JP5954197B2 - Oxygen-absorbing sealed container - Google Patents

Description

  The present invention relates to an oxygen-absorbing sealed container using an oxygen-absorbing multilayer body excellent in oxygen-barrier performance and oxygen-absorbing performance as a lid for a gas-barrier molded container under a wide range of humidity conditions from low humidity to high humidity. Is.

  Prevents oxygen oxidation of various products that are easily altered or deteriorated by the influence of oxygen, such as food, beverages, pharmaceuticals, and cosmetics, and removes oxygen in the package that contains them for the purpose of long-term storage Oxygen absorber is used.

  As the oxygen absorbent, an oxygen absorbent containing iron powder as a main reaction agent is generally used from the viewpoint of oxygen absorption capacity, ease of handling, and safety. However, since this iron-based oxygen absorbent is sensitive to a metal detector, it has been difficult to use the metal detector for foreign object inspection. Moreover, since the package which enclosed the iron-type oxygen absorber has a possibility of ignition, it cannot be heated with a microwave oven. Furthermore, since water is essential for the oxidation reaction of iron powder, the effect of oxygen absorption could only be exhibited if the material to be preserved was a high moisture type.

  In addition, the container is made of a multilayer material in which an oxygen absorbing layer made of an oxygen absorbing resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. Development of packaging containers having an oxygen absorbing function has been carried out (see Patent Document 1). However, this also has problems such as being unable to use a metal detector for foreign object inspection in order to respond to a metal detector, being unable to be heated by a microwave oven, and being only effective in high moisture content. doing. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity.

  In view of the above circumstances, an oxygen absorbent using an organic substance as a reaction main agent is desired. As an oxygen absorbent containing an organic substance as a main reaction agent, an oxygen absorbent containing ascorbic acid as a main agent is known (see Patent Document 2).

  On the other hand, an oxygen-absorbing resin composition comprising a resin and a transition metal catalyst is known. For example, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal catalyst as an oxidizable organic component is known (see Patent Document 3). Furthermore, Patent Document 3 also exemplifies an oxygen absorbent, a packaging material, and a multilayer laminated film for packaging obtained by molding this resin composition.

  As an oxygen-absorbing resin composition that does not require moisture for oxygen absorption, an oxygen-absorbing resin composition comprising a resin having a carbon-carbon unsaturated bond and a transition metal catalyst is known (see Patent Document 4). .

  Furthermore, as a composition for collecting oxygen, a composition comprising a polymer containing a substituted cyclohexene functional group or a low molecular weight substance to which the cyclohexene functional group is bonded and a transition metal is known (see Patent Document 5). .

Japanese Patent Laid-Open No. 9-234832 JP-A-51-136845 JP 2001-252560 A Japanese Patent Laid-Open No. 05-115776 Special table 2003-521552 gazette

  However, the oxygen absorbent of Patent Document 2 has a problem that oxygen absorption performance is low in the first place, and only a high-moisture material is effective and is relatively expensive.

  Moreover, since the resin composition of patent document 3 expresses an oxygen absorption function by containing a transition metal catalyst and oxidizing a xylylene group-containing polyamide resin, the polymer chain due to oxidative degradation of the resin after oxygen absorption. There is a problem that cutting occurs and the strength of the packaging container itself is reduced. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture.

  Furthermore, the oxygen-absorbing resin composition of Patent Document 4 generates a low molecular weight organic compound that becomes an odor component by breaking the polymer chain accompanying the oxidation of the resin in the same manner as described above, and generates odor after oxygen absorption. There's a problem.

  On the other hand, the composition of Patent Document 5 requires the use of a special material containing a cyclohexene functional group, and there is still a problem that this material is relatively odorous.

  The present invention has been made in view of the above problems, and its purpose is to suppress the generation of odor after oxygen absorption without using a material sensitive to a metal detector, and has excellent oxygen absorption performance. An object of the present invention is to provide an oxygen-absorbing sealed container using a novel oxygen-absorbing multilayer body as a cover material for a gas-barrier molded container. Another object of the present invention is to absorb oxygen using an oxygen-absorbing multilayer body as a lid for a gas-barrier molded container having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity. It is to provide a sealed container.

  As a result of intensive studies on the oxygen-absorbing multilayer body, the present inventors have found that the above-described problems can be solved by using a copolymerized polyolefin compound having a predetermined tetralin ring and a transition metal catalyst. Was completed.

（式中、Ｒ₁、Ｒ₂、Ｒ₃およびＲ₄は、それぞれ独立して水素原子または第１の一価の置換基を示し、前記第１の一価の置換基は、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよい。）
からなる群より選択される少なくとも１種の構成単位（ａ）と、下記一般式（２）および（３）で表される構成単位；

（式中、Ｒ₅、Ｒ₆およびＲ₇は、それぞれ独立して水素原子または第２の一価の置換基を示し、Ｒ₈、Ｒ₉、Ｒ₁₀およびＲ₁₁は、それぞれ独立して第３の一価の置換基を示し、前記第２の一価の置換基および前記第３の一価の置換基は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよく、前記Ｒ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁が複数存在する場合、複数の前記Ｒ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁は、互いに同一であっても異なっていてもよい。ｍは０〜３、ｎは０〜７、ｐは０〜６、ｑは０〜４の整数をそれぞれ示し、テトラリン環のベンジル位には少なくとも１つの水素原子が結合している。Ｘは−（Ｃ＝Ｏ）Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ（Ｃ＝Ｏ）−、−ＮＨ（Ｃ＝Ｏ）−および−（ＣＨＲ）ｓ−からなる群より選択される二価の基を示し、ｓは０〜１２の整数を示す。Ｙは−（ＣＨＲ）ｔ−であって、ｔは０〜１２の整数を示す。Ｒは水素原子、メチル基およびエチル基からなる群より選択される一価の化学種を示す。）
からなる群より選択される少なくとも１種のテトラリン環を有する構成単位（ｂ）と、を含有する共重合ポリオレフィン化合物である、酸素吸収性密封容器。
＜２＞ 前記遷移金属触媒が、マンガン、鉄、コバルト、ニッケルおよび銅からなる群より選択される少なくとも１種以上の遷移金属を含むものである、上記＜１＞記載の酸素吸収性密封容器。
＜３＞ 前記遷移金属触媒が、前記共重合ポリオレフィン化合物１００質量部に対し、遷移金属量として０．００１〜１０質量部含まれる、上記＜１＞または＜２＞に記載の酸素吸収性密封容器。
＜４＞ 前記共重合ポリオレフィン化合物に含まれる、前記構成単位（ｂ）の含有割合に対する前記構成単位（ａ）の含有割合が、モル比で１／９９〜９９／１である、上記＜１＞〜＜３＞のいずれか一項に記載の酸素吸収性密封容器。
＜５＞ 前記構成単位（ａ）が下記式（４）および（５）で表される構成単位；

からなる群より選択される少なくとも１種の構成単位であり、前記構成単位（ｂ）が下記式（６）および（７）で表される構成単位；

からなる群より選択される少なくとも１種の構成単位である、上記＜１＞〜＜４＞のいずれか一項に記載の酸素吸収性密封容器。 That is, the present invention provides the following <1> to <5>.
<1> A sealant layer containing a thermoplastic resin, an oxygen absorbing layer composed of an oxygen absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, and a gas barrier layer containing a gas barrier material were laminated in this order. A lid material containing an oxygen-absorbing multilayer body composed of at least three layers, an inner layer containing a thermoplastic resin, a gas barrier layer containing a gas barrier substance, and an outer layer containing a thermoplastic resin are laminated in this order, at least 3 A gas barrier molding container comprising a layer, and an oxygen-absorbing sealed container in which the sealant layer in the lid member and the inner layer in the gas barrier molding container are joined, wherein the copolymerized polyolefin compound is A structural unit represented by the following general formula (1);

Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a first monovalent substituent, wherein the first monovalent substituent is a halogen atom, an alkyl Group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio And at least one selected from the group consisting of a group, an arylthio group, a heterocyclic thio group, and an imide group, which may further have a substituent.)
At least one structural unit (a) selected from the group consisting of: structural units represented by the following general formulas (2) and (3);

(Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently 3 monovalent substituents, wherein the second monovalent substituent and the third monovalent substituent are each independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group , Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and And at least one selected from the group consisting of imide groups, which may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , a plurality of the R ₈ , R ₉ , R ₁₀ R ₁₁ may be the same or different from each other, m is 0 to 3, n is 0 to 7, p is 0 to 6, and q is an integer of 0 to 4, At least one hydrogen atom is bonded to the benzyl position, X is — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O )-And-(CHR) s- represents a divalent group selected from the group consisting of-and s represents an integer of 0 to 12. Y is-(CHR) t-, where t is 0-12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.)
An oxygen-absorbing sealed container, which is a copolymerized polyolefin compound containing a structural unit (b) having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing sealed container according to <1>, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.
<3> The oxygen-absorbing sealed container according to <1> or <2>, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the copolymer polyolefin compound. .
<4> The above <1>, wherein the content ratio of the structural unit (a) to the content ratio of the structural unit (b) contained in the copolymerized polyolefin compound is 1/99 to 99/1 in molar ratio. The oxygen-absorbing sealed container according to any one of to <3>.
<5> Structural units in which the structural unit (a) is represented by the following formulas (4) and (5);

At least one structural unit selected from the group consisting of: wherein the structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing sealed container according to any one of <1> to <4>, which is at least one structural unit selected from the group consisting of:

  According to the present invention, an oxygen-absorbing sealed container using an oxygen-absorbing multilayer body having excellent oxygen-absorbing performance under a wide range of humidity conditions from low humidity to high humidity is used as a lid for a gas barrier molded container. be able to. An oxygen-absorbing sealed container using this oxygen-absorbing multilayer body as a lid for a gas-barrier molded container can absorb oxygen regardless of the presence or absence of moisture in the object to be stored, and the odor after oxygen absorption. Since there is no generation | occurrence | production, it can be used for a wide use regardless of target objects, such as a foodstuff, cooked food, a drink, a pharmaceutical, health food, for example. It is also possible to realize an oxygen-absorbing sealed container using an oxygen-absorbing multilayer body that is insensitive to a metal detector as a cover material for a gas barrier molded container. Furthermore, according to a preferred embodiment of the present invention, the strength of the copolymerized polyolefin compound due to oxidation is very small even after oxygen absorption, and the oxygen absorbing layer strength is maintained even in long-term use. It is also possible to realize an oxygen-absorbing sealed container using the absorbent multilayer body as a lid for a gas barrier molded container.

  Embodiments of the present invention will be described below. In addition, the following embodiment is an illustration for demonstrating this invention, and this invention is not limited only to the embodiment.

[Oxygen-absorbing multilayer]
The oxygen-absorbing multilayer body of this embodiment includes a sealant layer (layer C) containing a thermoplastic resin, at least one ethylene selected from the group consisting of structural units represented by the general formula (1), or a substitution A substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural unit (a) which is an ethylene structural unit and the structural unit represented by the general formula (2) or (3). An oxygen-absorbing layer (layer) comprising an oxygen-absorbing resin composition containing a copolymerized polyolefin compound containing the structural unit (b) (hereinafter also simply referred to as “tetralin ring-containing copolymerized polyolefin compound”) and a transition metal catalyst. A) and at least three gas barrier layers (layer D) containing a gas barrier substance are laminated in this order. Moreover, the oxygen-absorbing multilayer body of the present embodiment may have a layer other than these three layers at an arbitrary position as necessary.

  The oxygen-absorbing multilayer body according to the present embodiment absorbs oxygen in the sealed container by using the layer C as an inner side for the lid of the sealed container, and transmits or enters the lid from the outside of the sealed container. If there is even a slight amount, the permeated or penetrated oxygen can be absorbed to prevent alteration of the stored content item (stored object) due to oxygen.

[Sealant layer (layer C)]
The sealant layer (layer C) of the oxygen-absorbing multilayer body of this embodiment contains a thermoplastic resin. In addition to the role as a sealant, this layer C allows oxygen in the container to permeate to the oxygen absorbing layer and at the same time isolates the oxygen absorbing layer (layer A) from the contents (stored material) (layer A and stored product). (Inhibiting physical contact with objects). Here, the oxygen permeability of the layer C is 300 mL / (m ² · day · atm) or more when measured with a film having a thickness of 20 μm under conditions of 23 ° C. and a relative humidity of 60%. It is preferably 400 mL / (m ² · day · atm) or more, more preferably 500 mL / (m ² · day · atm) or more. When the oxygen permeability is equal to or higher than the above preferable value, the rate of absorbing the oxygen in the layer A can be further increased as compared with the case where the oxygen permeability is not so.

  As the thermoplastic resin used for the layer C of the oxygen-absorbing multilayer body of this embodiment, high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, and metallocene catalyst are used. Polyethylenes such as polyethylene; polystyrene; polymethylpentene; polypropylenes such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer; PET, A-PET, PETG having heat sealability; Examples thereof include polyester such as PBT; amorphous nylon and the like. These can be used alone or in combination. These thermoplastic resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid, if necessary. A copolymer, ethylene-methyl methacrylate copolymer, or thermoplastic elastomer may be added. The thermoplastic resin used for the layer C of the oxygen-absorbing multilayer body of the present embodiment has a melt mass flow rate (hereinafter referred to as “MFR”) of 1 at 200 ° C. in consideration of the moldability and workability of the multilayer body. It is preferable to use ˜35 g / 10 minutes or MFR of 2 to 45 g / 10 minutes at 240 ° C. In the present specification, unless otherwise specified, MFR means a value when measured under the condition of a load of 2160 g at a specific temperature using an apparatus conforming to JIS K7210. Expressed with the measured temperature in units of “10 minutes”.

  Further, the layer C of the oxygen-absorbing multilayer body of the present embodiment may contain various additives known in the art in addition to the thermoplastic resin. Examples of such optional components include desiccants, coloring pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, plasticizers, stabilizers, additives such as lubricants, calcium carbonate, clay, mica, Examples thereof include fillers such as silica, deodorants and the like, but are not particularly limited thereto. In particular, it is preferable to add an antioxidant to the layer C from the viewpoint of recycling and reworking offcuts generated during production.

  The content ratio of the thermoplastic resin in the layer C can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably based on the total amount of the layer C. Is 90 to 100% by mass. In addition, the thermoplastic resin used for the layer C of the present embodiment preferably contains 50 to 100% by mass of the thermoplastic resin other than the tetralin ring-containing copolymer polyolefin compound, more preferably 70 to 100 mass%, More preferably, it is 90-100 mass%.

[Oxygen absorbing layer (layer A)]
The oxygen absorbing layer (A) of the oxygen-absorbing multilayer body of the present embodiment is a structural unit that is at least one ethylene or substituted ethylene structural unit selected from the group consisting of structural units represented by the general formula (1). And (a) and a structural unit (b) that is a substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural units represented by the general formula (2) or (3) And an oxygen-absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst.

  The content ratio of the tetralin ring-containing copolymer polyolefin compound in layer A is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass with respect to the total amount of layer A. That's it. When the content ratio of the tetralin ring-containing copolymer polyolefin compound is equal to or more than the preferable value, the oxygen absorption performance can be further improved as compared to the case where the content is not so.

<Tetralin ring-containing copolymer polyolefin compound>
The tetralin ring-containing copolymer polyolefin compound of this embodiment is a structural unit (a) that is at least one ethylene or substituted ethylene structural unit selected from the group consisting of structural units represented by the general formula (1), And a structural unit (b) which is a substituted ethylene structural unit having at least one tetralin ring selected from the group consisting of the structural units represented by the general formula (2) or (3).

  The structural unit (a) represented by the general formula (1) is preferably at least one selected from the group consisting of structural units represented by the above formulas (4) and (5). The structural unit (b) represented by the general formula (2) is preferably at least one selected from the group consisting of structural units represented by the above formulas (6) and (7). Here, “containing a structural unit” means that the compound has one or more of the structural unit. Such a structural unit is preferably contained as a repeating unit in the tetralin ring-containing copolymer polyolefin compound. The tetralin ring-containing copolymer polyolefin compound may be either a random copolymer of the structural unit (a) and the structural unit (b) or a block copolymer of the structural unit (a) and the structural unit (b). . Alternatively, the form of copolymerization of these structural units may be, for example, alternating copolymerization or graft copolymerization.

  Further, the tetralin ring-containing copolymer polyolefin compound may contain other structural units other than the structural unit (a) and the structural unit (b), and the structural unit (a), the structural unit (b), and the other structural units. Any of a random copolymer with a structural unit and the block copolymer of the said structural unit (a), a structural unit (b), and another structural unit may be sufficient. Alternatively, the form of copolymerization of these structural units may be, for example, alternating copolymerization or graft copolymerization.

In the structural units represented by the above general formulas (1) to (3), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ (Denoted as “R _{1 to} R ₁₁ ”, the same shall apply hereinafter) (first monovalent substituent, second monovalent substituent, and third monovalent substitution) As the group, a halogen atom (for example, chlorine atom, bromine atom, iodine atom), an alkyl group (preferably having a carbon number of 1 to 15, more preferably a straight chain, branched or cyclic having 1 to 6 carbon atoms) Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, 2-ethylhexyl group, cyclopropyl group, cyclopentyl group), alkenyl group (preferably having carbon number) 2-10, more preferably 2-6 straight chain, branched or cyclic Lucenyl group, for example, vinyl group, allyl group), alkynyl group (preferably alkynyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, for example, ethynyl group, propargyl group), aryl group (preferably Is an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 2 carbon atoms). A monovalent group obtained by removing one hydrogen atom from 5 to 6-membered or 6-membered aromatic or non-aromatic heterocyclic compound, for example, 1-pyrazolyl group, 1-imidazolyl group, 2-furyl group), cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 10 carbon atoms). 6 linear, branched or cyclic alkoxy groups such as methoxy and ethoxy groups, aryloxy groups (preferably having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, such as aryloxy groups such as A phenoxy group), an acyl group (including a formyl group, preferably an alkylcarbonyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, preferably 7 to 12 carbon atoms, more preferably a carbon number. Is an arylcarbonyl group having 7-9, for example, acetyl group, pivaloyl group, benzoyl group), amino group (preferably an alkylamino group having 1-10 carbon atoms, more preferably 1-6 carbon atoms, preferably carbon An anilino group having 6 to 12, more preferably 6 to 8 carbon atoms, preferably a heterocyclic amino group having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, , Amino group, methylamino group, anilino group), mercapto group, alkylthio group (preferably an alkylthio group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as methylthio group or ethylthio group), arylthio A group (preferably an arylthio group having 6 to 12 carbon atoms, more preferably an arylthio group having 6 to 8 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 2 to 10 carbon atoms, more preferably having a carbon number). 1-6 heterocyclic thio groups such as 2-benzothiazolylthio group), imide groups (preferably having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, such as N-succinimide) Group, N-phthalimide group) and the like, but are not particularly limited thereto.

In the case where the substituents R ₁ to R ₁₁ of the above monovalent have a hydrogen atom, with the hydrogen atoms substituent T (wherein the substituents T is a substituent R ₁ to R ₁₁ of the above monovalent It may be further substituted with the same meaning as described. Specific examples thereof include an alkyl group substituted with a hydroxy group (eg, hydroxyethyl group), an alkyl group substituted with an alkoxy group (eg, methoxyethyl group), and an alkyl group substituted with an aryl group (eg, benzyl). Group), an alkyl group substituted with a primary or secondary amino group (eg, aminoethyl group), an aryl group substituted with an alkyl group (eg, p-tolyl group), an aryl substituted with an alkyl group Examples thereof include, but are not particularly limited to, an oxy group (for example, 2-methylphenoxy group) and the like. Incidentally, the substituents R ₁ to R ₁₁ of the above monovalent may have a substituent group T monovalent The carbon number mentioned above, and shall not include the carbon number of the substituent T. For example, a benzyl group is regarded as a C 1 alkyl group substituted with a phenyl group, and is not regarded as a C 7 alkyl group substituted with a phenyl group. In addition, when the monovalent substituents R _{1 to} R ₁₁ have a substituent T, there may be a plurality of the substituents T.

In the structural unit represented by the general formula (2) or (3), X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH. A divalent group selected from the group consisting of (C = O)-and-(CHR) s- is shown, and s is an integer of 0-12. Y is-(CHR) t-, and t represents an integer of 0 to 12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom (—H), a methyl group (—CH ₃ ), and an ethyl group (—C ₂ H ₅ ).

  The tetralin ring-containing copolymer polyolefin compound of the present embodiment can be obtained by copolymerizing a vinyl compound (I) having a tetralin ring and another vinyl compound (II).

（式中、Ｒ₅〜Ｒ₇は、それぞれ独立して水素原子または第２の一価の置換基を示し、Ｒ₈〜Ｒ₁₁は、それぞれ独立して第３の一価の置換基を示し、第２の一価の置換基および第３の一価の置換基は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよく、Ｒ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁が複数存在する場合、複数のＲ₈、Ｒ₉、Ｒ₁₀またはＲ₁₁は、互いに同一であっても異なっていてもよい。ｍは０〜３、ｎは０〜７、ｐは０〜６、ｑは０〜４の整数をそれぞれ示し、テトラリン環のベンジル位には少なくとも１つの水素原子が結合している。Ｘは−（Ｃ＝Ｏ）Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ（Ｃ＝Ｏ）−、−ＮＨ（Ｃ＝Ｏ）−および−（ＣＨＲ）ｓ−からなる群より選択される二価の基を示し、ｓは０〜１２の整数を示す。Ｙは−（ＣＨＲ）ｔ−であって、ｔは０〜１２の整数を示す。Ｒは−Ｈ、−ＣＨ₃、および−Ｃ₂Ｈ₅からなる群より選択される一価の化学種を示す。） As vinyl compound (I) which has a tetralin ring used by this embodiment, the vinyl compound selected from the group which consists of a compound represented by the following general formula (8) or (9) is mentioned, for example. The vinyl compound (I) having a tetralin ring can be used singly or in combination of two or more.

(In the formula, R _{5 to} R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R _{8 to} R ₁₁ each independently represent a third monovalent substituent. , The second monovalent substituent and the third monovalent substituent are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, At least one selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group a seed, it may further have a substituent, and when R _8, R _9, R ₁₀ or R ₁₁ there are a plurality, the plurality of R _8, R _9, R ₁₀ or R ₁₁ are each Even if they are the same M is 0 to 3, n is 0 to 7, p is 0 to 6, q is an integer of 0 to 4, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring. X is selected from the group consisting of — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O) — and — (CHR) s—. S represents an integer of 0 to 12. Y represents — (CHR) t—, and t represents an integer of 0 to 12. R represents —H, —CH ₃ , And a monovalent chemical species selected from the group consisting of —C ₂ H _5. )

（式中、Ｒ₁〜Ｒ₄は、それぞれ独立して水素原子または第１の１価の置換基を示し、第１の一価の置換基は、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよい。） As vinyl compound (II) used by this embodiment, the vinyl compound selected from the group which consists of a compound represented by following General formula (10) is mentioned, for example. Vinyl compound (II) can be used individually by 1 type or in combination of 2 or more types.

(Wherein R _{1 to} R ₄ each independently represent a hydrogen atom or a first monovalent substituent, and the first monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, or an alkynyl group. , Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic ring It is at least one selected from the group consisting of a thio group and an imide group, and these may further have a substituent.)

  Examples of the vinyl compound represented by the general formula (10) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3 -Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene Ethylene or α-olefin having 2 to 20 carbon atoms such as 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene; Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohex Cycloolefins such as cene and cyclooctene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; butadiene, isoprene, Conjugated dienes such as 2,3-dimethylbutadiene, pentadiene, hexadiene; styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4 -Styrenes such as dodecylstyrene, 2-ethyl-4-benzylstyrene, 2,4,6-trimethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl ( (Meth) acrylate, n-butyl (meth) Acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, (meth) acrylic acid, crotonic acid , Cinnamic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monoethyl maleate, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxy Propyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, (meth) acrylonitrile, α-chloroacrylonitrile, ethacryl Ronitrile, 2-cyanoethyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, (meth) acrylamide, α-chloro (meth) acrylamide, ethacrylamide, N-methyl (meth) acrylamide, N-vinyl-ε-caprolactam, N-vinylpyrrolidone, 2-nitroethyl (meth) acrylate, 3-nitropropyl (meth) acrylate and the like can be mentioned. These can be used alone or in combination of two or more. In addition, (meth) acrylate means an acrylate and its corresponding methacrylate, and (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid.

（式中、Ｒ₅〜Ｒ₇は、それぞれ独立して水素原子または第２の一価の置換基を示し、Ｒ₈およびＲ₉は、それぞれ独立して第３の一価の置換基を示し、第２の一価の置換基および第３の一価の置換基は、それぞれ独立して、ハロゲン原子、アルキル基、アルケニル基、アルキニル基、アリール基、複素環基、シアノ基、ヒドロキシ基、カルボキシル基、エステル基、アミド基、ニトロ基、アルコキシ基、アリールオキシ基、アシル基、アミノ基、メルカプト基、アルキルチオ基、アリールチオ基、複素環チオ基およびイミド基からなる群より選択される少なくとも１種であり、これらはさらに置換基を有していてもよく、Ｒ₈またはＲ₉が複数存在する場合、複数のＲ₈またはＲ₉は、互いに同一であっても異なっていてもよい。ｍは０〜３、ｎは０〜４の整数をそれぞれ示し、Ｘは−（Ｃ＝Ｏ）Ｏ−、−（Ｃ＝Ｏ）ＮＨ−、−Ｏ（Ｃ＝Ｏ）−、−ＮＨ（Ｃ＝Ｏ）−および−（ＣＨＲ）ｓ−からなる群から選択される二価の基を示し、ｓは０〜１２の整数を示す。Ｙは−（ＣＨＲ）ｔ−であって、ｔは０〜１２の整数を示す。Ｒは−Ｈ、−ＣＨ₃、および−Ｃ₂Ｈ₅からなる群から選択される一価の化学種を示す。） The tetralin ring-containing copolymer polyolefin compound of this embodiment is a substituent having at least one naphthalene ring selected from the group consisting of the structural unit (a) and a structural unit represented by the following general formula (11). It can also be obtained by reacting a copolymerized polyolefin compound containing a structural unit (c) that is a substituted ethylene structural unit containing hydrogen with hydrogen.

Wherein R _{5 to} R ₇ each independently represents a hydrogen atom or a second monovalent substituent, and R ₈ and R ₉ each independently represent a third monovalent substituent. , The second monovalent substituent and the third monovalent substituent are each independently a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, At least one selected from the group consisting of carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and imide group a seed, it may further have a substituent, and when R ₈ or R ₉ there are a plurality, the plurality of R ₈ or R ₉ is optionally being the same or different .m Is 0-3, Represents an integer of 0 to 4, and X represents — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O) — and — ( CHR) represents a divalent group selected from the group consisting of s-, s represents an integer of 0 to 12. Y represents-(CHR) t-, and t represents an integer of 0-12. R represents a monovalent chemical species selected from the group consisting of —H, —CH ₃ , and —C ₂ H _5. )

  As another production method of the tetralin ring-containing copolymer polyolefin compound of the present embodiment, there is a method of reacting a polyolefin (III) having a reactive functional group in the side chain with a compound (IV) having a tetralin ring. It is done.

  Examples of the polyolefin (III) having a reactive functional group in the side chain include unsaturated carboxylic acid polymers such as poly (meth) acrylic acid; unsaturated carboxylic acid ester polymers such as poly (meth) acrylic acid methyl Polyvinyl acetate and polyvinyl acetate derivatives such as polyvinyl acetate; ethylene-unsaturated carboxylic acid copolymer; ethylene-unsaturated carboxylic acid ester copolymer; ethylene-vinyl alcohol copolymer; maleic anhydride-modified polyethylene, maleic anhydride Examples include maleic anhydride-modified polyolefin such as acid-modified polypropylene. These can be used alone or in combination of two or more.

  As the compound (IV) having a tetralin ring, a compound having a functional group that easily binds to the polyolefin (III) having a reactive functional group in the side chain is preferable, and an alcohol compound, an amine compound, a carboxyl having a tetralin ring is preferable. Examples thereof include acid compounds, acid anhydride compounds, and epoxide compounds. These can be used alone or in combination of two or more.

  In particular, a tetralin ring as the compound (IV) having the tetralin ring is added to a solution obtained by dissolving a polyolefin having an ester group in the side chain as a polyolefin (III) having a reactive functional group in the side chain in an organic solvent. A method of adding an alcohol compound having a transesterification catalyst and a transesterification reaction is preferable.

  The transesterification reaction can be performed by a known method. The reaction temperature and reaction time are not particularly limited as long as transesterification is possible, but the reaction temperature is preferably 50 to 300 ° C. and the reaction time is preferably 10 minutes to 24 hours. The organic solvent used for the transesterification reaction can be used without particular limitation as long as it is an organic solvent capable of dissolving the polymer. Examples of such an organic solvent include benzene, toluene, xylene, decalin and the like.

  As another method of transesterification, for example, a polyolefin (III) having a reactive functional group in the side chain as a polyolefin (III) having an ester group in the side chain and a tetralin ring as the compound (IV) having the tetralin ring are used. Examples thereof include a method of melt-kneading the alcohol compound having and the transesterification catalyst with a single screw extruder, a twin screw extruder, a kneader, or the like.

  As the transesterification catalyst used in the transesterification reaction, a known substance can be used. For example, sodium tert-butoxide, sodium propoxide, sodium ethoxide, sodium hydroxide, tetraisopropyl titanate, tetrabutyl titanate , Titanium oxide, titanium chloride, zirconium chloride, hafnium chloride, tin chloride, and metallocene complex catalysts of titanium, zirconium, and tin. These can be used alone or in combination of two.

  The content ratio ((a) / (b)) of the structural unit (a) to the content ratio of the structural unit (b) contained in the tetralin ring-containing copolymer polyolefin compound of the present embodiment is 1/99 in molar ratio. To 99/1, more preferably 1/19 to 19/1, and particularly preferably 1/9 to 9/1.

  The MFR (measured in accordance with JIS K7210 at 190 ° C. and a load of 2.16 kg) of the tetralin ring-containing copolymer polyolefin compound of the present embodiment is not particularly limited. ˜500 g / 10 min is preferable, and 0.2 to 100 g / 10 min is more preferable.

  Preferable specific examples of the structural unit (a) include, but are not limited to, the structural unit represented by the above formula (4) or (5).

Preferable specific examples of the structural unit (b) include structural units represented by the above formula (6) or (7) and structural units represented by the following formula (12) or (13). It is not limited to.

The molecular weight of the tetralin ring-containing copolymer polyolefin compound can be appropriately set in consideration of desired performance and handling properties, and is not particularly limited. In general, the weight average molecular weight (Mw) is preferably 1.0 × 10 ^{3 to} 8.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁵ . Similarly, the number average molecular weight (Mn) is preferably 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ , more preferably 5.0 × 10 ^{3 to} 1.0 × 10 ⁵ . In addition, all the molecular weights here mean the value of polystyrene conversion. In addition, said tetralin ring containing copolymer polyolefin compound can be used individually by 1 type or in combination of 2 or more types.

  All of the tetralin ring-containing copolymer polyolefin compounds described above have hydrogen at the benzylic position of the tetralin ring, and when used in combination with the transition metal catalyst described in detail later, the hydrogen at the benzylic position is extracted, which is excellent. Expresses oxygen absorption ability.

  Moreover, the oxygen-absorbing resin composition of the present embodiment is one in which odor generation after oxygen absorption is remarkably suppressed. Although the reason is not clear, for example, the following oxidation reaction mechanism is assumed. That is, in the above-described tetralin ring-containing copolymer polyolefin compound, hydrogen at the benzylic position of the tetralin ring is first extracted to generate a radical, and then the carbon at the benzylic position is oxidized by the reaction between the radical and oxygen, Group or ketone group is considered to be formed. Therefore, in the oxygen-absorbing resin composition of the present embodiment, the molecular chain of the oxygen-absorbing main agent is not broken by the oxidation reaction as in the prior art, the structure of the tetralin ring-containing copolymer polyolefin compound is maintained, and the odor is reduced. This is presumably because the low molecular weight organic compound that is the cause is difficult to be formed after oxygen absorption.

<Transition metal catalyst>
The transition metal catalyst used in the oxygen-absorbing resin composition of the present embodiment is appropriately selected from known ones as long as it can function as a catalyst for the oxidation reaction of the tetralin ring-containing copolymer polyolefin compound. It can be used and is not particularly limited.

  Specific examples of such transition metal catalysts include organic acid salts, halides, phosphates, phosphites, hypophosphites, nitrates, sulfates, oxides and hydroxides of transition metals. Here, examples of the transition metal contained in the transition metal catalyst include, but are not limited to, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, and rhodium. Among these, manganese, iron, cobalt, nickel, and copper are preferable. Examples of organic acids include acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, Examples include capric acid and naphthenic acid, but are not limited thereto. The transition metal catalyst is preferably a combination of the above-mentioned transition metal and an organic acid, more preferably the transition metal is manganese, iron, cobalt, nickel or copper, still more preferably manganese, iron or cobalt, organic More preferably, the acid is acetic acid, stearic acid, 2-ethylhexanoic acid, oleic acid or naphthenic acid, even more preferably acetic acid or stearic acid, and the combination of any of these transition metals with any of organic acids is particularly preferred preferable. In addition, a transition metal catalyst can be used individually by 1 type or in combination of 2 or more types.

  The content ratio of the tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst in the oxygen-absorbing resin composition of the present embodiment is appropriately determined according to the type and desired performance of the tetralin ring-containing copolymer polyolefin compound and the transition metal catalyst used. It can be set and is not particularly limited. From the viewpoint of the oxygen absorption amount of the oxygen-absorbing resin composition, the content of the transition metal catalyst is 0.001 to 10 parts by mass as the transition metal amount with respect to 100 parts by mass of the tetralin ring-containing copolymer polyolefin compound. Preferably, more preferably 0.002 to 2 parts by mass, still more preferably 0.005 to 1 part by mass, still more preferably 0.008 to 0.5 parts by mass, particularly preferably 0.01 to 0.2 parts by mass. Part.

<Other thermoplastic resins>
Moreover, the oxygen-absorbing resin composition of the present embodiment may further contain other thermoplastic resin other than the tetralin ring-containing copolymer polyolefin compound as necessary. By using another thermoplastic resin in combination, moldability and handleability can be improved.

  As other thermoplastic resins, known ones can be used as appropriate. Low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene, 1- Polyolefins such as random or block copolymers of α-olefins such as butene and 4-methyl-1-pentene; acid-modified polyolefins such as maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; ethylene-vinyl acetate copolymers , Ethylene-vinyl chloride copolymers, ethylene- (meth) acrylic acid copolymers and their ionic cross-linked products (ionomers), ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymers; polystyrene, acrylonitrile- Styrene copolymer, α -Styrenic resin such as methylstyrene-styrene copolymer; polyvinyl compounds such as polymethyl acrylate and polymethyl methacrylate, nylon 6, nylon 66, nylon 610, nylon 12, polymetaxylylene adipamide (MXD6), etc. Polyamides of polyethylene: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polyester such as polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate; polycarbonate; polyether such as polyethylene oxide, etc. Although such mixtures thereof, without limitation. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types.

  The tetralin ring-containing copolymer polyolefin compound, the transition metal catalyst, and other thermoplastic resins contained as necessary can be mixed by a known method. Moreover, the oxygen-absorbing resin composition which has higher dispersibility can also be obtained by kneading | mixing these using an extruder.

<Various additives>
Here, the oxygen-absorbing resin composition of the present embodiment may contain various additives known in the art as long as the effects of the present embodiment are not excessively impaired in addition to the components described above. . Examples of such optional additives include additives such as desiccants, pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, stabilizers, calcium carbonate, clay, mica, silica, and the like. An agent, a deodorant, etc. are mentioned, However, It does not specifically limit to these.

  Furthermore, the oxygen-absorbing resin composition of the present embodiment may further contain a radical generator and a photoinitiator as necessary in order to promote the oxygen absorption reaction. Specific examples of the radical generator include various N-hydroxyimide compounds. Specifically, N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxy Hexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3-hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxyphthalimide, 4-dimethylamino-N-hydroxyphthalimide, 4-carboxy-N-hydroxyhexahydride Examples include phthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide, N, N-dihydroxypyromellitic acid diimide and the like. However, it is not particularly limited to these. Specific examples of the photoinitiator include, but are not limited to, benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, and the like. These radical generators and photoinitiators can be used singly or in combination of two or more.

  In the oxygen-absorbing multilayer body of this embodiment, the thickness of the oxygen-absorbing layer (layer A) can be appropriately set according to the application and desired performance, and is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 10 μm. 100 μm. When the thickness is within the above preferable range, the performance of the layer A to absorb oxygen can be further enhanced, and the workability and economy can be maintained at a high level as compared with the case where the thickness is not. Further, the thickness of the sealant layer (layer C) can be appropriately set according to the application and desired performance, and is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 80 μm. When the thickness is within the above preferable range, the oxygen absorption rate of the layer A can be further increased and the workability and economy can be maintained at a high level as compared with the case where the thickness is not. Furthermore, considering the workability of the resulting oxygen-absorbing multilayer body, the thickness ratio of layer C to layer A is preferably 1: 0.5 to 1: 3, more preferably 1: 1.5 to 1: 2.5.

[Gas barrier layer (layer D)]
The gas barrier layer (layer D) of the oxygen-absorbing multilayer body of this embodiment contains a gas barrier substance. The oxygen permeability of layer D is preferably 100 mL / (m ² · day · atm) or less when measured under the conditions of 23 ° C. and 60% relative humidity for a film having a thickness of 20 μm. It is preferably 80 mL / (m ² · day · atm) or less, more preferably 50 mL / (m ² · day · atm) or less.

  Examples of the gas barrier material used for the layer D of the oxygen-absorbing multilayer body of the present embodiment include a gas barrier thermoplastic resin, a gas barrier thermosetting resin, various deposited films such as silica, alumina, and aluminum, and a metal such as an aluminum foil. A foil or the like can be used. Examples of the gas barrier thermoplastic resin include ethylene-vinyl alcohol copolymer, MXD6, and polyvinylidene chloride. Examples of the gas barrier thermosetting resin include a gas barrier epoxy resin such as “MAXIVE” manufactured by Mitsubishi Gas Chemical Co., Ltd.

  When a thermoplastic resin is used as the gas barrier substance, the thickness of the gas barrier layer (layer D) is preferably 5 to 200 μm, more preferably 10 to 100 μm. When a thermosetting resin such as an amine-epoxy curing agent is used as the gas barrier substance or as the gas barrier adhesive layer, the thickness of the layer D is preferably 0.1 to 100 μm, more preferably 0.00. 5 to 20 μm. When the thickness is within the above preferable range, the gas barrier property tends to be further improved as compared with the case where the thickness is not so, and the workability and economic efficiency can be maintained at a high level.

  Note that the oxygen-absorbing multilayer body of the present embodiment includes a resin layer between the layer C and the layer A, between the layer A and the layer D, or on the outer layer of the layer C or on the outer layer of the layer D. You may have at least 1 or more other layers, such as a metal foil layer or an adhesive bond layer. For example, in order to prevent damage to the layer D and pinholes, a protective layer made of a thermoplastic resin can be provided inside or outside the layer D. Examples of the resin used for this protective layer include polyethylenes such as high-density polyethylene, polypropylenes such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, nylon 6, nylon 6,6 Polyamides such as PET, polyesters such as PET, and combinations thereof. Moreover, a paper base material can be laminated | stacked on the outer layer of the layer D, and can also be used as an oxygen absorptive paper base material.

  In consideration of processability, the oxygen-absorbing multilayer body of the present embodiment preferably has an intermediate layer made of a polyolefin resin interposed between the layer D and the layer A. The thickness of the intermediate layer is preferably substantially the same as the thickness of the layer C from the viewpoint of workability. Here, in consideration of variations due to processing, thickness ratios within ± 10% are substantially the same.

  The oxygen-absorbing multilayer body of the present embodiment can be produced using a known method such as a co-extrusion method, various laminating methods, various coating methods, etc., depending on the properties of various materials, processing purposes, processing steps, and the like. The manufacturing method is not particularly limited. It is possible to apply a method for laminating ordinary packaging materials, for example, wet lamination method, dry lamination method, solventless dry lamination method, extrusion lamination method, T-die coextrusion molding method, coextrusion lamination method, inflation method, etc. it can. For example, for film or sheet molding, an adhesive is applied to an oxygen-absorbing film or sheet formed by extruding a melted resin composition from an extruder attached with a T die, a circular die, or the like. However, there is a method of manufacturing by pasting together with another film or sheet. Further, if necessary, for example, pretreatment such as corona treatment and ozone treatment can be applied to the film and the like, and for example, an isocyanate type (urethane type), polyethyleneimine type, polybutadiene type, organic titanium type anchor, etc. Coating agents, or known anchor coating agents such as adhesives for laminating, such as polyurethane, polyacrylic, polyester, epoxy, polyvinyl acetate, cellulose, etc., can also be used. .

[Gas barrier molding container]
The gas barrier molded container of the present embodiment is composed of at least three layers in which an inner layer containing a thermoplastic resin, a gas barrier layer containing a gas barrier substance, and an outer layer containing a thermoplastic resin are laminated in this order, It is possible to reduce the amount of oxygen that permeates or penetrates into the oxygen-absorbing sealed container from the outside of the gas-barrier molded container. Moreover, the gas-barrier molded object of this embodiment may have layers other than these three layers in arbitrary positions as needed.

  The thermoplastic resin used for the inner layer or outer layer of the gas barrier molding container of the present embodiment is not particularly limited, and for example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, linear ultra-high density Low-density polyethylene, various polyethylenes such as polyethylene by metallocene catalyst; polystyrene; polymethylpentene; polypropylenes such as propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer; PET having heat sealability , A-PET, PETG, PBT and other polyesters; amorphous nylon and the like. These can be used alone or in combination. These thermoplastic resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid, if necessary. A copolymer, ethylene-methyl methacrylate copolymer, or thermoplastic elastomer may be added.

  Moreover, the inner layer or the outer layer of the gas barrier molding container of the present embodiment may contain various additives known in the art in addition to the thermoplastic resin. Examples of such optional components include desiccants, coloring pigments such as titanium oxide, dyes, antioxidants, slip agents, antistatic agents, plasticizers, stabilizers, additives such as lubricants, calcium carbonate, clay, mica, Examples thereof include fillers such as silica, deodorants and the like, but are not particularly limited thereto. In particular, it is preferable to add an antioxidant from the viewpoint of recycling and reworking offcuts generated during production.

  The content ratio of the thermoplastic resin in the inner layer or the outer layer can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the layer C. Preferably it is 90-100 mass%.

  The thermoplastic resin used for the inner layer of the gas barrier molded container of the present embodiment is the same type as the thermoplastic resin used for the layer C of the oxygen-absorbing multilayer body from the viewpoint of ensuring the heat fusion strength of the sealed container. preferable.

The gas barrier layer of the gas barrier molding container of the present embodiment contains a gas barrier substance. The oxygen permeability of the gas barrier layer is preferably 100 mL / (m ² · day · atm) or less when measured at 23 ° C. and a relative humidity of 60% for a film having a thickness of 20 μm. It is preferably 80 mL / (m ² · day · atm) or less, more preferably 50 mL / (m ² · day · atm) or less.

  Examples of the gas barrier material used in the gas barrier layer of the gas barrier molding container of the present embodiment include a gas barrier thermoplastic resin, a gas barrier thermosetting resin, various vapor deposition films such as silica, alumina, and aluminum, and a metal foil such as an aluminum foil. Etc. can be used. Examples of the gas barrier thermoplastic resin include ethylene-vinyl alcohol copolymer, MXD6, and polyvinylidene chloride. Among these, MXD6 is preferable when heat sterilization treatment is performed at a temperature of 80 ° C. or higher on the object to be stored in the gas barrier molded container. Examples of the gas barrier thermosetting resin include a gas barrier epoxy resin such as “MAXIVE” manufactured by Mitsubishi Gas Chemical Co., Ltd.

  When a thermoplastic resin is used as the gas barrier substance, the thickness of the gas barrier layer is preferably 5 to 200 μm, more preferably 10 to 100 μm. When a thermosetting resin such as an amine-epoxy curing agent is used as the gas barrier substance or as the gas barrier adhesive layer, the thickness of the gas barrier layer is preferably 0.1 to 100 μm, more preferably 0.00. 5 to 20 μm. When the thickness is within the above preferable range, the gas barrier property tends to be further improved as compared with the case where the thickness is not so, and the workability and economic efficiency can be maintained at a high level.

[Oxygen absorbing sealed container]
The oxygen-absorbing sealed container of this embodiment includes a lid material containing the above-described oxygen-absorbing multilayer body and a gas barrier molding container, and the sealant layer of the lid material and the inner layer of the gas barrier molding container are joined together. This is an oxygen-absorbing sealed container. The oxygen-absorbing sealed container according to the present embodiment absorbs oxygen in the container, and if a small amount of oxygen enters from the outside of the container, the oxygen-absorbing sealed container also absorbs the intruded oxygen and stores the contents (stored object) Can be prevented from being deteriorated by oxygen.

  The joining mode of the sealant layer of the lid material and the inner layer of the gas barrier molding container is not particularly limited, and examples thereof include heat fusion and adhesion with an adhesive. These joining modes can be used singly or in combination of two or more. Among these, heat fusion is preferable. The joining conditions may be appropriately determined in consideration of the material, shape, dimensions, etc. of the sealant layer and the inner layer.

  In using the oxygen-absorbing sealed container of this embodiment, energy rays can be irradiated to promote the start of the oxygen absorption reaction or increase the oxygen absorption rate. As the energy ray, for example, visible light, ultraviolet ray, X-ray, electron beam, γ-ray or the like can be used. The amount of irradiation energy can be appropriately selected according to the type of energy beam used.

  The oxygen-absorbing sealed container of the present embodiment does not require moisture for oxygen absorption, in other words, it can absorb oxygen regardless of the presence or absence of moisture in the object to be preserved. Can be used in applications. In particular, since there is no generation of odor after oxygen absorption, it can be particularly suitably used in, for example, foods, cooked foods, beverages, health foods, pharmaceuticals and the like. That is, the oxygen-absorbing sealed container of the present embodiment is excellent in oxygen absorption performance under a wide range of humidity conditions (relative humidity 0% to 100%) from low humidity to high humidity, and has a good flavor retention. Since it is excellent, it is suitable for packaging of various articles. In addition, the oxygen-absorbing resin composition of the present embodiment is different from the oxygen-absorbing resin composition using conventional iron powder, and is not stored due to the presence of iron (for example, alcoholic beverages or carbonated beverages). Can be suitably used.

Specific examples of stored items include beverages such as milk, juice, coffee, teas, alcoholic beverages; liquid seasonings such as sauces, soy sauce, noodle soups, dressings; cooked foods such as soups, stews, and curries; jams, mayonnaise Pasty foods such as tuna, fish and shellfish; processed milk products such as cheese, butter and eggs; processed meat products such as meat, salami, sausage and ham; carrots, potatoes, asparagus, shiitake mushrooms Fruits; Eggs; Noodles; Rices such as rice and milled rice; Grains such as beans; Rice processed foods such as cooked rice, red rice, rice cakes and rice bran; Sweets such as buns; powder seasonings, powdered coffee, coffee beans, tea, infant milk powder, infant foods, powder diet foods, nursing foods, dried vegetables, rice crackers, rice crackers, etc. Dry foods (foods with low water activity); chemicals such as adhesives, adhesives, pesticides and insecticides; pharmaceuticals; health foods such as vitamins; pet foods; miscellaneous goods such as cosmetics, shampoos, rinses and detergents; However, the present invention is not particularly limited thereto. In particular, preserved items that are prone to deterioration in the presence of oxygen, such as beer, wine, sake, shochu, fruit juice drinks, fruit juices, vegetable juices, soft carbonated drinks, teas in beverages, fruits, nuts, vegetables in foods , Meat products, infant food, coffee, jam, mayonnaise, ketchup, cooking oil, dressing, sauces, boiled foods, dairy products, etc. The water activity is a scale indicating the free water content in an article, and is indicated by a number from 0 to 1, with 0 for an article without moisture and 1 for pure water. That is, the water activity Aw of a certain article is expressed as follows. The water vapor pressure in the space after the article is sealed and reached an equilibrium state is P, the water vapor pressure of pure water is P ₀ , and the relative humidity in the space is RH (%). , And
Aw = P / P ₀ = RH / 100
Is defined.

  In addition, before and after filling (packaging) of these objects to be preserved, the container or the object to be preserved can be sterilized in a form suitable for the object to be preserved. As the sterilization method, for example, heat sterilization at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultrahigh temperature heat treatment at 130 ° C. or higher, sterilization by electromagnetic waves such as ultraviolet rays, microwaves, gamma rays Examples thereof include gas treatment such as ethylene oxide, and chemical sterilization such as hydrogen peroxide and hypochlorous acid.

  The shape and size of the oxygen-absorbing sealed container including the lid material and gas barrier molded container of the present embodiment may be any shape and size suitable for the above-mentioned use or storage of non-preserved materials. For example, it is not particularly limited, and may be a conventionally known shape and size. Moreover, the manufacturing method is not particularly limited. For example, the above-mentioned oxygen-absorbing multilayer body in the form of a film or sheet can be used as a lid material. On the other hand, a laminate comprising a film-like or sheet-like inner layer containing a thermoplastic resin, a gas barrier layer containing a gas barrier substance, and an outer layer containing a thermoplastic resin, while applying heat as necessary, A gas barrier molding container having a predetermined shape such as a cup, a bottle, or a tube can be produced by molding by a method such as vacuum molding, pressure molding, or plug assist molding. Moreover, it can also be set as the container of arbitrary shapes by performing thermoforming. Alternatively, the molten resin can be formed into a multilayer container having a predetermined shape by co-injecting or sequentially injecting the molten resin into an injection mold through a multilayer multiple die using an injection machine. And the oxygen absorptive sealed container of this embodiment can be obtained by joining the obtained lid | cover material and a gas-barrier shaping | molding container by the above-mentioned joining method.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

(Production Example 1)
In a four-necked separable flask with an internal volume of 1000 mL, 100 g of ethylene-methyl methacrylate copolymer (product name: “Acrylift WK402” manufactured by Sumitomo Chemical Co., Ltd.) having a methyl methacrylate content of 25 mass%, 6-hydroxylmethyl -1,2,3,4-tetrahydronaphthalene 81g, decalin 160g, tetrabutyl titanate 0.2g as a transesterification catalyst were charged, and the temperature of the reaction solution was raised to 210 ° C in a nitrogen atmosphere while stirring, and methanol was distilled. The reaction was carried out for 3 hours while leaving. After methanol was not distilled off, the pressure was gradually reduced to distill off unreacted 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene and decalin. Then, it returned to normal pressure and cooled and the solid reaction crude product was obtained. Next, toluene is added to the obtained reaction crude product so that the concentration thereof becomes 3 to 4% by mass, and the solution is heated to 80 ° C. to dissolve, then the solution is cooled to about 40 ° C., methanol is added, The precipitated tetralin ring-containing copolymer polyolefin compound (1) was recovered by filtration.

As a result of measuring the weight average molecular weight and the number average molecular weight of the obtained tetralin ring-containing copolymer polyolefin compound (1) by GPC (gel permeation chromatography), the weight average molecular weight in terms of polystyrene was 9.5 × 10 ⁴ , number. The average molecular weight was 3.1 × 10 ⁴ . As a result of measuring the melting point by DSC, the melting point was 71 ° C.

(Production Example 2)
1,5-Dimethyl-8-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was used instead of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene in Production Example 1, and the mass was 95. A tetralin ring-containing copolymer polyolefin compound (2) was synthesized in the same manner as in Production Example 1 except that the amount was 0.0 g. This tetralin ring-containing copolymer polyolefin compound (2) had a polystyrene equivalent weight average molecular weight of 9.1 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ and a melting point of 71 ° C.

(Production Example 3)
Instead of the ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass in Production Example 1, an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 5% by mass (product name: Sumitomo Chemical Co., Ltd.) Tetralin ring in the same manner as in Production Example 1 except that the amount of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was changed from 81 g to 16.2 g. The containing copolymer polyolefin compound (3) was synthesized. The copolymerized polyolefin compound (3) had a polystyrene equivalent weight average molecular weight of 9.6 × 10 ⁴ , a number average molecular weight of 3.0 × 10 ⁴ , and a melting point of 98 ° C.

(Production Example 4)
Instead of the ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass in Production Example 1, an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 10% by mass (product name: Sumitomo Chemical Co., Ltd.) Tetralin ring in the same manner as in Production Example 1 except that the amount of 6-hydroxylmethyl-1,2,3,4-tetrahydronaphthalene was changed from 81 g to 32.4 g. A copolymerized polyolefin compound (4) was synthesized. This tetralin ring-containing copolymer polyolefin compound (4) had a polystyrene equivalent weight average molecular weight of 9.3 × 10 ⁴ , a number average molecular weight of 3.1 × 10 ⁴ and a melting point of 92 ° C.

Example 1
First, 100 parts by mass of the copolymerized polyolefin compound (1) and 0.05 parts by mass of cobalt stearate (II) as a cobalt amount were dry blended into a twin screw extruder having two screws with a diameter of 37 mm. The obtained mixture was supplied and kneaded under conditions of an extrusion temperature of 220 ° C. and a screw rotation speed of 100 rpm to obtain an oxygen-absorbing resin composition (1).

  Next, using a multilayer film manufacturing apparatus equipped with an extruder, a T-die, a cooling roll, a corona discharge treatment apparatus, a winder, etc., a sealant film having a thickness of 40 μm (product name: “VMX XB15FT” manufactured by J Film Co., Ltd.) The oxygen-absorbing resin composition (1) was extruded and laminated at a thickness of 30 μm as an oxygen-absorbing layer, and then the surface of the oxygen-absorbing layer was subjected to corona discharge treatment at 60 m / min to obtain a laminate film. Next, a nylon 6 film (product name: Toyo) was used on the corona-treated surface side of the laminate film using an urethane dry laminate adhesive (product name: “AD-817 / CAT-RT86L-60” manufactured by Toyo Morton Co., Ltd.). “N1202” manufactured by Spinning Co., Ltd.) and alumina-deposited PET film (product name: “GL-ARH-F” manufactured by Toppan Printing Co., Ltd.) were laminated by dry lamination, and alumina-deposited PET film (12 μm) / urethane-based dry laminate -Absorbing multilayer film consisting of an oxygen-absorbing multilayered body of adhesive (3 μm) / nylon 6 film (15 μm) / adhesive for urethane-based dry laminate (3 μm) / oxygen-absorbing layer (30 μm) / sealant film (40 μm) Got. In addition, the number of the micrometer unit in a parenthesis shows thickness.

  On the other hand, an ethylene-propylene random copolymer (from the first extruder (using a three-kind five-layer multilayer sheet molding apparatus equipped with a first to third extruder, a feed block, a T die, a cooling roll, and a sheet take-up machine) ( Product name: “Novatec PP EG7F” manufactured by Nippon Polypro Co., Ltd., hereinafter referred to as “PP”), Nylon MXD6 (product name: “MX Nylon S7007” manufactured by Mitsubishi Gas Chemical Co., Ltd.), No. 3 Maleic anhydride-modified polypropylene (product name: “Admer QF500” manufactured by Mitsui Chemicals, Inc.) was extruded from the extruder, and PP (80 μm) / maleic anhydride-modified polypropylene (15 μm) / nylon from the inner layer through a feed block. MXD6 (40 μm) / maleic anhydride modified polypropylene (15 μm) / PP (350 μm) A gas barrier multilayer sheet was obtained.

  Next, the obtained gas barrier multilayer sheet was placed with the inner layer (PP having a thickness of 80 μm) inside, and using a vacuum molding machine, a cup-shaped container (inner volume 70 cc, aperture 62 mm × bottom diameter) as a gas barrier molding container 52 mm × depth 28 mm). This cup-shaped container was filled with 10 g of a humidity control agent, and the relative humidity in the container was adjusted to 100% or 30%. Next, the oxygen-absorbing multilayer film was used as a lid, and sealed by thermal fusion bonding while adjusting the initial oxygen concentration to 2% by nitrogen substitution to obtain an oxygen-absorbing sealed container. The heat fusion was performed using a pack sealing machine manufactured by Aisin Pack Industry Co., Ltd., with a fusion temperature of 240 ° C., a fusion time of 2 seconds, and a fusion pressure of 0.3 MPa. After that, store under conditions of 23 ° C and 50% relative humidity, measure the oxygen concentration in the container after storage for 1 month, the sealing strength between the cover and gas barrier molded container after storage for 1 month, and open the cover The odor inside the container was confirmed. In the measurement of the seal strength, a 15 mm wide section was cut out from the heat-sealed portion, and the seal strength of the section was measured with a tensile tester (the same applies hereinafter).

(Example 2)
An oxygen-absorbing sealed container was produced in the same manner as in Example 1 except that cobalt (II) stearate was dry blended so that the cobalt amount was 0.01 parts by mass instead of 0.05 parts by mass. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

Example 3
An oxygen-absorbing sealed container was produced in the same manner as in Example 1 except that cobalt (II) stearate was dry blended so that the cobalt content was changed to 0.05 parts by mass instead of 0.05 parts by mass. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

Example 4
An oxygen-absorbing sealed container was produced in the same manner as in Example 1 except that cobalt acetate (II) was used instead of cobalt stearate (II). About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Example 5)
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.05 parts by mass, manganese stearate (II) is dry blended so that the amount of manganese is 0.05 parts by mass. In the same manner as in Example 1, an oxygen-absorbing sealed container was produced. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Example 6)
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.05 parts by mass, iron stearate (III) is dry blended so that the amount of iron is 0.05 parts by mass. In the same manner as in Example 1, an oxygen-absorbing sealed container was produced. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Example 7)
An oxygen-absorbing sealed container was produced in the same manner as in Example 1 except that the tetralin ring-containing copolymer polyolefin compound (2) was used instead of the tetralin ring-containing copolymer polyolefin compound (1). About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Example 8)
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.05 parts by mass, manganese stearate (II) is dry blended so that the amount of manganese is 0.05 parts by mass. In the same manner as in Example 7, an oxygen-absorbing sealed container was produced. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

Example 9
Instead of dry blending cobalt stearate (II) so that the amount of cobalt is 0.05 parts by mass, iron stearate (III) is dry blended so that the amount of iron is 0.05 parts by mass. In the same manner as in Example 7, an oxygen-absorbing sealed container was produced. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Example 10)
An oxygen-absorbing sealed container was prepared in the same manner as in Example 1 except that the tetralin ring-containing copolymer polyolefin compound (3) was used in place of the tetralin ring-containing copolymer polyolefin compound (1). About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Example 11)
An oxygen-absorbing sealed container was produced in the same manner as in Example 1 except that the tetralin ring-containing copolymer polyolefin compound (4) was used instead of the tetralin ring-containing copolymer polyolefin compound (1). About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Comparative Example 1)
Instead of using a tetralin ring-containing copolymer polyolefin compound (1), an ethylene-methyl methacrylate copolymer having a methyl methacrylate content of 25% by mass (product name: “ACRIFT WK402” manufactured by Sumitomo Chemical Co., Ltd.) is used. Produced a sealed container in the same manner as in Example 1. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Comparative Example 2)
A sealed container was produced in the same manner as in Example 1 except that cobalt stearate (II) was not used. About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

(Comparative Example 3)
Iron powder with an average particle size of 30 μm and calcium chloride were mixed at a mass ratio of 100: 1, and this mixture was mixed with linear low-density polyethylene (product name: “Novatech LL UF641” manufactured by Nippon Polyethylene Co., Ltd. And an iron-based oxygen-absorbing resin composition were obtained by kneading at a mass ratio of 30:70. Next, a sealed container was produced in the same manner as in Example 1 except that the iron-based oxygen-absorbing resin composition was used in place of the oxygen-absorbing resin composition (1). About the sealed container, it carried out similarly to Example 1, and measured the oxygen concentration in a container and seal strength, and the odor confirmation in the container was performed. These results are shown in Table 1.

  As is clear from Examples 1 to 11, the oxygen-absorbing sealed container of the present invention exhibits good oxygen absorption performance at high humidity and low humidity, maintains the sealing strength, and is free from odor after oxygen absorption. There was no outbreak.

  Since the oxygen-absorbing sealed container of the present invention has excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, it can be used widely and effectively in general technical fields that require oxygen absorption. It is. In addition, oxygen can be absorbed regardless of the presence or absence of moisture in the object to be stored, and furthermore, since no odor is generated after oxygen absorption, for example, in foods, cooked foods, beverages, pharmaceuticals, health foods, etc. It can be used effectively. In addition, since it is possible to realize a mode insensitive to a metal detector, it can be used widely and effectively in a container for inspecting a metal, a metal piece, or the like from the outside with a metal detector.

Claims (5)

At least three layers in which a sealant layer containing a thermoplastic resin, an oxygen absorbing layer composed of an oxygen absorbing resin composition containing a copolymerized polyolefin compound and a transition metal catalyst, and a gas barrier layer containing a gas barrier material are laminated in this order. A lid containing an oxygen-absorbing multilayer body comprising:
An inner layer containing a thermoplastic resin, a gas barrier layer containing a gas barrier material, and an outer layer containing a thermoplastic resin in this order, and a gas barrier molding container comprising at least three layers,
An oxygen-absorbing sealed container in which the sealant layer in the lid member and the inner layer in the gas barrier molding container are joined;
The copolymer polyolefin compound is a structural unit represented by the following general formula (1);

Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a first monovalent substituent, wherein the first monovalent substituent is a halogen atom, an alkyl Group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio And at least one selected from the group consisting of a group, an arylthio group, a heterocyclic thio group, and an imide group, which may further have a substituent.)
At least one structural unit (a) selected from the group consisting of:
Structural units represented by the following general formulas (2) and (3);

(Wherein R ₅ , R ₆ and R ₇ each independently represent a hydrogen atom or a second monovalent substituent, and R ₈ , R ₉ , R ₁₀ and R ₁₁ are each independently 3 monovalent substituents, wherein the second monovalent substituent and the third monovalent substituent are each independently a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group , Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group and And at least one selected from the group consisting of imide groups, which may further have a substituent, and when there are a plurality of R ₈ , R ₉ , R ₁₀ or R ₁₁ , a plurality of the R ₈ , R ₉ , R ₁₀ R ₁₁ may be the same or different from each other, m is 0 to 3, n is 0 to 7, p is 0 to 6, and q is an integer of 0 to 4, At least one hydrogen atom is bonded to the benzyl position, X is — (C═O) O—, — (C═O) NH—, —O (C═O) —, —NH (C═O )-And-(CHR) s- represents a divalent group selected from the group consisting of-and s represents an integer of 0 to 12. Y is-(CHR) t-, where t is 0-12. R represents a monovalent chemical species selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group.)
An oxygen-absorbing sealed container, which is a copolymerized polyolefin compound containing a structural unit (b) having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing sealed container according to claim 1, wherein the transition metal catalyst contains at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.   The oxygen-absorbing sealed container according to claim 1 or 2, wherein the transition metal catalyst is contained in an amount of 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the copolymer polyolefin compound.   The content rate of the said structural unit (a) with respect to the content rate of the said structural unit (b) contained in the said copolymerization polyolefin compound is 1 / 99-99 / 1 in molar ratio, Any of Claims 1-3 An oxygen-absorbing sealed container according to claim 1. The structural unit (a) is represented by the following formulas (4) and (5);

At least one structural unit selected from the group consisting of:
The structural unit (b) is represented by the following formulas (6) and (7);

The oxygen-absorbing sealed container according to any one of claims 1 to 4, wherein the oxygen-absorbing sealed container is at least one structural unit selected from the group consisting of: