JP3903997B2 - Packaging container - Google Patents

Description

  The present invention relates to a packaging container having functionality such as gas barrier properties and oxygen absorption properties. More specifically, the present invention relates to a packaging container that exhibits a function excellent in gas barrier property, oxygen absorption property, and the like from the initial stage when the container is filled with contents.

Polyester resins typified by polyethylene terephthalate have excellent properties such as moldability, transparency, mechanical strength, chemical resistance, and relatively high gas barrier properties such as oxygen. It is used in various fields as packaging materials for bottles and the like.
On the other hand, oxygen scavengers have also been used for a long time. As an example of applying them to container walls, oxygen scrubbing resins are blended with oxygen scavengers mainly composed of reducing substances such as iron powder. A multilayer structure for packaging in which a layer and a layer having an oxygen gas barrier property are laminated is known (see Patent Document 1).
In order to improve the gas barrier property of the packaging material as described above, a packaging material having a functional resin layer having gas barrier properties such as saponified ethylene-vinyl acetate copolymer and polyamide as an intermediate layer between the inner and outer layers Is also known (see Patent Document 2).

A gas barrier having an oxygen permeability coefficient of 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less at 20 ° C. and 0% RH and a water adsorption amount of 0.5% or more at 20 ° C. and 100% RH. A multilayer plastic container comprising a laminated structure in which a resin composition in which an organometallic complex of a transition metal is blended with a heat-resistant thermoplastic resin is used as an intermediate layer, and layers of moisture-resistant thermoplastic resin are provided on both sides of the intermediate layer is known. (See Patent Document 3).
Further, in a packaging barrier comprising a composition comprising a polymer and having oxygen scavenging properties or a layer of the composition, the composition collects oxygen by metal-catalyzed oxidation of an oxidizable organic component. A barrier for packaging has been proposed, and it is also known that polyamides, particularly xylylene group-containing polyamides can be used as oxidizable organic components (see Patent Document 4).
Furthermore, an oxygen-absorbing resin composition containing a polyamide resin, an oxidizing organic component and a transition metal catalyst, a packaging material obtained by molding the resin composition, and a packaging multilayer container are also known ( (See Patent Document 5).

Japanese Examined Patent Publication No. 62-1824 JP-A-63-203540 JP-A-1-278344 Japanese National Patent Publication No. 2-500846 JP 2002-241608 A

However, normally, when a container is filled with an aqueous solution (oxygen-free water) in which oxygen is not dissolved, the oxygen-free water absorbs oxygen gas contained in the air and the resin remaining in the space of the container and in the aqueous solution. The oxygen concentration of the water gradually increases.
In addition, filling oxygen-free water in a multilayer container with a gas barrier layer made of polyamide resin or the like as an intermediate layer has the effect of reducing the amount of gas permeated from the outside to the inside of the container, but oxygen-free water is not contained in the container. Oxygen gas contained in the air and the innermost layer resin is absorbed, and the oxygen concentration in the oxygen-free water gradually increases.

On the other hand, in the case of a multi-layer container having an intermediate layer in which a transition metal is blended in a gas barrier resin layer made of polyamide resin or the like to provide an oxygen absorption function, the filled oxygen-free water is still in the container for several days. Oxygen remaining in the inner layer resin may be absorbed and the oxygen concentration in the water in the multilayer container may continue to increase. This is because even if a transition metal or the like that promotes oxygen absorption is added to the gas barrier resin layer, the gas barrier resin shields diffusion of oxygen gas remaining in the container and the innermost resin into the oxygen absorbing layer. It seems to act to do.
As shown in FIG. 2, this is because the resin constituting the intermediate layer (two intermediate layers located between the inner and outer layers and the central layer) of the five-layer container (inner volume of 327 ml) is a gas barrier resin, an oxidizing organic material. Oxygen-absorbing functional resin composition comprising a component and a transition metal-based catalyst (polymetaxylylene adipamide: 94.75% by weight, polyene-based oxidizable organic component: 5% by weight, and transition metal-based catalyst: 350 ppm) Is increased from 1.5 wt% to 3 wt% with respect to the container weight, the dissolved oxygen concentration after 3 days and the dissolved oxygen concentration after 14 days (both 22 ° C., 60 RH) It is also clear from the fact that both of them are almost the same as about 400 ppm and do not decrease.
Further, as a middle layer of a multilayer container, even if a resin having a gas barrier property that forms an island part and an oxygen absorbing function resin that has an oxygen absorptivity is mixed in a base resin that forms a sea part, the multilayer container If the ratio of the surface area of the island portion to the inner volume of the water is below a certain value, the initial dissolved oxygen concentration of the oxygen-free water in the container will not increase and decrease.

The present inventors provide a resin composition having an oxygen absorption function for forming a discontinuous phase of an island part in a base resin that forms a continuous phase of a sea part as an intermediate layer of a packaging container, particularly a multilayer container. When forming the sea-island structure by blending, the dissolved oxygen concentration in the oxygen-free water filled in the container is reduced from the initial filling stage by making the total surface area of the island part a certain ratio or more with respect to the inner volume of the multilayer container. The inventors found that the concentration can be maintained, and completed the present invention.
That is, an object of the present invention is to provide a packaging container that is excellent in gas barrier properties and oxygen absorption properties from the beginning of filling into the container.
Another object of the present invention is to provide a packaging container capable of continuously reducing the initial oxygen concentration of the contents from the beginning of filling the container.

According to the present invention, an oxygen-absorbing layer comprising a base resin component (component A) comprising a thermoplastic polyester resin and an oxygen-absorbing functional component (component B) comprising a gas barrier resin, an oxidizing organic component and a transition metal catalyst. A base container resin component (component A) in which the oxygen absorption layer forms a continuous phase of the sea portion and an oxygen absorption functional component (component B) that forms a discontinuous phase of the island portion. The ratio (N / M) of the total surface area (Ncm ² ) of the island portion composed of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer to the inner volume (Mcm ³ ) of the packaging container is 20 ( A packaging container characterized by being equal to or more than cm ⁻¹ ) is provided.

In the present invention,
(1) The average particle size of the oxygen-absorbing functional component (component B) that forms the island portion in the oxygen-absorbing layer is 3.0 μm or less,
(2) The thermoplastic polyester resin is polyethylene terephthalate,
(3) The gas barrier resin is a polyamide resin obtained by polycondensation reaction of a diamine component mainly composed of xylylenediamine having a terminal amino group concentration of 40 eq / 10 ⁶ g or more and a dicarboxylic acid component ,
(4) the oxidizable organic component comprises a polymer derived from polyene ,
(5) The polymer derived from polyene is an acid-modified polyene polymer ,
(6) The oxygen-absorbing functional component (component B) contains an oxidizing organic component in a proportion of 0.01 to 10% by weight ,
(7) The oxygen-absorbing functional component (component B) contains a transition metal catalyst as a transition metal atom in a proportion of 100 to 3000 ppm ,
(8) The transition metal catalyst is a cobalt salt of carboxylic acid ,
(9) a multilayer structure in which another layer is laminated on the oxygen absorbing layer ;
(10) The oxygen-absorbing functional component (component B) is contained in a proportion of 10 to 60% by weight in the oxygen-absorbing layer in the packaging container having a multilayer structure ,
Is desirable.

  The packaging container of the present invention is excellent in gas barrier property and oxygen absorption from the beginning when the contents are filled into the container, and keeps the initial oxygen concentration of the contents low from the beginning when the contents are filled into the packaging container. Is possible.

The packaging container of the present invention is a packaging container having an oxygen absorbing layer composed of a base resin component (component A) and an oxygen absorbing functional component (component B), and the oxygen absorbing layer forms a continuous phase of the sea portion. A base resin component (component A) and an oxygen-absorbing functional component (component B) that forms a discontinuous phase of the island portion, and the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer. The ratio (N / M) of the total surface area (Ncm ² ) of the island portion to the inner volume (Mcm ³ ) of the packaging container is 20 (cm ⁻¹ ) or more, and the container was filled with the contents. The gas barrier property and oxygen absorption property are excellent from the beginning, and the initial oxygen concentration of the contents can be kept low from the beginning of filling.

On the other hand, even in a packaging container having an oxygen absorption layer having the above-mentioned sea-island structure, the total surface area (Ncm ² ) of the island portion composed of the oxygen-absorbing functional component (component B) in the oxygen absorption layer and the packaging container When the ratio (N / M) of the internal volume (Mcm ³ ) is less than 20 (cm ⁻¹ ), the oxygen absorption function is not sufficiently exhibited from the beginning of filling the container, and the oxygen concentration from the beginning of filling the contents into the container. Is difficult to keep low.

1. Method for measuring the total surface area of the island portion composed of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer In the case of an extruded film or sheet (unstretched), the total surface area can be determined from the result of an enlarged observation of the cross section. . In addition, in the case of a bottle or sheet that has been preformed by biaxial stretch blow molding, or a cup that has been vacuum- or air-pressure molded (stretching process), the sea-island structure is fundamentally formed during the primary molding of the preform or sheet, and the bottleneck ring The total surface area of the island part can be obtained from the observation result of the enlarged cross section of the unextended part such as the lower part or the vicinity of the cup flange.
That is, when the final form is the above-described bottle or cup, the main part, particularly the side wall part is thinned by stretching or the like, and the cross-sectional enlarged observation is difficult. Therefore, in the present invention, the sea island (oxygen absorption layer) The weight of the island portion does not change before and after stretching, and the relationship of the total surface area of the island portion in the stretching process at the same magnification does not change. The total surface area of the island when the container was used.
For cross-sectional observation, each part mentioned above was cut out and the cut surface was carefully surfaced with an ultramicrotome, followed by platinum deposition and a photograph of the sea-island structure portion at a magnification of 3000 with an electron microscope (SEM). Take a picture.
Next, the shortest diameter and the longest diameter of the island part are measured, and the average is taken as the particle diameter of the island part. Similarly, all the particle diameters of the island part in the photograph are obtained, and the total of the particle diameters is the number of particles. The average particle diameter was r (cm).
The total surface area of the island portion is N (cm ² ), the container weight is X (g), the oxygen absorbing layer in the container is Y (wt%), and the proportion of the oxygen absorbing functional component B in the oxygen absorbing layer is Z ( %) And the specific gravity of the component B is d (g / cm ³ ), the weight of one island is 4πr ³ d / 3, and the weight of the component B in the oxygen absorption layer is (XY / 100) · ( Z / 100), the total surface area N (cm ² ) of the island portion is N = (XYZ / 10000) / (4πr ³ d / 3) · (4πr ² ) = 3XYZ / 10000 / r / d.

2. Molding conditions for the oxygen absorption layer in the container to have a sea-island structure The total surface area (Ncm ² ) of the island portion comprising the oxygen-absorbing functional component (component B) in the oxygen absorption layer in the present invention and the inner volume (Mcm) of the packaging container ³ ) The molding conditions necessary to obtain a sea-island structure with a ratio (N / M) of 20 (cm ⁻¹ ) or more include resin blending ratio, resin melt viscosity, viscosity ratio, shear condition of the melted resin, and the like. can give.
Of these, the resin blend ratio and the resin melt viscosity ratio are particularly important.
Therefore, in order to achieve the target sea-island structure, it is necessary to consider the balance between melt viscosity and composition. In order to reduce the average particle size of the island part and increase the total surface area of the island part, a) lowering the melt viscosity of the oxygen-absorbing functional component (component B) constituting the island portion than the base resin component (component A) constituting the sea portion; and (b) the oxygen-absorbing functional component in the oxygen-absorbing layer. It is desirable that (Component B) is 10 to 60% by weight and the base resin component (Component A) is 40 to 90% by weight.

The ratio (N / M) of the total surface area (Ncm ² ) of the island portion composed of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer to the inner volume (Mcm ³ ) of the packaging container is 20 (cm ^{− 1} ) or more, preferably 25 (cm ⁻¹ ) or more, particularly preferably 28 (cm ⁻¹ ) or more, so that the contents can be gas barrier and oxygen absorbing from the beginning of filling the packaging container of the present invention. It is excellent and it becomes possible to reduce the initial oxygen concentration of the contents continuously from the beginning of filling the container.
In addition, the average particle diameter of the oxygen-absorbing functional component (component B) constituting the island portion of the oxygen absorbing layer in the unstretched and unstretched portion described above is preferably 3.0 μm or less. By setting the average particle size to 3.0 μm or less, mechanical strength, transparency, and oxygen absorption performance due to an increase in surface area are improved.

3. Base resin component (component A)
The base resin component (component A) used in the present invention forms the sea portion, and specific examples include thermoplastic polyester resin, polycarbonate resin, polyacrylonitrile resin, polyolefin resin, polyvinyl chloride resin, Of these, a thermoplastic polyester resin is preferred. Among thermoplastic polyester resins, polyethylene terephthalate, a copolymer using isophthalic acid as a part of terephthalic acid in polyethylene terephthalate, and polyethylene naphthalate are particularly preferable.
In addition, when a multilayer container formed of at least an inner and outer layer and an intermediate layer is used as a packaging container, an oxygen absorbing layer composed of a base resin component (component A) and an oxygen absorbing functional component (component B) is used as the intermediate layer. For the base resin component (component A), those having adhesiveness to the resin constituting the layer in contact with the intermediate layer can be used.

  That is, grafting with what is conventionally used as an adhesive resin for forming an adhesive layer, for example, carboxylic acids such as maleic acid, itaconic acid and fumaric acid, or anhydrides, amides and esters of these carboxylic acids A modified graft-modified olefin resin or the like can be used as a base resin component (component A). In such a graft-modified olefin resin, the olefin resin to be graft-modified is preferably polyethylene, polypropylene, ethylene-α-olefin copolymer or the like. In addition to such graft-modified olefin resin, for example, ethylene-acrylic acid copolymer, ion-crosslinked olefin copolymer, ethylene-vinyl acetate copolymer, copolymerized polyester, copolymerized polyamide, etc. It can be used as a resin. In these adhesive resins, from the viewpoint of adhesiveness, the amount of carbonyl group (> C = O) in the main chain or side chain is 1 to 100 milliquivalent (meq) / 100 g resin, particularly 10 to 100 meq / 100 g resin. It is preferable to contain.

4). Oxygen-absorbing functional component (B)
The oxygen-absorbing functional component (component B) used in the present invention includes (i) a component comprising a gas barrier resin, an oxidizing organic component and a transition metal catalyst, or (ii) from an oxidizing organic component and a transition metal catalyst. More preferably, the component (i) is composed of the gas barrier resin, the oxidizing organic component, and the transition metal catalyst.
In the present specification, the oxygen-absorbing functional component (component B) is a term used to indicate that it is different from the resin component related to the base resin component (component A).

(I) When a component comprising a gas barrier resin, an oxidizing organic component and a transition metal catalyst is used as the oxygen-absorbing functional component (component B) From the gas barrier resin, oxidizing organic component and transition metal catalyst of the present invention The oxygen-absorbing functional component (component B) formed forms an island portion in the oxygen-absorbing layer.
The content ratio of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer is preferably 10 to 60% by weight, more preferably 10 to 40% by weight when the packaging container is a multilayer structure. Moreover, when making a packaging container into a single layer structure, Preferably it is 0.5 to 3 weight%, More preferably, it is 0.5 to 2 weight%.
By setting the content ratio of the oxygen-absorbing functional component (component B) in the above range, both the oxygen-absorbing function and the gas-barrier function can be effectively exhibited from the initial stage when the contents are filled in the packaging container.
(I-1) Gas barrier resin The gas barrier resin referred to here has gas shielding properties against various gases, and is an ethylene-vinyl alcohol copolymer or polyamide resin generally used in the field of packaging materials. However, other known gas barrier resins can be used.

Examples of the ethylene-vinyl alcohol copolymer include an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, particularly 25 to 50 mol%, and a saponification degree of 96% or more, particularly 99 mol%. A copolymer saponified product obtained by saponification as described above is preferred. The ethylene-vinyl alcohol copolymer (saponified ethylene-vinyl acetate copolymer) should have a molecular weight sufficient to form a film, and generally has a [phenol / water] weight ratio of 85/15. It is desirable to have an intrinsic viscosity of 0.01 dl / g or more, particularly 0.05 dl / g or more, measured at 30 ° C. in a mixed solvent.
Examples of the gas barrier resin other than the ethylene-vinyl alcohol copolymer include the following polyamide resins.

Polyamide resins include (a) aliphatic, alicyclic or semi-aromatic polyamides derived from dicarboxylic acid components and diamine components, (b) polyamides derived from aminocarboxylic acids or lactams thereof, or (c) These copolyamides or blends thereof may be mentioned.
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids having 4 to 15 carbon atoms such as succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. Examples include acids.

Moreover, as a diamine component, C4-C25, especially 6-18 linear, such as 1, 6- diaminohexane, 1, 8- diamino octane, 1, 10- diamino decane, 1, 12- diamino dodecane, etc. Or branched alkylene diamine, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, especially bis (4-aminocyclohexyl) methane, Examples include alicyclic diamines such as 1,3-bis (aminocyclohexyl) methane and 1,3-bis (aminomethyl) cyclohexane, and araliphatic diamines such as m-xylylenediamine and / or p-xylylenediamine. .
As the aminocarboxylic acid component, aliphatic aminocarboxylic acids such as α, β, ω-aminocaproic acid, ω-aminooctanoic acid, ω-aminoundecanoic acid, ω-aminododecanoic acid and, for example, para-aminomethylbenzoic acid, para -An araliphatic aminocarboxylic acid such as aminophenylacetic acid.

For the purpose of the present invention, among these polyamide resins, a xylylene group-containing polyamide is preferable, and specifically, polymetaxylylene adipamide, polymetaxylylene sebacamide, polymetaxylylene veramide, polyparaxylylene. Homopolymers such as lenpimelamide, polymetaxylylene azelamide, and metaxylylene / paraxylylene adipamide copolymer, metaxylylene / paraxylylene pimeramide copolymer, metaxylylene / paraxylylene sebacamide co Polymers, copolymers such as metaxylylene / paraxylylene azelamide copolymers, or homopolymers or copolymer components thereof, aliphatic diamines such as hexamethylene diamine, alicyclic diamines such as piperazine, para -Aromatic diamines such as bis (2aminoethyl) benzene, terephthal A copolymer obtained by copolymerizing an aromatic dicarboxylic acid such as an acid, a lactam such as ε-caprolactam, an ω-aminocarboxylic acid such as 7-aminoheptanoic acid, an aromatic aminocarboxylic acid such as para-aminomethylbenzoic acid, etc. Examples thereof include polyamides obtained from a diamine component mainly composed of m-xylylenediamine and / or p-xylylenediamine and an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid. .
These xylylene group-containing polyamides are excellent in oxygen barrier properties as compared with other polyamide resins, and are preferable for the purpose of the present invention.

These polyamides should also have a molecular weight sufficient to form a film. For example, in concentrated sulfuric acid (concentration 1.0 g / dl), the relative viscosity measured at 30 ° C. is 1.1 or more, particularly 1.5 or more. It is desirable to be.
When polymetaxylylene adipamide is used, a polyamide resin obtained by polycondensation reaction between a diamine component mainly composed of xylylenediamine having a terminal amino group concentration of 40 eq / 10 ⁶ g or more and a dicarboxylic acid component However, it is desirable because there is no oxidative deterioration during oxygen absorption.

(I-2) Oxidizing organic component As the oxidizing organic component, an ethylenically unsaturated group-containing polymer can be exemplified. This polymer has a carbon-carbon double bond, and this methylene bond adjacent to the double bond portion and particularly the double bond portion is easily oxidized by oxygen, whereby oxygen is trapped.
Such an ethylenically unsaturated group-containing polymer is derived, for example, using polyene as a monomer. Suitable examples of polyenes include, but are not limited to, conjugated dienes such as butadiene and isoprene; 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4- Chain non-conjugated dienes such as hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2 -Cyclic non-conjugated such as norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, dicyclopentadiene Diene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene- - norbornene, 2-propenyl-2,2-norbornadiene, etc. triene, chloroprene, and the like.

  That is, a homopolymer of the polyene, or a random copolymer, a block copolymer, or the like obtained by combining two or more of the polyenes with other monomers can be used as the oxidizing polymer. Examples of other monomers copolymerized with the polyene include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-hexene, Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicosene, Examples thereof include 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Besides these, styrene, vinyltriene, acrylonitrile, methacrylonitrile, acetic acid Vinyl, methyl methacrylate, ethyl acrylate and the like can also be used.

  In the present invention, among the polymers derived from the polyene described above, polybutadiene (BR), polyisoprene (IR), natural rubber, nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber, Ethylene-propylene-diene rubber (EPDM) and the like are suitable, but of course not limited thereto.

In addition to the above-mentioned ethylenically unsaturated group-containing polymer, a polymer that is easily oxidized, such as polypropylene and an ethylene / propylene copolymer, can also be used as the oxidizing organic component.
In the present invention, from the viewpoint of moldability and the like, it is preferable that the above-mentioned oxidizing polymer or copolymer thereof has a viscosity at 40 ° C. in the range of 1 to 200 Pa · s.

  These polyene polymers are preferably acid-modified polyene polymers into which a carboxylic acid group, a carboxylic anhydride group, or a hydroxyl group has been introduced. Examples of the monomer used for introducing these functional groups include ethylenically unsaturated monomers having a functional group.

  As the ethylenically unsaturated monomer having a functional group, it is desirable to use an unsaturated carboxylic acid or a derivative thereof. Specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citracone Α, β-unsaturated carboxylic acids (such as acid and tetrahydrophthalic acid), unsaturated carboxylic acids such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid, maleic anhydride, and itaconic anhydride Α, β-unsaturated carboxylic anhydrides such as acid, citraconic anhydride, tetrahydrophthalic anhydride, and unsaturated carboxylic acids such as bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Examples include acid anhydrides.

  The acid modification of a polyene polymer is produced by using a resin having a carbon-carbon double bond as a base polymer, and graft-copolymerizing an unsaturated carboxylic acid or a derivative thereof to the base polymer by a method known per se. However, it can also be produced by random copolymerization of the aforementioned polyene with an unsaturated carboxylic acid or derivative thereof.

The acid-modified polyene polymer particularly suitable for the purpose of the present invention preferably contains an unsaturated carboxylic acid or a derivative thereof in an amount of 0.01 to 10 mol%.
When the content of the unsaturated carboxylic acid or its derivative is within the above range, the acid-modified polyene polymer is favorably dispersed in the polyamide resin and oxygen is smoothly absorbed. Further, a hydroxyl group-modified polyene polymer having a hydroxyl group at the terminal can also be used favorably.

In addition, as the oxidizing organic component, polymetaxylylene diadipamide having a terminal amino group concentration of less than 40 eq / 10 ⁶ g may be used.

In the present invention, the viscosity at 40 ° C. of the above-described oxidizing polymer or copolymer thereof is preferably in the range of 1 to 200 Pa · s from the viewpoint of moldability and the like.
Further, the oxidizing organic component comprising these oxidizing polymers or copolymers thereof is contained in the oxygen-absorbing functional component (component B) in a proportion of 0.01 to 10% by weight, particularly 1 to 8% by weight. It is preferable to blend so that the ratio is%.

(I-3) Transition metal-based catalyst As the transition metal-based catalyst, Group VIII metals of the periodic table such as iron, cobalt, nickel and the like are suitable, but also Group I metals such as copper and silver, tin, It may be a Group IV metal such as titanium or zirconium, a Group V metal such as vanadium, a Group VI metal such as chromium, or a Group VII metal such as manganese. Of these, cobalt is particularly suitable for the purpose of the present invention because it significantly promotes oxygen absorption (oxidation of the oxidizing organic component).

The transition metal catalyst is generally used in the form of a low-valent inorganic salt, organic salt or complex salt of the transition metal. Examples of inorganic salts include halides such as chlorides, sulfur oxysalts such as sulfates, nitrogen oxysalts such as nitrates, phosphorus oxysalts such as phosphates, and silicates.
Examples of organic salts include carboxylates, sulfonates, phosphonates, and the like, and carboxylates are preferred for the purposes of the present invention. Specific examples thereof include acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid, 2-ethylhexanoic acid, nonanoic acid, 3, 5, 5 -Trimethylhexanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, Linderic acid, tuzuic acid, petroceric acid, oleic acid, linoleic acid, linolenic acid And transition metal salts such as arachidonic acid, formic acid, oxalic acid, sulfamic acid, and naphthenic acid.

  Examples of the transition metal complex include complexes with β-diketone or β-keto acid ester. Examples of β-diketone and β-keto acid ester include acetylacetone, ethyl acetoacetate, 1,3-cyclohexadione, methylenebis-1,3-cyclohexadione, 2-benzyl-1,3-cyclohexadione, Acetyltetralone, palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone, 2-benzoylcyclohexanone, 2-acetyl-1,3-cyclohexadione, benzoyl-p-chlorobenzoylmethane, bis (4- Methylbenzoyl) methane, bis (2-hydroxybenzoyl) methane, benzoylacetone, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, di Benzoylmethane, bis (4-chlorobenzoyl) methane, benzoylacetylphenylmethane, stearoyl (4-methoxybenzoyl) methane, butanoylacetone, distearoylmethane, stearoylacetone, bis (cyclohexanoyl) methane and dipivaloylmethane Etc. can be used.

  In the present invention, the transition metal catalyst in the oxygen-absorbing functional component (component B) has a transition metal atom concentration (based on weight concentration, the same shall apply hereinafter) in the range of 100 to 3000 ppm, specifically Is preferably blended to a concentration of 100 to 2000 ppm for cobalt, 150 to 1500 ppm for iron, and 200 to 2000 ppm for manganese.

(Ii) In the case of using a component comprising an oxidizing organic component and a transition metal catalyst as the oxygen-absorbing functional component (component B), an oxygen-absorbing functional component (component B) comprising the oxidizing organic component and the transition metal catalyst of the present invention Forms islands in the oxygen absorbing layer.
The content ratio of the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer is preferably 10 to 60% by weight, more preferably 20 to 60% by weight when the packaging container is a multilayer structure. Moreover, when making a packaging container into a single layer structure, Preferably it is 0.5 to 3 weight%, More preferably, it is 1 to 3 weight%.
By setting the content ratio of the oxygen-absorbing functional component (component B) in the above range, both the oxygen-absorbing function and the gas-barrier function can be effectively exhibited from the initial stage when the contents are filled in the multilayer container.
(Ii-1) Oxidizing organic component Since polymetaxylylene diadipamide having a terminal amino group concentration of less than 40 eq / 10 ⁶ g functions as an oxygen-absorbing resin in the presence of a transition metal catalyst, an oxidizing organic component is used. It can be used as a component.
(Ii-2) Transition metal catalyst The type and blending ratio of the transition metal catalyst used are the same as described above.

5). Forming method of packaging container (i) Various means for blending gas barrier resin with oxidizing organic component and transition metal catalyst, or (ii) blending transition metal catalyst with oxidizing organic component There is no particular order for this formulation, and blending may be performed in any order.
For example, a blend of both can be easily prepared by dry blending or melt blending an oxidizing organic component to a gas barrier resin.
On the other hand, since the transition metal catalyst is a small amount as compared with the gas barrier resin and the oxidizing organic component, in order to perform the blending homogeneously, the transition metal catalyst is generally dissolved in an organic solvent, and this solution and the powder or granular form are dissolved. The gas barrier resin and the oxidizing organic component are mixed, and if necessary, the mixture is dried under an inert atmosphere.

  Solvents for dissolving the transition metal catalyst include alcohol solvents such as methanol, ethanol and butanol, ether solvents such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran and dioxane, ketone solvents such as methyl ethyl ketone and cyclohexanone, n -Hydrocarbon solvents such as hexane and cyclohexane can be used, and it is generally preferable that the transition metal catalyst is used at a concentration of 5 to 90% by weight.

Mixing (i) gas barrier resin, oxidizing organic component and transition metal-based catalyst, or (ii) oxygen-absorbing functional component (component B) consisting of oxidizing organic component and transition metal-based catalyst, and subsequent storage In order to prevent oxidation in the previous stage, it is preferable to perform in a non-oxidizing atmosphere. For this purpose, mixing or drying under reduced pressure or in a nitrogen stream is preferred.
This mixing and drying can be performed at a stage prior to the molding process using an extruder or an injection machine with a vent type or a dryer.
In addition, a gas barrier resin containing a transition metal catalyst at a relatively high concentration and / or a masterbatch of an oxidizing organic component is prepared, and this masterbatch is dry blended with an unblended gas barrier resin. The oxygen-absorbing functional component (component B) of the invention can also be prepared.

In general, the oxygen-absorbing functional component (component B) of the present invention is not necessary, but an activator known per se can be blended if desired. Suitable examples of activators include, but are not limited to, polymers containing hydroxyl and / or carboxyl groups such as polyethylene glycol, polypropylene glycol, ethylene vinyl alcohol copolymers, ethylene / methacrylic acid copolymers, and various ionomers. is there.
These hydroxyl group and / or carboxyl group-containing polymers can be blended in an amount of 30 parts by weight or less, particularly 0.01 to 10 parts by weight, based on 100 parts by weight of the gas barrier resin.
The oxygen-absorbing functional component (component B) used in the present invention includes a filler, a colorant, a heat stabilizer, a weather stabilizer, an antioxidant, an antioxidant, a light stabilizer, an ultraviolet absorber, and an antistatic agent. A known resin compounding agent such as a lubricant, a lubricant such as metal soap or wax, a modifying resin or rubber, and the like can be blended according to a formulation known per se.

For example, by incorporating a lubricant, the bite of the resin into the screw is improved. Lubricants include metal soaps such as magnesium stearate and calcium stearate, hydrocarbons such as fluid, natural or synthetic paraffin, micro wax, polyethylene wax and chlorinated polyethylene wax, and fatty acid systems such as stearic acid and lauric acid. Fatty acid monoamides or bisamides such as stearic acid amide, valmitic acid amide, oleic acid amide, esylic acid amide, methylene bisstearamide, ethylene bisstearamide, butyl stearate, hydrogenated castor oil, ethylene An ester type such as glycol monostearate, an alcohol type such as cetyl alcohol and stearyl alcohol, and a mixed system thereof are generally used.
The amount of lubricant added is (i) in the case of an oxygen-absorbing functional component (component B) composed of a gas barrier resin, an oxidizing organic component and a transition metal catalyst, or (ii) an oxidizing property. In the case of an oxygen-absorbing functional component (component B) comprising an organic component and a transition metal catalyst, a range of 50 to 1000 ppm is appropriate on the basis of the oxidizing organic component.

  Further, the packaging container of the present invention can be a multilayer container including at least one oxygen absorption layer composed of a base resin component (component A) and an oxygen absorption functional component (component B). The oxygen absorbing layer is preferably provided on the inner side of the outer surface of the container so as not to be exposed on the outer surface of the container, and is disposed on the outer side of the inner surface of the container for the purpose of avoiding direct contact with the contents. It is preferable to provide it. Thus, it is desirable to use the oxygen absorbing layer as at least one intermediate layer of a multilayer container.

The packaging container shown in FIG. 1 is a typical example of a multilayer container 1 composed of a multilayer structure, and represents an unstretched portion that has not undergone stretching processing. The multilayer container 1 includes an inner layer 1a, an outer layer 1b, an intermediate layer 2, and an oxygen absorbing layer. The oxygen absorbing layer 3 is provided between the inner layer 1 a and the intermediate layer 2 and between the outer layer 1 b and the intermediate layer 2.
Moreover, it can also be set as the 2 type | mold 3 layer multilayer container which provided the oxygen absorption layer between the inner layer and the outer layer.

Examples of the thermoplastic resin of the other layer combined with the oxygen absorbing layer in the multilayer container include a thermoplastic polyester resin, a polycarbonate resin, a polyacrylonitrile resin, a polyolefin resin, a polyvinyl chloride resin, and other gas barrier resins. .
The thermoplastic polyester resin is the same as that described above.
Examples of the polyolefin resin include polyethylene (PE) such as low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and linear ultra low density polyethylene (LVLDPE). , Polypropylene (PP), ethylene-propylene copolymer, polybutene-1, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer, ethylene-vinyl acetate Examples thereof include copolymers, ion-crosslinked olefin copolymers (ionomers), and blends thereof. Further, as the most suitable example of the gas barrier resin, there can be mentioned an ethylene-vinyl alcohol copolymer (EVOH). For example, the ethylene content is 20 to 60 mol%, particularly 25 to 50 mol%. A saponified copolymer obtained by saponifying an ethylene-vinyl acetate copolymer so that the saponification degree is 96 mol% or more, particularly 99 mol% or more is used. The saponified ethylene vinyl alcohol copolymer should have a molecular weight sufficient to form a film and is generally measured under a concentration condition of 30% by weight in a mixed solvent of 85:15 by weight ratio of phenol: water. Thus, it is desirable to have a viscosity of 0.01 dl / g or more, particularly 0.05 dl / g or more. In addition, as another example of the gas barrier resin, a cyclic olefin copolymer (COC), particularly a copolymer of ethylene and a cyclic olefin can also be used.
The polycarbonate resin, polyacrylonitrile resin, or polyvinyl chloride resin is not particularly limited, and those commercially available for films and sheets can be widely used.

In manufacturing the multilayer container, an adhesive resin may be interposed between the resin layers as necessary.
Examples of such adhesive resins include carbonyl (—CO—) groups based on carboxylic acids, carboxylic acid anhydrides, carboxylates, carboxylic acid amides, carboxylic acid esters and the like having 1 to 700 meq / Examples include thermoplastic resins containing 100 g resin, particularly 10 to 500 meq / 100 g resin. Suitable examples of adhesive resins include ethylene-acrylic acid copolymers, ionically crosslinked olefin copolymers, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, acrylic acid grafted polyolefins, ethylene-vinyl acetate copolymers, copolymers. One type or a combination of two or more types such as polymerized polyester and copolymerized polyamide. These resins are useful for lamination by coextrusion or sandwich lamination.
In addition, an isocyanate-based or epoxy-based thermosetting adhesive resin is also used for adhesive lamination of a gas barrier resin film and a moisture-resistant resin film that are formed in advance.

  In the packaging container of the present invention, the thickness of the oxygen absorbing layer is not particularly limited, but in the case of a packaging container composed of a single oxygen absorbing layer, it is generally preferably in the range of 10 to 1000 μm, particularly 100 to 500 μm. When used as a multilayer container, it is generally 1 to 300 μm, particularly 3 to 50 μm. That is, when the thickness of the oxygen absorbing layer becomes thinner than a certain range, the barrier property or oxygen absorbing performance is inferior, and even if it becomes thicker than a certain range, there is no particular advantage in terms of oxygen absorbing property, and the amount of resin increases. This is because it is disadvantageous in terms of economics and container characteristics such as a decrease in flexibility and flexibility of the material.

The packaging container of the present invention is obtained by melt-kneading the resin composition with an extruder, then performing primary molding of a film, a sheet, etc. through a T-die, a circular die (ring die), etc. A packaging container is formed in the form of a tray, a tube container or the like.
Moreover, when using an injection machine, after melt-kneading, it injects into an injection mold, and manufactures the container and the preform for container manufacture.
Further, when the compression molding method is employed, a container or a preform for manufacturing a container is manufactured by extruding the molten resin mass into a certain molten resin mass with an extruder and compressing it with a mold.

6). Packaging container
The packaging container of the present invention can be used as a packaging container in the form of bottles, cups, trays, tube containers, etc., and its layer structure is the multilayer structure described above from the viewpoints of aesthetics, appearance suitability, and flavor. Although desirable, it may be a single layer structure.
The packaging container of the present invention is useful as a container that can prevent a decrease in flavor of the contents due to oxygen. Contents that can be filled include tea, coffee, beer, wine, fruit drinks, carbonated soft drinks for beverages, fruits, nuts, vegetables, meat products, infant foods for food, coffee, jam, mayonnaise, ketchup, cooking oil, Examples include dressings, sauces, boiled dairy products, dairy products, and the like, and other products such as pharmaceuticals, cosmetics, gasoline, etc. that are susceptible to deterioration in the presence of oxygen, but are not limited to these examples.

The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.
In addition, the evaluation method in a present Example is as follows.
(1) [Measurement of dissolved oxygen concentration in multilayer bottles in water]
In Examples and Comparative Examples, oxygen-free water was produced with an oxygen-free water generator (LOW DISSOLVED OXYGEN: manufactured by Miura Kogyo Co., Ltd.), and air bubbles were not mixed while flowing nitrogen gas into the prepared multilayer bottle. It was filled with oxygen-free water and sealed with an aluminum cap. The dissolved oxygen concentration in the water in the multi-layer bottle when stored in a constant temperature and humidity chamber at 22 ° C. and 60% for 14 days was measured with an oxygen indicator (orbisphere laboratories).

(2) [Measurement of total surface area of domain]
Cut out a sample piece with a width of 2 mm and a length of 10 mm from the unstretched part of the multilayer bottle (under the neck ring) and the preform, surface the sample piece cross section with an ultramicrotome, and then deposit Pt at 10 mA in vacuum for 60 seconds. And preprocessed. The cross section of the sample piece pretreated with a scanning electron microscope (JMS-6300F: manufactured by JEOL Ltd.) at an acceleration voltage of 3 kV was observed to evaluate the phase structure.
Using a photograph of the sea-island phase structure of a bottle (bottom neck ring or preform) with a magnification of 3000 times observed with a scanning electron microscope (JMS-6300F: manufactured by JEOL Ltd.), the total number of islands in the above photograph Count. Further, paying attention to the island portion, the longest diameter and the shortest diameter of each particle were measured, and each particle diameter and the average particle diameter of the whole were obtained. From this average particle size, the total surface area of the islands in the bottle was determined.

The gas barrier resin is a polymetaxylylene adipamide resin [T-600: manufactured by Toyobo Co., Ltd.] having a terminal amino group concentration of 87 eq / 10 ⁶ g immediately after opening the moisture-proof packaging as a base material, and is oxidized. Liquid maleic anhydride-modified polybutadiene [M-2000-20: manufactured by Nippon Petrochemical Co., Ltd.] is used as an organic component, and 5 wt% of transition metal catalyst (component G). The oxygen-absorbing functional resin composition containing 350 ppm in terms of metal was kneaded to prepare oxygen-absorbing functional resin composition pellets.
Using a co-injection molding machine equipped with three injection machines: an inner and outer layer PET injection machine (a), an intermediate layer PET injection machine (b), and an oxygen absorption intermediate layer component A, B) injection machine (c). , A and b were polyethylene terephthalate [RT543C: manufactured by Nihon Unipet Co., Ltd.] which was dried at 150 ° C. for 4 hours, and c was dried at 150 ° C. for 4 hours as a base resin component (component A). Base resin component (component A) and oxygen absorption using polyethylene terephthalate [RT543C: manufactured by Nippon Unipet Co., Ltd.] and oxygen-absorbing functional resin component pellets as oxygen-absorbing functional component (component B) Supplying a dry blend having a composition ratio of the functional component (component B) of 50:50, the inner and outer layers and the intermediate layer are PET layers, and the oxygen absorbing intermediate layer (oxygen absorbing layer) is between them 5 layers (a / c / b / The multilayer preform of c / a) was sequentially injection molded.
The preform weight was 26.5 g, of which the oxygen absorption intermediate layer was 3% by weight. The resulting preform was biaxially stretched and blow molded to form a two-kind five-layer multilayer bottle. After filling with oxygen-free water for 14 days at 22 ° C. and 60%, the dissolved oxygen concentration in the water was measured. . The cross section of the multilayer bottle preform was observed with an electron microscope, and the average particle diameter and the ratio (N / M) of the total surface area of the island portion to the internal volume of the multilayer container were determined.

  As in Example 1, except that polyethylene terephthalate [NES2040: manufactured by Unitika Co., Ltd.] having a lower melt viscosity than that of Example 1 was used as the base resin component (component A) for c, A bottle was created, and the dissolved oxygen concentration in the water was measured, and the phase structure was analyzed by electron microscopy.

  In addition to c, a polymetaxylylene adipamide resin [T-660: manufactured by Toyobo Co., Ltd.] having a higher melt viscosity than that of Example 1 was used as the gas barrier resin of the oxygen-absorbing functional component (component B). Prepared the 2 type 5 layer multilayer bottle like Example 1, and performed the phase structure analysis by the measurement of the dissolved oxygen concentration in water, and electron microscope observation.

  2 types 5 layers multilayer bottle like Example 1 except having supplied the dry blend which consists of a base resin component (component A) and oxygen absorption functional component (component B) which consists of 60:40 to c. Were prepared, and the dissolved oxygen concentration in the water was measured, and the phase structure was analyzed by electron microscope observation.

  2 types 5 layers multilayer bottle like Example 1 except having supplied the dry blend material which the composition ratio of a base resin component (component A) and an oxygen absorption functional component (component B) consists of 70:30 to c. Were prepared, and the dissolved oxygen concentration in the water was measured, and the phase structure was analyzed by electron microscope observation.

  A two-type five-layer multilayer bottle was prepared in the same manner as in Example 5 except that the two-type five-layer multilayer preform was sequentially injection-molded, and the oxygen absorption intermediate layer was changed to 8% by weight, and the dissolved oxygen concentration in water was measured. Then, the phase structure analysis by electron microscope observation was performed.

  Except that the oxidizing organic component of the oxygen-absorbing functional component (component B) was 2.5% by weight, a two-kind five-layer multilayer bottle was prepared in the same manner as in Example 5, and the dissolved oxygen concentration in water was measured. The phase structure was analyzed by observation.

  A two-kind five-layer multilayer bottle was prepared in the same manner as in Example 7 except that the two-kind five-layer multilayer preform was sequentially injection-molded and the oxygen absorption layer was 8% by weight. The phase structure was analyzed by microscopic observation.

In c, as an oxygen-absorbing functional component (component B), polymetaxylylene adipamide resin pellets with a terminal amino group concentration of 24 eq / 10 ⁶ g immediately after opening the moisture-proof packaging [6007: manufactured by Mitsubishi Gas Chemical Co., Ltd.] Cobalt neodecanoate [DICANATE 5000: manufactured by Dainippon Ink & Chemicals, Inc.] was deposited in an amount equivalent to 400 ppm in terms of cobalt and melt-kneaded with a twin screw extruder to produce and use oxygen-absorbing functional resin composition pellets. Multilayer preforms of layers were sequentially injection molded.
Among them, except that the oxygen-absorbing functional component (component B) of the oxygen-absorbing layer was changed to 10% by weight, a two-kind 5-layer multilayer bottle was prepared in the same manner as in Example 6, and the dissolved oxygen concentration in water was measured and observed with an electron microscope. Phase structure analysis was performed.

[Comparative Example 1]
As a base resin component (component A) for c, polyethylene terephthalate [NES2040: manufactured by Unitika Co., Ltd.] having a melt viscosity lower than that of Example 1 was used, and as a gas barrier resin of an oxygen-absorbing functional component (component B) Except that the polymetaxylylene adipamide resin [T-660: manufactured by Toyobo Co., Ltd.] having a higher melt viscosity than that of Example 1 was used, a two-kind five-layer multilayer bottle was prepared in the same manner as in Example 2, and the Measurement of dissolved oxygen concentration and phase structure analysis by electron microscope observation were performed.

[Comparative Example 2]
As the base resin component (component A), polyethylene terephthalate [TR4550BH: manufactured by Teijin Ltd.] having a melt viscosity lower than that of Example 1 was used as the base resin component (component A), and the base resin component (component A) and the oxygen-absorbing functional component ( A two-kind five-layer multi-layer bottle was prepared in the same manner as in Example 1 except that the composition B was supplied as a dry blend having a composition ratio of 40:60, and the dissolved oxygen concentration in water was measured and observed by an electron microscope. Structural analysis was performed.

[Comparative Example 3]
Except that the oxygen-absorbing functional component (component B) in the oxygen-absorbing layer was changed to 5% by weight, a two-kind five-layer multilayer bottle was prepared in the same manner as in Example 9, and the dissolved oxygen concentration in water was measured and observed by an electron microscope. Structural analysis was performed.
The results are shown in Table 1.

  The packaging container of the present invention is tea, coffee, beer, wine, fruit drink, carbonated soft drink, etc. for beverages, fruits, nuts, vegetables, meat products, infant foods, coffee, jam, mayonnaise, ketchup, cooking oil for foods, It can be widely used as a container for dressings, sauces, boiled dairy products, dairy products, etc., and other items such as pharmaceuticals, cosmetics, gasoline, etc. that easily deteriorate in the presence of oxygen.

The figure which shows the representative example of the packaging container of this invention The figure which shows the relationship between a composition of an oxygen absorptive resin composition, and dissolved oxygen concentration

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a: Inner layer 1b: Outer layer 2: Intermediate layer 3: Oxygen absorption layer A: Base resin component B: Functional resin component

Claims (11)

A packaging container having a base resin component (component A) composed of a thermoplastic polyester resin and an oxygen absorbing layer composed of an oxygen absorbing functional component (component B) composed of a gas barrier resin, an oxidizing organic component and a transition metal catalyst. The oxygen absorption layer is composed of a base resin component (component A) that forms a continuous phase of the sea portion and an oxygen absorption functional component (component B) that forms a discontinuous phase of the island portion, and oxygen absorption The ratio (N / M) of the total surface area (Ncm ² ) of the island portion composed of the oxygen-absorbing functional component (component B) in the layer to the inner volume (Mcm ³ ) of the packaging container is 20 (cm ⁻¹ ) or more. A packaging container characterized by being.   The packaging container according to claim 1, wherein an average particle diameter of the oxygen-absorbing functional component (component B) forming the island portion in the oxygen-absorbing layer is 3.0 µm or less. The packaging container according to claim 1 or 2, wherein the thermoplastic polyester resin is polyethylene terephthalate. Gas barrier resin, according to claim 1 to 3 terminal amino group concentration of a polyamide resin obtained by polycondensation reaction of a diamine component and a dicarboxylic acid component composed mainly of 40 eq / 10 6 ^g or more xylylenediamine A packaging container according to any one of the above. The packaging container according to any one of claims 1 to 4, wherein the oxidizing organic component comprises a polymer derived from polyene. The packaging container according to claim 5 , wherein the polymer derived from polyene is an acid-modified polyene polymer. The packaging container according to any one of claims 1 to 6, wherein the oxygen-absorbing functional component (component B) contains an oxidizing organic component in a proportion of 0.01 to 10% by weight. The packaging container according to any one of claims 1 to 7, wherein the oxygen-absorbing functional component (component B) contains a transition metal catalyst in a proportion of 100 to 3000 ppm as a transition metal atom. The packaging container according to claim 8 , wherein the transition metal catalyst is a cobalt salt of carboxylic acid. Packaging container according to any one of claims 1 to 9 is a multilayered structure formed by another layer laminated on the oxygen absorbing layer. The packaging container according to claim 10, wherein the oxygen-absorbing layer contains an oxygen-absorbing functional component (component B) in a proportion of 10 to 60% by weight.

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