Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers

【0001】<u style="single">Background of the invention</u>This application is a partial continuation application of application number 09 / 575,094 filed on May 19, 2000, and a partial continuation application of application number 09 / 595,410 filed on June 16, 2000. There is a partial continuation application of application number 09 / 666,642 filed on September 21, 2000, and a partial continuation application of application number 09 / 800,418 filed on March 6, 2001. [0002] (Field of invention) The present invention relates generally to the field of oxygen blocking polymers. More specifically, the present invention is such as poly (ethylene / vinyl alcohol) (EVOH), polyvinylidene dichloride (PVDC), polyethylene terephthalate (PET), or polyamides other than MXD6 with oxygen degassing polymers. The present invention relates to a blend of oxygen-blocking polymers, a method for producing the blend, a packaging (package) article containing the blend, and a method for producing the packaging (package) article. [0003] (Description of related technology) It is well known to limit the exposure of oxygen-sensitive products to oxygen to maintain and enhance product quality and shelf life. For example, in packaging (packaging) systems, limiting the exposure of oxygen-sensitive foods to oxygen maintains food quality and avoids food damage. In addition, such packaging also keeps the product longer in inventory material, thereby reducing waste and the costs incurred from new supplies. In the food packaging industry, some to limit exposure to oxygen, including packaging in a modified atmosphere (MAP), vacuum packaging (package) and oxygen blocking film packaging (package). Means have already been developed. In the first two cases, the reduced oxygen environment is used in the packaging, while in the latter case, it physically prevents oxygen from entering the packaging environment. [0004] Other recent techniques for limiting exposure to oxygen include introducing an oxygen degassing agent into the packaging (for packaging) structure. The introduction of the degassing agent in the package is mainly used to remove the upper oxygen in the package in a short time, thus the oxygen degassing polymer is such that the upper oxygen in the package is removed. It is typically based on a type of polymer with a high oxygen permeation rate that quickly reaches the oxygen degassing site and ensures that the oxygen level decreases over a short period of time. [0005] Oxygen blocking polymers such as cast, blown or oriented poly (ethylene / vinyl alcohol) (EVOH), polyethylene terephthalate (PET), polyvinylidene dichloride (PVDC), and polyamide. Is (O₂And CO₂It is widely known to have very strong blocking properties against gases and other fluids (such as), and widespread applications have been found in packaging applications where blocking properties are desired. However, their oxygen blocking properties are conventional packaging, such as glass or metal (suitable for packaging applications that require high oxygen blocking properties over a long period of time, such as beer packages). It is generally believed that it is not as strong as the blocking properties of materials for use (for packaging). This requires that the oxygen blocking performance of existing blocking polymers be significantly improved or that their performance approaches that of, for example, glass or metal. [0006] Therefore, an oxygen-blocking polymer in which a packaging (packaging) article is more suitable for applying higher oxygen blocking properties over a longer period of time than currently known packaging (packaging) articles. And it would be desirable to have packaging (packaging) articles containing additional ingredients (s). [0007] U.S. Pat. No. 5,021,515 by Cochran et al. Discloses a layer of packaging article consisting of 96% polyethylene terephthalate, 4% nylon MXD6 and 200 ppm cobalt. [0008] US Pat. No. 6,063,417 by Paleari et al. Describes a core layer consisting of approximately 40% to 85% by weight nylon 6/12 and approximately 15% to 60% by weight ethylene / vinyl alcohol copolymer (EVOH). Discloses packaging (packaging) films including. [0009] U.S. Pat. No. 5,153,038 by Koyama et al. Discloses packaging articles that include a layer consisting of an oxygen degassing agent such as polyhydric phenol and an oxygen blocking resin such as EVOH or polyamide. [0010] U.S. Pat. No. 5,281,360 by Hong et al. Describes (i) moldable polyester or polycarbonate-like polymers; (ii) EVOH, aromatic or aliphatic nylon (including nylon MXD6 according to Hong et al.), Or amorphous. Disclosed are blends of oxygen blocking materials such as nylon; (iii) transition metal catalysts. If component (ii) is nylon MXD6, it can be present up to about 30% by weight of the blend, and component (i) is preferably polyethylene terephthalate (PET). [0011] U.S. Pat. No. 5,759,653, such as Collette, discloses a blend of PET with an oxygen degassing agent such as nylon MXD6. The blend can also further include a metal catalyst. [0012] US Pat. No. 5,641,825 by Bacskai et al. Discloses compositions containing (i) polyolefins crosslinked with unsaturated carboxylic acids or unsaturated carboxylic acids anhydride, (ii) nylon MXD6, and (iii) cobalt as an oxidation catalyst. ing. [0013] (Disclosure of Invention)<u style="single">Outline of the invention</u>In one set of embodiments, the present invention relates to a composition comprising a blend of an oxygen blocking polymer, an oxygen degassing polymer, and an oxidation catalyst. The blend can be miscible or affinity (compatible). In one embodiment, the composition can further comprise an affinity agent (compatibilizer). Preferred oxygen blocking polymers are polymers or copolymers of vinyl alcohols such as ethylene / vinyl alcohol copolymers (EVOH), polyesters (such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)). Kind, polymers or copolymers of vinylidene dichloride (such as polyvinylidene dichloride (PVDC)), polymers or copolymers of epoxys, polysulfones, acrylonitrile (such as polyacrylonitrile (PAN)) Includes polymers and copolymers, polymers or copolymers of isocyanates, or polyamides other than MXD6 (eg, nylon 6; nylon 6,6; or nylon 6,12, among others). [0014] One preferred oxygen degassing polymer of the blend is a polyamide derived from a monomer containing a xylene diamine moiety by at least one moiety, and the blend further comprises a transition metal oxidation catalyst. More preferably, the polyamides are MXD6 polymers or oligomers, and the transition metal catalyst is a cobalt salt with an organic counterion. [0015] In a related aspect, the invention also relates to a packaging article comprising at least one layer, comprising a blend of an oxygen blocking polymer and an oxygen degassing polymer. The packaging (packaging) article can be a single-layer or multi-layer article and can be flexible or rigid. Articles for multi-layer packaging (for packaging) include, among other things, a structural layer (single layer or multiple layers), an oxygen blocking layer (single layer or multiple layers) containing no oxygen degassing polymer, an oxygen degassing layer, and an oxygen permeable layer. (Single layer or multiple layers), or an adhesive layer (single layer or multiple layers) can be further included. [0016] In still another aspect, the present invention is a blend of an oxygen-blocking polymer and an oxygen-degassing polymer, which comprises preparing an oxygen-blocking polymer and an oxygen-degassing polymer, and blending the materials thereof. Regarding how to make. Preferably, the blend comprises an oxidation catalyst, and the preparing step further comprises preparing the oxidation catalyst. The blending step can further include increasing the miscibility or affinity (compatibility) and improving the affinity (compatibility) of the blend by using any suitable affinity agent (harmonic agent). Oxidation catalysts can be introduced at the appropriate stage of the blending process, and with the catalyst, and in the appropriate form as either a solution or a masterbatch. [0017] The present invention is high over a long period of time by incorporating, for example, the inherent oxygen blocking properties of polyamides other than EVOH, PET, PVDC, PAN, or MXD6, and the oxygen degassing activity of oxygen degassing polymers. Provide packaging (packaging) articles having oxygen blocking properties. Because it is an oxygen-blocking polymer, only trace amounts of oxygen reach the OSP due to the low accessibility of oxygen to the oxygen degassing polymer (OSP); therefore, the OSP is typically rapid. It is not consumed and therefore has a useful life for a very long period of time. Due to the inherent blocking properties of the blocking resin, the invention also presents because OSP is only introduced at levels below the level at which the effect on the physical blocking of the oxygen blocking polymer is minimal. CO (useful for maintaining carbonation of packaged soft drinks, beer, and sparkling wines)₂Provide packaging (packaging) articles that have the advantage of providing barrier properties. In addition, blends of oxygen blocking polymers and carbon degassing polymers typically have good clarity (transparency) and can be easily processed into a variety of formulations. An additional advantage is realized when the oxygen blocking polymer is EVOH and the oxygen degassing polymer is a polyamide derived at least one part from a xylene diamine-based monomer, i.e. with EVOH and polyamides. Seems to be very inherently compatible (compatible) due to the favorable hydrogen bond interaction between the hydroxyl group of EVOH and the amide group of the polyamide, and the affinity (harmonious agent). Further use would generally not be necessary. [0018]<u style="single">Description of exemplary embodiments</u><u style="single">Oxygen blocking composition</u>In one embodiment, the invention relates to a composition comprising a blend of an oxygen blocking polymer and an oxygen degassing polymer. Such compositions are useful as components of the oxygen barrier layer of packaging (packaging) articles. By "oxygen blocking layer" is meant a layer containing a blend of an oxygen blocking polymer and an oxygen degassing polymer. Due to the presence of OSP, the oxygen blocking layer can be referred to as the "active oxygen blocking" layer. [0019] Packaging (packaging) articles typically fall into several forms, including single-layer flexible articles, multi-layer flexible articles, single-layer rigid articles or multi-layer rigid articles. Typical hard or semi-rigid articles are plastic, paper or cardboard cartons, or bottles such as juice containers, soft drink containers, heat forming trays or with wall thicknesses in the range of 100-1000 micrometer. Includes a cup. A typical flexible article includes an article used to wrap a large number of single food items, and will probably have a thickness of 5 to 250 micrometers. The wall of such articles consists of either single-layer or multi-layer material. [0020] Packaging (packaging) articles containing the active oxygen blocking composition can be any product for which it is desirable to prevent oxygen damage during storage, such as foods, beverages, formulations, pharmaceuticals, cosmetics, corrosive metals or It can be used to package electronic devices. It is particularly useful for packaging products where it is desirable to maintain high oxygen barrier properties over a long period of time, such as beer, wine and other beverages. It is also particularly useful for packaging products for which it is desirable to maintain carbon dioxide, such as beer, sparkling wines and soft drinks. [0021] [0021] The packaging (packaging) article containing the active oxygen blocking composition may contain a single layer containing the composition, that is, an oxygen blocking layer, and an oxygen degassing layer and an oxygen degassing polymer, alone or in any combination. It can include additional layers such as an oxygen blocking layer, a food-contact layer, a structural layer or an adhesive layer that do not contain. Single-layer packaging (packaging) articles can, in particular, be manufactured by solvent injection, injection molding, blow molding, stretch blow molding, or extrusion, as a technique in particular. Packaging (packaging) articles with multiple layers can typically be made using co-extrusion molding, injection molding, blow molding, stretch blow molding, coating, or lamination, especially as a technique. [0022] The packaging (packaging) article can include any of the active oxygen blocking compositions described below. As described above, the active oxygen blocking composition comprises a blend of an oxygen blocking polymer and an oxygen degassing polymer. Preferably it further comprises an oxidation catalyst. When formed on a film, the composition preferably has an oxygen permeation rate that is at least twice as low as the oxygen permeation rate of the oxygen blocking polymer alone. [0023] An oxygen-blocking polymer, for example, has a 1-mil layer essentially composed of an oxygen-blocking polymer at 1 atm.₂And about 100cc / m at room temperature under 0% humidity²Any polymer generally believed to provide blocking against oxygen passage, with an oxygen permeation rate of less than / day. Preferably, the oxygen blocking polymer is a polymer or copolymer of vinyl alcohol (such as ethylene / vinyl alcohol copolymer (EVOH)), such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN). Polypolymers, polymers or copolymers of vinylidene dichloride (such as polyvinylidene dichloride (PVDC)), polymers or copolymers of epoxys, polysulfones, (such as polyacrylonitrile (PAN)) ) It is selected from polymers or copolymers of acrylonitrile, polymers or copolymers of isocyanates, and polyamides other than MXD6. [0024] In one preferred embodiment, the oxygen blocking polymer is poly (ethylene vinyl alcohol) (EVOH). In yet another preferred embodiment, the oxygen blocking polymer is a polyacrylonitrile (PAN) or a copolymer containing acrylonitrile. In a more preferred embodiment, the oxygen blocking polymer is polyvinylidene dichloride (PVDC). In an additional preferred embodiment, the oxygen blocking polymer is polyethylene terephthalate (PET). In an even more preferred embodiment, the oxygen blocking polymer is polyethylene naphthalate (PEN). In an additional preferred embodiment, the oxygen blocking polymer is a polyamide other than MXD6. The polyamide can be aliphatic or aromatic. Preferred polyamides include nylon 6; nylon 6,6; and nylon 6,12. [0025] PVDC has many desirable properties. For one, it has water resistance, which means that it does not typically reduce its oxygen barrier properties when exposed to water with PVDC. Elsewhere, PVDC can be readily compounded as a coating, as a molded product, or as an extruded film. Yet otherwise, PVDCs are generally less costly than some other oxygen blocking polymers such as EVOH. [0026] Two or more oxygen blocking polymers can be used. The suitability of a particular oxygen blocking polymer can vary depending on the intended use, composition of the polymer or the packaging (packaging) article made from it. [0027] The oxygen degassing polymer can be any organic compound that reacts irreversibly with oxygen. Preferably, the OSP is a thermoplastic that is miscible or compatible with the oxygen blocking polymer. The polymer can be an addition polymer or a condensation polymer. Examples of addition polymers are ethylene / methyl acrylate / cyclohexenyl methyl acrylate ternary polymer (terpolymer) (EMCM), ethylene / vinyl cyclohexene copolymer (EVCH), or ethylene / cyclohexenyl methyl acrylate copolymer (ECHA). ), Or a polymer or copolymer containing a cyclic olefin group of either the main chain or pendant, such as a cyclohexenylmethyl acrylate homopolymer (CHAA), preferably a cyclic olefin group having a cyclohexene structure. Includes, but is not limited to. These examples also include, but are not limited to, polymers or copolymers containing pendant benzyl groups such as ethylene / methyl acrylate / benzyl methyl acrylate ternary polymers (terpolymers) (EMBZ). .. Those examples also include polyisoprene, polybutadiene, and copolymers thereof, such as diene polymers such as styrene-butadiene. Polypentenamer, polyoctenamer, and other polymers made by olefin metathesis; diene oligomers such as squalene; and dicyclopentadiene, norbornadiene, 5-ethylidene-2-norbornen, or (conjugated) Polymer compounds such as polymers or copolymers derived from other monomers having more than one (or unconjugated) carbon-carbon double bond are also included. [0028] Examples of condensation polymers include, but are not limited to, condensation polymers such as polyester polymers or copolymers containing carbon-carbon double bonds. More preferably, the polyester contains a cyclic olefin and cyclic olefin group, either the main chain or the pendant, preferably a cyclohexene moiety. [0029] Preferably, the oxygen degassing polymer comprises an ethylene backbone and at least one cyclic olefin pendant group. More preferably, the cyclic olefin pendant group is a cycloalkenyl group having the following structural formula I:<img file="JP4852214B2_D0001.tif" />(In the formula, q₁, Q₂, Q₃, Q₄And r are independently selected from hydrogen, methyl or ethyl; m is-(CH₂)_n-(However, n is an integer from 0 to 4); X is absent or a linking group; and if r is hydrogen, q₁, Q₂, Q₃And q₄At least one of them is also hydrogen). Preferably, in structural formula I, q₁, Q₂, Q₃, Q₄And r are hydrogen, respectively, and m is CH₂(Ie the cycloalkenyl group is cyclohexenyl). [0030] One of the most preferred oxygen degassing compounds is ethylene / vinyl cyclohexene copolymer (EVCH). Preferably, X is a linking group that binds the ethylene backbone to the cyclic olefin group. Its linking group is -O- (CHR)_n-; -(C = O) -O- (CHR)_n-; -NH- (CHR)_n-; -O- (C = O)-(CHR)_n-;-(C = O) -NH- (CHR)_n-; Or-(C = O) -O-CHOH-CH₂Selected from -O-. [0031] Preferably, the oxygen degassing polymer is a homopolymer or copolymer of cyclohexenylmethyl acrylate. The most preferred oxygen degassing polymer is ethylene / methyl acrylate / cyclohexenyl methyl acrylate ternary polymer (EMCM). A more preferred oxygen degassing polymer is an ethylene / cyclohexenyl methyl acrylate copolymer (ECHA). The most preferable oxygen degassing polymer is cyclohexenylmethyl acrylate homopolymer (CHAA). [0032] In another embodiment, the oxygen degassing polymer is a polyester polymer comprising the following Structural Formula II or the following Structural Formula III:<img file="JP4852214B2_D0002.tif" />(In the formula, q₁, Q₂, Q₃, Q₄And r are independently selected from hydrogen, methyl or ethyl, preferably q₁, Q₂, Q₃, Q₄And r are hydrogen (ie, its polymer is derived from tetrahydrophthalic anhydride): [0033]<img file="JP4852214B2_D0003.tif" />(In the formula, q₁, Q₂, Q₃, Q₄And r are independently selected from hydrogen, methyl or ethyl; m is-(CH₂)_n-(However, n is an integer from 0 to 4); and if r is hydrogen, then q₁, Q₂, Q₃And q₄At least one of them is also hydrogen). Preferably the polymer is derived from 3-cyclohexene-1,1-dimethanol. [0034] In a preferred embodiment of the other set, the oxygen degassing polymer is a polyamide derived at least in part from a monomer containing a xylene diamine moiety (also known as a "xylene diamine-based monomer"). A "xylene diamine-based monomer" is any substituted or unsubstituted xylene in which an amine group can form a polyamide bond during polymerization with a diamine, diic acid halide, etc. Means diamine. The polyamide can be a homopolymer derived from a xylene diamine and a diamine, or a copolymer containing any mol% of a monomer containing a xylene diamine moiety; preferably the polyamide contains a xylene diamine. Contains about 10 mol% to about 50 mol% units derived from the base monomer. [0035] If the oxygen degassing polymer is a polyamide at least partially derived from a xylene diamine-based monomer, then preferably the oxygen blocking polymer is a copolymer containing EVOH, PAN, acrylonitrile, PVDC, or It is selected from polyamides that are not derived from xylenediamine-based monomers. [0036] Two or more oxygen degassing polymers can be used. It should be recognized that a suitable oxygen degassing polymer for a given application depends on the intended application, its workability with the oxygen blocking polymer and other parameters. [0037] The blend can include from about 0.1% to about 50% by weight of oxygen degassing polymer. Preferably the blend comprises from about 1% to about 30% by weight of oxygen degassing polymer. That level of OSP should not plasticize the blocking polymer so seriously that it causes a significant reduction in the nature of passive oxygen blocking. [0038] The blend accounts for at least about 50%, preferably at least about 80% by weight of the oxygen blocking composition, the rest being occupied by other ingredients as described below. [0039] The blend is preferably in the form of a miscible or affinity (compatible) blend. Alternatively, the oxygen degassing polymer can be present in the composition as an insoluble filler (ie, the oxygen degassing polymer is crosslinked by itself and introduced into the oxygen blocking polymer matrix as a filler). .. [0040] Typically, the blend is a miscible blend or is occupied by a matrix, i.e. an oxygen blocking polymer as the dispersion phase, and the oxygen degassing polymer is occupied as a dispersed phase. [0041] From the standpoint of both performance and processability, it is typically desirable that the oxygen degassing polymer be efficiently dispersed in the blocking polymer. Therefore, an affinity agent (compatibilizer) may be needed to improve the miscibility or affinity (compatibility) of the blend. [0042] Preferred affinity agents (harmonizing agents) are acid anhydride-modified or acid-modified poly (ethylene acrylate), poly (ethylene vinyl acetate) or polyethylene. Other preferred affinity agents (admixtures) include oxygen blocking polymers (especially EVOH, PET, PVDC, polyethylene naphthalate (PEN), or polyamides other than MXD6) or similar polymers, and EMCM. , ECHA, EVCH, CHAA, or a block copolymer with a polymer similar to it (such as other polymers with an ethylene backbone and cycloalkenyl side chains). [0043] In the affinity agent (harmonic agent), the block of the oxygen blocking polymer or a polymer similar thereto is formed by any suitable bond such as an ester bond, a carbonate bond, an amide bond, an ether bond, a urethane bond, or a urea bond. , EMCM, ECHA, EVCH, CHAA, or similar polymers. Those bonds are made by attaching the components of the bond to the ends of two different types of blocks, or of two different types, such as the hydroxy and ester components of an ester bond, as used in polyester synthesis. It can be easily formed by forming a bond from that component that is already present at the end of the block. The latter technique uses or two types of monomers with oxygen blocking polymers or similar polymers and monomers with EMCM, ECHA, EVCH, CHAA or similar polymers. It can be used with a block of monomers. Alternatively, their binding forms monomers or blocks of polymers similar to those with reactive end groups such as EMCM, ECHA, EVCH, CHAA, or hydroxy, ester or acid end groups. It can then be formed by blending it with an oxygen blocking polymer or a similar polymer to form a block polymer in situ during the blend. [0044] More preferably, the affinity agent (harmonic agent) is a block copolymer of one of the polyamides other than EVOH, PET, PVDC, PEN, or MXD6 with one of EMCM, ECHA, EVCH or CHAA. Acrylic acid-containing affinity agents (harmonizing agents) can also be used. Preferably the affinity (adaptant) is not more than about 50% by weight and is preferably present in the blend in the range of about 1% to about 20% by weight. [0045] Alternatively, the oxygen degassing polymer is crosslinked by any suitable mechanism, eg, by reacting the oxygen degassing polymer with a chemical crosslinker, or by polymerizing the oxygen degassing polymer with itself. By forming the structure, it can be made insoluble (meaning "internal cross-linking"). The insoluble oxygen degassing polymer can then be mixed into the oxygen blocking polymer phase as a filler. [0046] If the oxygen degassing polymer is a polyamide at least partially derived from a xylene diamine-based polymer, then the polyamide is generally miscible with the oxygen blocking polymer and is typically an affinity agent. (Reconciliation agent) is not required. However, given the polyamides used, the oxygen blocking polymers used, and other obvious parameters, one of ordinary skill in the art may wish to include an affinity agent (adaptant). [0047] Other compounds oxygen degas to enhance (enhance) the function of the oxygen degassing polymer in storage, the processability into layers of packaging (packaging) goods or the use of packaging (packaging) goods. Used with polymers for use. Such enhancement (elevation) limits the rate of oxygen degassing by the oxygen degassing polymer, among other things, before putting the product in the packaging (packaging) article, the oxygen degassing polymer when desired. Initiate oxygen degassing by, limit the induction period (the period between the initiation of oxygen degassing and oxygen degassing at the desired rate), or make the layer containing the oxygen degassing polymer stronger. Including, but not limited to, making things or making them more transparent. These compounds can be added to an active oxygen blocking composition comprising a blend of the oxygen blocking polymer and the oxygen degassing polymer to enhance the function of the oxygen degassing polymer in the composition. [0048] The composition further comprises an oxidation catalyst such as a transition metal. Transition metals serve to catalyze oxygen degassing by oxygen degassing polymers, increasing the rate of degassing, and reducing the induction period. Although not bound by theory, useful transition metals include metals that can be easily interconverted between at least two oxidation states. See "Metal-Catalyzed Oxidations of Organic Compounds" by Sheldon, RA, Kochi, JK, published by Academic Press in New York in 1981. [0049] Preferably, the transition metal is in the form of a salt with a transition metal selected from the first, second or third transition series of the periodic table. Suitable metals include, but are not limited to, manganese, iron, cobalt, nickel, copper, rhodium, and ruthenium. The oxidized state of the metal at the time of introduction does not necessarily have to be in the active state. The metal is preferably iron, nickel, manganese, cobalt or copper, more preferably manganese or cobalt, and most preferably cobalt. Suitable counterions for metals include, but include, chlorine ion, acetate ion, oleate ion, stearate ion, palmitic acid ion, 2-ethylhexanoate ion, neodecanoate ion or naphthenate ion. Not limited: preferably the counterion is C₁~ C₂₀Selected from alkanoic acid ions. Preferably, the salts, transition metals, and counterions are on the US Food and Drug Administration GRAS list (generally considered safe) or substantially transfer from packaging (packaging) articles to products. It is either not shown (less than about 500 ppb in the product, preferably less than about 50 ppb). Particularly preferred salts include cobalt oleate, cobalt stearate, cobalt 2-ethylhexanoate and cobalt neodecanoate. The metal salt can also be an ionomer (also referred to as an ionomer: a general term for synthetic resins having a group that dissociates as an ion such as a carboxyl group in the side chain), in which case a polymer counterion is used. Such ionomers are well known in the industry. [0050] Typically, the amount of transition metal catalyst is in the range of 0.001 to 1% (10 to 10,000 ppm) of the composition, based solely on the metal content (excluding ligands, counterions, etc.). be able to. In packaging (packaging) articles, transition metals can be formed in the oxygen blocking layer containing the oxygen blocking composition of the present invention, or in a layer adjacent to the oxygen blocking layer. [0051] Other compounds that can be added to the composition are photoinitiators or blends of various photoinitiators. Photoinitiators are preferred if antioxidants are included in the composition to prevent premature oxidation of the oxygen degassing polymer. [0052] Suitable photoinitiators are well known to those of skill in the art. Specific examples include, among others, benzophenone, o-methoxybenzophenone, acetophenone, o-methoxy-acetophenone, acenaphtenquinone, methylethylketone, valerophenone, hexanophenone, α-phenyl-butyrophenone, p-morpholinopropiophenone, Dibenzosverone, 4-morpholinobenzophenone, benzoin, benzoin methyl ether, 4-o-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenantrene, 2- Acetophenone, 10-thioxanthenone, 3-acetylphenantene, 3-acetylindole, 9-fluorenone, 1-indanone, 1,3,5-triacetylbenzene, thioxanthene-9-one, xanthen-9-on, 7- H-benzo [de] -anthracene-7-one, benzointetrahydropyranyl ether, 4,4'-bis (dimethylamino) -benzophenone, 1'-acetophenone, 2'-acetylnaphthone, acetonaphthone and 2,3-butandione , Benzene [a] anthracene-7,12-dione, 2,2-dimethoxy-2-phenylacetophenone, α, α-diethoxyacetophenone and α, α-dibutoxyacetophenone, but not limited to them. Single oxygen-producing photosensitizers such as rose bengal, methylene blue, and tetraphenylporphyrin can also be used as photoinitiators. Polymer initiators include poly (ethylene carbon monoxide) and oligos [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]. [0053] The use of a photoinitiator is preferred as it generally provides a faster and more effective initiation of oxygen degassing by the oxygen degassing polymer. However, due to the high cost of the photoinitiator, it is preferable to use the minimum amount of photoinitiator required to initiate oxygen degassing. This minimum amount will vary depending on the photoinitiator used, the wavelength and intensity of the UV light used to initiate and other factors. Preferably the photoinitiator is on the US Food and Drug Administration GRAS list (generally considered safe) or does not show a substantial transition from packaging (packaging) articles to the product (ie less than 50 ppb in the product). It is either a thing. [0054] Photoinitiators that are particularly useful in the present invention include benzophenone derivatives containing at least two benzophenone moieties, as described in US Pat. No. 6,139,770 by Katsumoto et al. These compounds act as effective photoinitiators to initiate oxygen degassing activity in the oxygen blocking compositions of the present invention. Such benzophenone derivatives have a very low degree of extraction from the oxygen degassing composition, which reduces the amount of packaged (packaged) food, beverage or oral pharmaceutical products by the extracted photoinitiator. May lead to off-taste or off-taste. [0055] A "benzophenone moiety" is a substituted or unsubstituted benzophenone group. Suitable substituents include alkyl, aryl, alkoxy, phenoxy and alicyclic groups, or halides containing 1 to 24 carbon atoms. [0056] Benzophenone derivatives include dimers, trimers, tetramers and oligomers of benzophenones and substituted benzophenones. [0057] Benzophenone photoinitiators are represented by the following formula: A_a(B)_b(In the formula, A is sulfur; oxygen; carbonyl; -SiR ₂-(However, each R "is an individual from an alkyl group containing 1 to 12 carbon atoms, an aryl group containing 6 to 12 carbon atoms, or an alkoxy group containing 1 to 12 carbon atoms. (Selected as); -NR "'-(where R"'is an alkyl group containing 1-12 carbon atoms, an aryl group containing 6-12 carbon atoms, or hydrogen); or A bridging group selected from organic groups containing 1 to 50 carbon atoms; a is an integer from 0 to 11; B is a substituted or unsubstituted benzophenone group; and b is It is an integer from 2 to 12). [0058] [0058] The cross-linking group A can be a divalent group or a polyvalent group having 3 or more benzophenone moieties. Organic groups, if present, can be linear, branched, cyclic (including fused cyclic groups, or separate cyclic groups), or (fused or unfused polyaryl groups). It can be an Airen group. The organic group can contain one or more heteroatoms such as oxygen, nitrogen, phosphorus, silicon or sulfur, or a combination thereof. Oxygen can exist, for example, as ethers, ketones, aldehydes, esters or alcohols. [0059] Substituents of B, which are R "in the present specification, if present, are individually from alkyl, aryl, alkoxy, phenoxy, or alicyclic groups, or halides containing 1 to 24 carbon atoms. Each benzophenone moiety can have 0-9 substituents. Substituents are chosen to make the photoinitiator more compatible with the oxygen blocking composition. be able to. [0060] Examples of such benzophenone derivatives containing two or more benzophenone moieties include dibenzoylbiphenyl, substituted dibenzoylbiphenyl, benzoylated terphenyl, substituted benzoylated terphenyl, tribenzoyltriphenylbenzene, substituted. Tribenzoyl triphenylbenzene, benzoylated styrene oligomers (dibenzoylated 1,1-diphenylethane, dibenzoylated 1,3-diphenylpropane, dibenzoylated 1-phenylnaphthalene, dibenzoylated styrene dimer, dibenzoylated styrene trimeric Includes (mixtures of compounds containing 2-12 repeating styrene groups), including the form and tribenzoylated styrene trimeric, and substituted benzoylated styrene oligomers. Tribenzoyltriphenylbenzene and substituted tribenzoyltriphenylbenzene are particularly preferred. [0061] When a photoinitiator is used, its main function is to enhance and facilitate the initiation of oxygen degassing by the oxygen blocking layer containing the oxygen degassing polymer when exposed to radiation. The amount of photoinitiator can be varied. In many cases, the amount is the blend ratio or the particular oxygen degassing polymer used, the wavelength and intensity of the UV rays used, the type and amount of antioxidant used, and the photoinitiator used. It will depend on the type of agent. The amount of photoinitiator also depends on the intended use of the composition. For example, if the photoinitiator-containing component is placed under a layer that is somewhat opaque to the radiation used, more initiator will be needed. However, for most purposes, the amount of photoinitiator when used will be in the range of 0.01-10% by weight of the oxygen blocking composition. [0062] Antioxidants can be used in compositions to control the initiation of degassing. As defined herein, an antioxidant is a substance that prevents oxidative degradation or cross-linking of a polymer. Antioxidants are typically added to facilitate the processing of polymeric materials or to extend their useful service life. In the context of this invention, such additives extend the induction period for oxygen degassing in the absence of radiation. When it is desired to initiate oxygen degassing by an oxygen degassing polymer of an active oxygen blocking layer in a packaging (packaging) article, the packaging (packaging) article (and any introduced light initiator). The agent) can be exposed to the irradiation line. [0063] 2,6-di (t-butyl) -4-methylphenol (BHT), 2,2'-methylene-bis (6-t-butyl-p-cresol), triphenyl phosphite, tris- (nonylphenyl) Antioxidants such as phosphite, vitamin E, tetra-bismethylene 3- (3,5-di (t-butyl) -4-hydroxyphenyl) -propionate methane, and dilaurylthiodipropionate have the invention. Suitable for use with. [0064] The amount of antioxidant that can be present will also have an effect on oxygen degassing. As mentioned earlier, such substances are usually present in oxidizable organic compounds or structural polymers to prevent oxidation and gelation of the polymers. Typically, they are present in about 0.01-1% by weight of the composition. However, additional amounts of antioxidants can also be added if it is desired to properly align the induction periods as described above. [0065] Other additives that can be included in the reactive oxygen species blocking layer include, among other things, fillers, pigments, dyes, stabilizers, processing aids, plasticizers, flame retardants, and anti-fog agents, but Not necessarily limited to them. [0066] Any other additives commonly used do not contain more than 10% by weight by weight, preferably less than 5% by weight of the composition. [0067] After being made, the active oxygen blocking composition can be stored or made as part of the process of forming a packaging (packaging) article, as described below. [0068] In addition to the reactive oxygen species blocking layer, if the packaging (packaging) article is a multi-layer article, it can include other layers useful in a flexible or rigid multi-layer packaging (package) article. [0069] As described above, if a transition metal salt is included in a packaging (packaging) article to increase the rate of oxygen degassing or reduce the induction period, the transition metal is active oxygen. It can be included in either a blocking layer or in a layer adjacent to an active oxygen blocking layer. Any of the transition metal salts described above can be formed in adjacent layers. [0070] The active oxygen blocking layer can also include photoinitiators, antioxidants, or both as described above. Other additives can also be included as described. [0071] The multi-layer packaging (packaging) article of the present invention can also include at least one structural layer located inside, outside, or both of the active oxygen blocking layers. The structural layer (one or more layers) consists of a structural polymer that imparts useful structural properties such as hardness, flexibility or strength to the packaging (packaging) article. Suitable structural polymers are polyethylene, low density polyethylene, very low density polyethylene, ultra low density polyethylene, high density polyethylene, polyvinyl chloride, ethylene-vinyl acetate, ethylene-alkyl (meth) acrylate, ethylene- (meth). ) Acrylic acid, PET, polyamides, polypropylene or ethylene- (meth) acrylic acid ionomers, but not limited to them. Blends of different structural polymers can also be used. However, the choice of structural polymer depends largely on the article to be produced and the use of its ends. Factors of such choice are well known in the industry. [0072] Preferably, the structural polymers are PET, polyamides, polypropylene, polyethylene, low density polyethylene, very low density polyethylene, ultra low density polyethylene, high density polyethylene, polyvinyl chloride, ethylene-vinyl acetate, ethylene-alkyl ( It is selected from ( meth ) acrylate, polyethylene- (meth) acrylic acid, or polyethylene- (meth) acrylic acid ionomers. [0073] If the packaging (packaging) article is a rigid carton such as a juice carton, the structural layer can consist of paperboard or cardboard. [0074] Also, multi-layer packaging (packaging) articles, alone or in any combination, are oxygen degassed polymers and, optionally, photoinitiators, transition metal catalysts, antioxidants, structures as described above. It can include an oxygen degassing layer containing a polymer, or other additive such as. The oxygen degassing layer is an integral component of the packaging (packaging) article, or it is a liner, coating, sealant, gasket, adhesive, non-adhesive insert, or fiber in the packaging (packaging) article. It can be a matte insert. [0075] In addition, multi-layer packaging (packaging) articles according to the present invention will have at least one oxygen blocking layer (without the oxygen degassing polymer), ie, at room temperature (about 25 ° C) and 0% humidity per atmosphere. 100 cubic centimeters per square meter per day (cc / m)²) Can be further included, with oxygen permeation rates less than or equal to). Typical oxygen blocking layers are poly (ethylene / vinyl alcohol) (EVOH), polyacrylonitrile, copolymers containing acrylonitrile, poly (vinylidene dichloride), polyethylene terephthalate (PET), silica, polyamides other than MXD6, or Contains a mixture of them. However, the blend of the oxygen blocking polymer and the oxygen degassing polymer blocks the permeation of oxygen to a high degree, reducing the need for a separate oxygen blocking layer and in the form of packaging (packaging) articles. And depending on the intended use, it may not be present at all if desired. [0076] Other additional layers of the multi-layer packaging (packaging) article may include one or more layers that are permeable to oxygen. In one packaging (packaging) article preferred for flexible packaging (packaging) of foods found in packaged (packaged) foodstuffs and degassing of oxygen, multiple layers are packaged (packaged). In order from the outside of the package to the innermost layer of the packaging, it includes (i) an oxygen blocking layer, (ii) an oxygen degassing layer that is present in some cases, and (iii) an oxygen permeable layer that is present in some cases. To do. The control of the oxygen blocking property of (i) controls the rate of oxygen entry into the oxygen degassing portion of layer (ii) and thus delays the consumption of oxygen degassing capacity by the oxygen in the atmosphere. Controlling the oxygen permeability of layer (iii) affects the rate of oxygen degassing across the overall structure. In addition, layer (iii) can provide a block against the transfer of components of the outer layer or by-products of the reaction of such components with oxygen or other reactants into the packaging. .. Furthermore, layer (iii) can improve the heat sealability, clarity (transparency), and resistance to blocking of multi-layer packaging (packaging) articles. [0077] In multi-layer packaging (packaging) articles, additional layers such as an adhesive layer can also be used. Compositions typically used for adhesive layers include acid anhydride functional polyolefins and other well-known adhesive layers. [0078] If the oxygen blocking layer of the present invention contains PVDC as an oxygen blocking polymer, and especially as a major oxygen blocking polymer, then the oxygen blocking layer is as an extruded film or a co-extruded film. It can be present as molded; or as a coating. If an oxygen blocking layer containing PVDC is used as the coating, a preferred embodiment is as an external coating for packaging articles containing polypropylene (PP) or PET as the structural layer. [0079] In another aspect, the present invention is a method for producing an active oxygen blocking composition containing an oxygen blocking polymer and an oxygen degassing polymer, which comprises blending an oxygen blocking polymer and an oxygen degassing polymer. Regarding. [0080] [0080] The oxygen blocking polymer and the oxygen degassing polymer are as described above. Typically, the oxygen blocking polymer and the oxygen degassing polymer are prepared as a solid formulation, such as pellets or powders. [0081] The blend can be made by mixing the oxygen blocking polymer and the oxygen degassing polymer in any suitable device. Typically, the oxygen blocking polymer and the oxygen degassing polymer are mixed together, heated and melted, and stirred until homogeneous, and the homogeneous melt is then extruded. The extruded melt is then typically cooled and pelletized to form pellets of the blend. However, other forms of blending, such as powder, are possible. Other techniques for making blends will be apparent to those skilled in the art. [0082] To aid in the mixing of the oxygen blocking polymer with the oxygen degassing polymer, the blending step further involves blending an affinity agent (compatibilizer) with the oxygen blocking polymer and the oxygen degassing polymer. Can be included. Affinities (adaptants) are as described above. The blending can also be combined during the manufacturing process or forming process of the final packaging (packaging) article as a feed material. [0083] Alternatively, if the oxygen degassing polymer is desired as a filler in the oxygen blocking polymer phase, then firstly the oxygen degassing polymer, such as chemical cross-linking or polymerization, is internalized. The composition can be made by cross-linking the composition and, secondly, mixing the insoluble oxygen degassing polymer with an oxygen blocking polymer. [0084] Blends can also contain other components, such as transition metal oxidation catalysts, photoinitiators, antioxidants or any combination thereof, as described above. Those constituents can generally be added in the blending process. If OSPs are provided as fillers, their constituents are typically blended with the phase of the oxygen blocking polymer. The oxidation catalyst can be introduced either at the mixing stage or at the processing stage of the final article shown below, i.e. at any stage of the method. [0085] After being made, the blend can be stored for at least a few days, and preferably irregularly, or it forms an oxygen blocking layer in the packaging (packaging) article as described below. Can be built as part of the method for. In such a method, the blended composition is fed directly from an extruder or other blending device to additional steps of the method. [0086] In other embodiments, the present invention provides an oxygen blocking composition comprising (i) an oxygen blocking polymer and an oxygen degassing polymer; and (ii) the composition for packaging (packaging) articles or articles thereof. The present invention relates to a method for forming an active oxygen blocking layer in a packaging (packaging) article comprising forming the oxygen blocking layer. [0087] The packaging (packaging) article can be a flexible or rigid single layer or multi-layer, as described above. Oxygen blocking polymers and oxygen degassing polymers are also as described above. Preferably the oxygen degassing polymer can include an ethylene backbone and a cycloalkenyl group having the following structural formula I:<img file="JP4852214B2_D0004.tif" />(In the formula, q₁, Q₂, Q₃, Q₄And r are independently selected from hydrogen, methyl or ethyl; m is-(CH₂)_n-(However, n is an integer from 0 to 4); X is absent or a linking group; and if r is hydrogen, q₁, Q₂, Q₃And q₄At least one of them is also hydrogen). Preferably, in structural formula I, q₁, Q₂, Q₃, Q₄And r are hydrogen, respectively, and n is 1 (ie, the cycloalkenyl group is cyclohexenyl). [0088] One of the most preferred oxygen degassing compounds is ethylene / vinyl cyclohexene copolymer (EVCH). Preferably, X is a linking group that binds the ethylene backbone to the cyclic olefin group. Its linking group is -O- (CHR)_n-; -(C = O) -O- (CHR)_n-; -NH- (CHR)_n-; -O- (C = O)-(CHR)_n-;-(C = O) -NH- (CHR)_n-; Or-(C = O) -O-CHOH-CH₂Selected from -O-. [0089] Preferably, the oxygen degassing polymer is a homopolymer or copolymer of cyclohexenylmethyl acrylate. The most preferred oxygen degassing polymer is ethylene / methyl acrylate / cyclohexenyl methyl acrylate ternary polymer (EMCM). A more preferred oxygen degassing polymer is an ethylene / cyclohexenyl methyl acrylate copolymer (ECHA). The most preferable oxygen degassing polymer is cyclohexenylmethyl acrylate homopolymer (CHAA). [0090] In another embodiment, the oxygen degassing polymer is a polyester polymer comprising the following Structural Formula II or the following Structural Formula III:<img file="JP4852214B2_D0005.tif" />(In the formula, q₁, Q₂, Q₃, Q₄And r are independently selected from hydrogen, methyl or ethyl, preferably q₁, Q₂, Q₃, Q₄And r are hydrogen (ie, its monomer is tetrahydrophthalic anhydride): [0091]<img file="JP4852214B2_D0006.tif" />(In the formula, q₁, Q₂, Q₃, Q₄And r are independently selected from hydrogen, methyl or ethyl; m is-(CH₂)_n-(However, n is an integer from 0 to 4); and if r is hydrogen, then q₁, Q₂, Q₃And q₄At least one of them is also hydrogen). Preferably the monomer is 3-cyclohexene-1,1-dimethanol (ie, q).₁, Q₂, Q₃, Q₄And r is hydrogen, and n is 1). [0092] Yet another preferred oxygen degassing polymer is EMBZ as discussed above. In another embodiment, the oxygen degassing polymer is preferably a polyamide derived at least one part from a xylene diamine-based monomer. The packaging (packaging) article is one or more containing the compositions of the present invention. It can include an oxygen blocking layer. [0093] The forming step can be carried out by any suitable technique, depending on the oxygen blocking composition, the packaging (packaging) article and other parameters. As described above, single-layer packaging (packaging) articles can be made, among other things, by solvent injection, injection molding, blow molding, injection blow molding, or extrusion. Packaging (packaging) articles with multiple layers are typically made using, among other things, co-extrusion molding, injection molding, blow molding, injection blow molding, coating or lamination. [0094] In an embodiment in which the oxygen blocking polymer is PVDC, the oxygen blocking layer of the present invention can be formed by film extrusion, molding or coating, as a particular technique. [0095] If the transition metal catalyst is desired to be included in the packaging (packaging) article to catalyze oxygen degassing by the composition, the forming step is oxygen in the packaging (packaging) article. It includes forming in a blocking layer or a layer adjacent to an oxygen blocking layer. [0096] The active oxygen blocking composition can also include photoinitiators, antioxidants, structural polymers or other additives as described above. [0097] In addition to the active oxygen blocking layer, the packaging (packaging) article to be formed is, among other things, an oxygen blocking layer, a structural layer, an oxygen degassing layer, or a packaging (for packaging) that does not contain an oxygen degassing polymer. ) Other layers can be included, such as a sealing layer or a food contact layer that forms the inner surface of the article. Depending on the desired shape of the packaging (packaging) article, the forming process forms the packaging (packaging) article as a single-layer flexible article, a multi-layer flexible article, a single-layer rigid article or a multi-layer rigid article. Can include doing. [0098] The following examples are included to show preferred embodiments of the present invention. It is believed that the techniques disclosed in the examples presented below represent the techniques found by the present invention to perform well in the practice of the present invention and thus constitute a preferred mode for the practice of the present invention. It should be recognized by those skilled in the art that it can be done. However, in view of these disclosures, in certain aspects disclosed, many changes can be made without departing from the spirit and scope of the invention, yet with similar or similar results. Those skilled in the art should be aware that they can. [0099] (Best mode for carrying out the invention)<u style="single">Example 1</u><u style="single">Manufacture of multilayer films with an oxygen blocking core layer</u>Ethylene-vinyl alcohol copolymer (EVOH), ethylene / methyl acrylate / cyclohexenyl methyl acrylate ternary polymer (terpolymer) (EMCM), and ethylene / methyl acrylate copolymer (EMCM), by mixing in a polyethylene bag. EMAC) -based cobalt master batch (1 wt% tribenzoyltriphenylbenzene (BBP)³) And (containing 1% by weight cobalt as cobalt oleate) pellets were used to make a series of four dry blend samples. Those samples differed in weight ratio between EVOH, EMCM, and cobalt masterbatch. A fifth sample consisting of EVOH was made as a control. The proportions of the ingredients in the blend are shown in Table 1. [0100]<img file="JP4852214B2_D0007.tif" />[0101] The EVOH used (Soarnol A4412 class manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) has an ethylene content of 44 mol%, and at 210 ° C, a melt index of 12 g / min and a loading of 2.64 kg. , And had a melting point of 164 ° C. The EVOH resin was dried under vacuum at 90 ° C for 3 hours to remove residual moisture. [0102] The EMCM, oxygen degassing polymer used was as described in the previous section and was obtained from Chevron Chemical Co. (1% by weight BBP³And an EMAC-based cobalt masterbatch (containing 1% by weight cobalt as cobalt oleate) was obtained from Chevron Chemical Co. [0103] The above four dry blends and controls (Samples 1-5) were melt-blended on a Hakke twin screw extruder at a screw speed of 30 rpm at temperatures in the range 190 ° C-220 ° C. A three-layer film was formed from each composition from a Randcastle co-extruder, with an oxygen blocking blend composition or control as the core layer and commercially available polyethylene as the inner and outer skin layers. The dimensions of the three-layer film were controlled at 0.5 mil / 1.0 mil / 0.5 mil. The temperature settings for film forming were in the range of 430 ° F, and the screw speeds were in the range of 15 rpm to 30 rpm. Individual layers of material for each were supplied to one of the two extruders of the Randcastle machine. On the one hand, in the die mold, the layers were juxtaposed and combined and then removed from the die mold as a three-layer film. After leaving the die, the film was uniaxially oriented: the extruded material was formed on a first control temperature forming roll while stretching in the mechanical direction, and then the film was collected on a second roll. .. All the films produced were bright in color and transparent. [0104]<u style="single">Example 2</u><u style="single">Oxygen permeation test on Mocon</u>The film made in Example 1 at 23 ° C, Mocon Ox-Trans Oxygen permeation was tested using a 2 / 20ML system. Prior to the test, nitrogen containing 2% hydrogen was used as the carrier gas to flush both sides of the film at a flow rate of 10 cc / min for 1-4 hours. Air was used as the test gas at a flow rate of 10 cc / min. Oxygen permeability was measured in centimeters per square meter per 24 hours. The size of the film for the test is 50 cm²Met. Oxygen degassing by EMCM in the oxygen barrier layer was induced by exposing the film to UV light at 254 nm. [0105]<img file="JP4852214B2_D0008.tif" />[0106] From the table above, the presence of the oxygen degassing polymer EMCM in the EVOH matrix (ie, having active oxygen blocking) includes an oxygen blocking polymer free of oxygen degassing polymers, as is known in the art. It is clear that the oxygen permeability of the film can be significantly reduced as compared to the film. With 9% by weight charge of EMCM (Sample 3), oxygen permeability was reduced by about 7-fold in the presence of sufficient cobalt masterbatch. With 18% by weight of EMCM charged, oxygen permeability was reduced to virtually zero. [0107]<u style="single">Example 3</u><u style="single">Manufacture of multilayer films with an oxygen blocking core layer</u>By mixing in a polyethylene bag, ethylene-vinyl alcohol copolymer (EVOH; Evalca Co. commercially available, containing 68 mol% vinyl alcohol, Eval F101A), MXD6 nylon (Mitsubishi Gas Chemical Co., Ltd. commercially available MX nylon) A series of three dry blend samples were made from pellets of 6007) and ethylene / methyl acrylate copolymer (EMCA) based cobalt masterbatch (containing 1 wt% cobalt as cobalt oleate). Those samples differed in weight ratio between EVOH, MXD6 and cobalt-catalyzed masterbatch. The proportions of the ingredients in the blend, as well as the composition of the core layer of the three-layer film, are shown in Table 3. [0108]<img file="JP4852214B2_D0009.tif" />[0109] The two formulations (Samples 2 and 3) were melt-blended on a Haake twin screw extruder at a screw speed of 20 rpm and a temperature of 260 ° C. Using each of the above formulations (Samples 1-3) as the core layer and polyethylene resin (Chevron PE4517) as the skin layer, the three-layer film sample was then molded on a Randcastle co-extruder. The structure of the layer was PE / sample / PE (1.0 / 1.0 / 1.0 mil). On the Randcastle aircraft, the temperature settings were 460 ° F, 510 ° F and 520 ° F for bands 1-3, respectively. The screw speed was set to 40 rpm. The temperature was set to 510 ° F for the feed block and 500 ° F for the die die. After leaving the die, the film was uniaxially oriented: the extruded material was formed on a first controlled temperature forming roll while stretching in the mechanical direction, then the film was collected on a second roll. It was. All films were transparent and showed sufficient affinity (compatibility) for the blend. [0110]<u style="single">Example 4</u><u style="single">Oxygen permeation test on Mocon Oxtran</u>The films made in Example 3 were tested for oxygen permeability using the Mocon Ox-Trans 2/20 system at 23 ° C under dry conditions. Prior to the test, nitrogen containing 2% hydrogen was used as the carrier gas to flush both sides of the film at a flow rate of 10 cc / min for 1-4 hours. Air was used as the test gas at a flow rate of 10 cc / min. Oxygen permeability was measured in cubic centimeters per square meter per 24 hours. The size of the film for the test is 50 cm²Met. [0111]<img file="JP4852214B2_D0010.tif" />[0112] From the table above, the presence of the oxygen degassing polymer MXD6, along with a small amount of cobalt catalyst in the EVOH matrix, includes an oxygen blocking layer without the oxygen degassing polymer, as is known in the art. It is clear that the oxygen permeability of the film can be significantly reduced as compared to the film. With a 5 wt% charge of MXD6 (Sample 3), oxygen permeability was reduced below the detection limit in the presence of a very small amount of cobalt masterbatch. [0113] All of the compositions and methods disclosed and claimed herein can be carried out and practiced in view of this disclosure without undue experimentation. Although the compositions and methods of the present invention have been described with respect to preferred embodiments, without departing from the concepts, spirits and scope of the invention, in the compositions and methods described herein and in the steps of the method. Alternatively, it will be apparent to those skilled in the art that various changes can be applied in the sequence of steps. More specifically, certain agents (chemical agents) that are both chemically and physiologically relevant can be used in place of the agents (chemical agents) described herein. Moreover, on the other hand, it will be clear that the same or similar results will be achieved. All such similar replacements and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the claims.