through the polymeric barrier layer, selectively from the layer having the organic oxygen removal material. The selective polymeric barrier layer also allows oxygen to migrate through it to make contact with the layer having an organic oxygen scavenging material. In a preferred embodiment, the selective polymeric barrier layer allows sufficient oxygen to migrate through it, such that the effective rate of oxygen removal from the packaged volume for the composition of this invention (i.e., the oxygen scavenging layer) with the selective polymeric barrier layer present) is at least about 0.1 ce of 02 / gram of organic oxygen removal material / day / atm. Preferably, the selective polymeric barrier layer allows sufficient oxygen to migrate therethrough, from the packaged volume, such that the rate of oxygen scavenging for the oxygen scavenging layer is at least about 1, and preferred, about 5 ce of 02 / gram of organic oxygen removal material / day / atm.

In another preferred embodiment, the selective polymeric barrier layer has an oxygen transmission rate (OTR) of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) of selective, polymeric barrier layer. / day / atm; as measured by ASTM D-3985, which is incorporated by reference herein in its entirety. Preferably, the OTR is at least about 5, and most preferably at least about 10 cm2 / 645.16 cm2 (100 in2) of polymer barrier layer, selective / day to / atm. The glass transition temperature (Tg) as measured by ASTM D-3418, which is hereby incorporated in its entirety, by reference, has been found to provide a means to determine whether a polymeric layer will be a polymer barrier layer, selective, effective for many of the odorous and / or non-consumable oxidation compounds. In general, if the Tg of a polymeric layer is at least about 5 ° C above the use temperature of the composition of this invention, the polymeric layer will be a selective, polymeric barrier layer. Preferably, the Tq of a selective, psi, barrier layer is at least about 10 ° C above, and more preferably at least about 20 ° C above the use temperature. For some polymers, it may be necessary to orient the polymer so that it is an effective, selective polymer barrier layer. See U.S. Patent Nos. 3,903,294, 3,880,974, 3,857,917 and 3,510,522, all of which are incorporated herein by reference in their entirety, for some examples of polymer orientation methods. Where it is necessary to orient a polymer to make it a selective, effective, polymeric barrier layer, the temperature of use of that polymer is the highest temperature at which the selective, polymeric barrier layer is exposed after orientation of the polymer. The temperature of use in this case can be found at any time after the polymer has been oriented, such as film processing, during lamination or for as long as the oriented polymer is functioning as a selective barrier. By assumption, if the selective polymeric barrier layer is exposed to a temperature higher than the use temperature, but is subsequently oriented, the use temperature is the highest temperature at which the selective, polymeric barrier layer is exposes after this subsequent orientation of the polymer layer. It has also been found that certain polymeric layers that have been oriented (i.e., elongated in at least one direction in the plane of the layer) are selective, effective polymer barrier layers. For example, oriented poly (ethylene terephthalate) (OPET) and biaxially oriented nylon 6 are selective, polymeric barrier layers effective for many of the oxidation products of the polymeric oxygen scavenging material. For polymers in which the orientation of the film is not necessary for the polymer to be a selective, effective polymeric barrier layer, the temperature of use is the temperature at which the composition of this invention is exposed, while the The composition is removing oxygen from the packaged volume and protecting the contents (for example food) of the container in which the composition of this invention has been incorporated. For example, if the composition of this invention is incorporated into a meat pack, the temperature of use will be the highest temperature that the meat pack will find while the composition of this invention was removing oxygen to protect the meat from oxygen. It is speculated that polymers having crystalline and / or ordered structures, particular as indicated by Tg, by the crystallinity of the polymer, and / or by the fact that the polymer has been oriented, provides channels within the polymer that have blocking dimensions. selectively the diffusion of some larger molecules, such as the odorous or extractable oxidation products, but allow smaller molecules such as oxygen to pass through the polymer. This theory is provided only for the purpose of helping to explain why certain polymers are effective as polymer barrier layers., selective and is not limiting the scope of the invention. In a preferred embodiment, the Tg of the selective polymeric barrier layer is at least about 40 ° C. Preferably, the Tg of the selective polymeric barrier layer is at least about 50 ° C, and more preferably the Tg of the selective, polymeric barrier layer is at least about 60 ° C. The solubility of the oxidation products in the selective polymeric barrier layer can also be a factor in determining whether a selected polymer will act as a selective, polymeric barrier layer. If an oxidation product is very soluble in a polymer, it is likely to migrate through the polymer, and therefore the polymer will not be useful as a selective, polymeric barrier layer. An oxidation product that is soluble in a polymer can change the Tg of the polymer. As a result, a polymer having a sufficient Tg to block the oxidation products can have its Tg reduced by an oxidation product at a level that the polymer can not be used as a selective, polymeric barrier layer. Since this effect occurs over time, a polymer can be a polymer barrier layer, selective, effective in some applications, ta. such as where the food product contained within the container is more readily consumed after packaging, but can not be a selective, effective, polymer barrier layer in other situations, such as where the food product is expected to have shelf life. several years. A selective polymeric barrier layer may contain plasticizers such as esters of ptalaphthates and / or poly (ethylene glycols). A selective polymeric barrier layer can be a mixture of polymers, such as a compatibilized mixture of PET and nylon 6 which is then oriented. The selective polymer barrier layer can be modified (for example, with fillers such as calcium carbonate and / or Ti02). The selective polymeric barrier layer can also be a multilayer construction, in which any layer does not necessarily qualify as a selective, polymeric barrier layer alone, but together the multi-layer construction is a selective, polymeric barrier layer.

Laying the Two Layers The selective polymeric barrier layer is located between the enclosed space or packaged volume from which the oxygen is going to be removed and the layer that has an organic oxygen scavenging material. The layers can be two separate layers or multilayer structures that do not make physical contact with each other, the two layers can be part of the same multilayer structure. In a preferred embodiment, the composition of this invention comprises two layers that have been extruded or laminated together. In another embodiment of this invention, the composition comprises three layers that have been co-extruded or laminated together, where a bonding layer between the layer having an organic oxygen scavenging material and the selective polymer barrier layer is used. Suitable tie layers include ethylene-acrylic acid ionomers and ethylene-alkyl acrylate ionomers, such as those described in US Application Serial No. 08 / 144,173, filed October 27, 1993, inventors J. Wang, D Rosendale, V. Kurkov and L. Theard, which is incorporated herein by reference in its entirety. In a further embodiment of this invention, the composition comprises three layers that have been co-extruded or laminated together: 2 ° ¿.

An oxygen barrier layer, having an OTR of not more than about 1 c of 02 / 645.16 cm2 (100 inches2) of oxygen barrier layer / day / atm; a layer having an organic oxygen scavenging material; and a selective, polymeric barrier layer. Examples of layers of 02 include copolymers of ethylene-vinyl alcohol and poly (vinylidene chloride). When the selective polymeric barrier layer is an oriented layer such as OPET or oriented nylon, the selective polymeric barrier layer can be oriented before it is coiled with the layer having an organic oxygen scavenging material. Alternatively, a selective, non-oriented polymeric barrier layer can be co-extruded with the layer having an organic oxygen scavenging material, and this multilayer structure can then be oriented. The following examples are illustrative and not limiting of the scope of the invention.

EXAMPLES Example 1-2 and Comparative Example A An organic ethylene-methyl acrylate-benzyl acrylate oxygen scavenging material is made by the method described in the North American application Serial No. 08 / 091,120, filed July 13, 1993, inventors T. Ching, K. Katsumoto, S. Current, and L. Theard. This material had approximately 17% by weight of methyl acrylate, 11% of benzyl acrylate, and approximately 1000 ppm of cobalt from cobalt neodecanoate. For analysis of the odorous compounds, this organic oxygen scavenging material was extruded to form a one-layer film approximately 0.0127 mm (0.5 mil) thick. The film was irradiated with UV by the method described in US Patent No. 5,211,875, and the film was allowed to remove oxygen for 3-5 weeks. A film of a polymer selected for the evaluation of its performance as a selective, polymeric barrier layer was also extruded to a thickness of approximately 0.0127 mm (0.5 mil). The film of ethylene-methyl acrylate-benzyl acrylate, oxygen scavenging material and the selected polymer film was then placed between two rectangular aluminum blocks, each 0.95 cm (3/8 inch) wide and 5.08 mm thick. cm (2 inches) long, and each having a top channel approximately 0.635 cm (0.25 inches) deep for most of the length of the blocks it faces towards each of the two films. The blocks were pressed together, so that the films were secured essentially in an airtight manner between the blocks. The assembly was placed in an oven and maintained at 49 ° C for 120 hours. The upper channels in the two blocks were equipped to be maintained at isobaric conditions. The samples were removed from each upper part, and gas chromatography was used to determine the presence of odorous compounds. The samples were also sniffed to determine if odors were present. The results of these tests are given in Table 1 and in Figures 1-3.

Figures 1-3 show the CG traces for three two-layer structures, where the OPET, biaxially oriented nylon 6, and biaxially oriented polypropylene (BOPP) were used individually as the polymer barrier layers, selective, candidate, and ethylene-methyl acrylate-benzyl acrylate material, oxygen scavenging as discussed above, was used as the layer having the organic oxygen scavenging material. The nylon 6 oriented biaxially (poly (eta-caprolactam)) is available from Allied Signal, grade CE1500, with a thickness of 0.0152 mm (0.60 mils). The nylon 6 oriented biaxially is available from Mobil Chem, Co. Degree IOC 4CM. The OPET with normal packing degree is available from American Hoechst. Each figure contains two strokes. The trace on the left is the GC analysis of the organic materials in the top space above the layer that has an organic oxygen scavenging material (ie, the ethylene-methyl acrylate-acrylate material). benzyl, oxygen removal). The trace on the right is the GC analysis of the organic materials in the space of the upper part above the polymer barrier layer, selective, candidate. These strokes were generated by keeping the temperature constant for the first part of the test, then slowly increasing the temperature to the maximum indicated on the trace. Each maximum value (peak) represents at least one compound or oxidation product that developed at the indicated temperature, and the area under the maximum value is a function of the amount of the oxidation product that developed at this temperature. The traces for the films containing OPET (Figure 1) and nylon 6 oriented biaxially (Figure 2) have very few maximum values present in the upper part above the polymeric barrier layer, selective, that the trace for the film that uses BOPP (Figure 3). These GC tracings illustrate the effectiveness of OPET and biaxially oriented nylon 6 as the selective polymeric barrier layers, and also show that BOPP is not useful as a selective, polymeric barrier layer. For the analysis of the extractables, low density polyethylene (Chevron Chemical Co., Grade 1017) and the material of ethylene-methyl acrylate-benzyl acrylate, oxygen removal, with OPET, nylon 6 oriented biaxially and coextruded were co-extruded. BOPP to form films having three layers, the polymeric barrier layer, selective, candidate (i.e., OPET, nylon 6 oriented biaxially or BOPP), the layer having the organic oxygen removal material (i.e. material ethylene-methyl acrylate-benzyl acrylate, oxygen removal), and polyethylene, respectively. Each layer was approximately 0.0127 mm (0.5 thousandths of an inch) thick. Each of the three-layer films was then placed separately between two rectangular aluminum blocks, each being 0.95 cm (3/8 inches) wide and 5.08 cm (2 inches) long, and a block that It has a channel of approximately 0.0762 cm (0.03 inches) in depth over most of the length of its face that abuts the selected polymer layer to be analyzed for its performance as a selective, polymeric barrier layer. The blocks are tightened together so that the three-layer film is essentially secured in an airtight manner between the blocks. Mazola corn oil was injected into the canal through a hole. The assembly was placed in an oven and kept at 49 ° C for 120 hours. The corn oil was sampled after this time, and the oxidation products extracted in the corn oil were analyzed using GC and GC with mass spectrometry. Toluene was used as an internal standard in corn oil to calibrate the results. These tests generate GC traces similar to those shown in Figures 1 and 3 and show few extractables for films using OPET and nylon 6 oriented biaxially, while the film using BOPP had extensive extractables.

TABLE 1 EJ. No. Layer 1; Layer 2: Tg of the OTR of the Results of Re- results (layer that (candidate Layer 2 / c Layer 2, ce the proof of the test has the for the of 02 / 645.16 odor of the side of the material layer of cm '(100 barrier organic barrier substances, inches7) (sniffing) extractable polymer removal / day / atm oxygen) selective) copolymer of poly (ethylene 125 10 Odors no ethylene-terephthalate detectable extractable acrylate substances) oriented blocked methyl- benzyl acrylate containing 1000 ppm cobalt Same as Ex. nylon 6 40-60 1.4 Odors no No) 1 oriented detectable available V £ > biaxially Compt, A Same as E. Polipropi • 20 155 Were not se 1 leno apparent blocked oriented stale smells so biaxialy penetrating effective mind extractable substances It is noted that in relation to this date, the best method known by the applicant to carry out the present invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property:

Claims

1. A composition comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer characterized in that the selective polymeric barrier layer has a vitreous transition temperature of at least about 5 ° C above the polymeric barrier layer. temperature of use, and the selective polymeric barrier layer has an oxygen transmission rate of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) of polymeric barrier layer, selective / day / atm.

2. A composition comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer characterized in that the selective polymeric barrier layer has a vitreous transition temperature of at least about 5 ° C above the polymeric barrier layer. temperature of use, and the composition has an effective rate of oxygen removal of at least about 0.5 ce of 02 / gm of organic oxygen removal material / day / atm.

3. A composition comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer characterized in that the selective polymeric barrier layer has a vitreous transition temperature of at least about 40 ° C, and the polymer barrier, selective has an oxygen transmission rate of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) polymer barrier layer, selective / day / atm.

4. A composition comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer characterized in that the selective polymeric barrier layer has a vitreous transition temperature of at least about 40 ° C and the composition has an effective oxygen scavenging rate of at least about 0.5 ce of 02 / gm of organic oxygen scavenging material / day / atm.

5. The composition according to claim 1, Z, 3, or 4, characterized in that the layer having an organic oxygen scavenging material comprises a polymer having oxidizable sites in the polymer and containing a transition metal salt catalyst. .

6. The composition according to claim 5, characterized in that the organic elimination material comprises the ethylene-methyl acrylate-benzyl acrylate copolymer and a quantity of transition metal salt which is effective to promote the removal of oxygen.

7. The composition according to claim 5, characterized in that the selective polymeric barrier layer is a polymer that has been oriented in at least the direction of the machine.

8. The composition according to claim 5, characterized in that the selective polymeric barrier layer comprises oriented poly (ethylene terephthalate).

9. The composition according to claim 5, characterized in that the selective polymeric barrier layer comprises nylon 6 oriented biaxially.

10. The composition according to claim 6, characterized in that the selective polymeric barrier layer comprises oriented poly (ethylene terephthalate).

11. The composition according to claim 6, characterized in that the selective polymeric barrier layer comprises oriented nylon 6.

12. The composition according to claim 1, 2, 3, or 4, characterized in that the composition is a film.

13. A container comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, characterized in that the selective polymeric barrier layer is located between the packaged volume and the layer having an organic material for elimination. of oxygen, the selective polymeric barrier layer has a vitreous transition temperature of at least about 5 ° C above the use temperature, and the selective, polymeric barrier layer has an oxygen transmission rate of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) of polymeric barrier layer, selective / day / atm.

14. A container comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, characterized in that the selective polymeric barrier layer is located between the packaged volume and the layer having an organic material for eliminating oxygen, the selective polymeric barrier layer has a vitreous transition temperature of at least about 5 ° C above the use temperature, and the composition has an effective oxygen removal rate of at least about 0.5 ce of 02 / gm of organic oxygen removal material / day / atm.

15. A container comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, characterized in that the selective polymeric barrier layer is located between the packaged volume and the layer having an organic material for eliminating oxygen, the selective polymeric barrier layer has a vitreous transition temperature of at least about 40 ° C and the selective, polymeric barrier layer has an oxygen transmission rate of at least about 1 cc of 02 / 645.16 cm2 (100 Inch2) polymer barrier layer, selective / day / at.

16. A container comprising a layer having an organic oxygen scavenging material and a selective polymeric barrier layer, characterized in that the selective polymeric barrier layer is located between the packaged volume and the layer having an organic material for eliminating oxygen, the selective polymeric barrier layer has a vitreous transition temperature of at least about 40 ° C and the composition has an effective oxygen scavenging rate of at least about 0.5 ce of 02 / gm of organic oxygen scavenging material / day / atm.

17. A method for reducing the amount and / or type of organic oxidation products, which enter a packaged volume, organic oxidation products that are produced by the oxidation of an organic oxygen scavenging material, characterized in that it comprises placing a layer of selective, polymeric barrier having a vitreous transition temperature of at least about 40 ° C, between the packaged volume and a layer having an organic oxygen scavenging material.

18. The method according to claim 17, characterized in that the selective polymeric barrier layer has an oxygen transmission rate of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) of polymer barrier layer, selective / day / atm

19. The method according to claim 17, characterized in that at least 0.5 ce 02 are removed from the packed volume / gram of organic oxygen removal material / day / atm.

20. A method for reducing the amount and / or type of organic oxidation products that enter a packaged volume, organic oxidation products that are produced by the oxidation of an organic oxygen scavenging material, characterized in that it comprises placing a barrier layer polymeric, selective having a vitreous transition temperature of at least about 5 ° C above the use temperature between the packaged volume and a layer having an organic oxygen scavenging material.

21. The method according to claim 20, characterized in that the selective polymeric barrier layer has an oxygen transmission rate of at least about 1 ce of 02 / 645.16 cm2 (100 inches2) of selective, polymeric barrier layer / day / atm

22. The method according to claim 20, characterized in that at least 0.5 ce 02 are removed from the packed volume / gm of organic oxygen removal material / day / atm. SUMMARY OF THE INVENTION A composition comprising a layer having an organic oxygen scavenging material and a polymer barrier layer is disclosed., selective. The selective polymeric barrier layer allows oxygen to migrate from the packaged volume to the organic oxygen scavenging material, and the selective polymer barrier layer blocks the migration of the compounds created during the oxidation of the organic oxygen scavenging material of the layer having the organic oxygen removal material towards the interior of the container in which the composition of this invention is incorporated. In one embodiment, the selective polymeric barrier layer has a vitreous transition temperature greater than about 5 ° C above the use temperature of the container in which the composition of this invention is incorporated. In another embodiment, the selective polymeric barrier layer has a glass transition temperature greater than about 40 ° C. In yet another embodiment, the selective polymeric barrier layer is an oriented polymer. In a further embodiment, the layer having the organic oxygen scavenging material is a polymer having oxidizable sites in the polymer containing a transition metal salt catalyst.