JP5974871B2 - Oxygen-absorbing multilayer injection molding - Google Patents

Description

  The present invention relates to a multilayer injection molded article having an oxygen absorption function, and a container obtained by processing the multilayer injection molded article.

  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. The oxygen absorber to be used 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). Specifically, in an oxygen-absorbing multilayer film, an oxygen absorbent is dispersed between a conventional gas-barrier multilayer film formed by laminating a heat seal layer and a gas barrier layer, optionally via an intermediate layer made of a thermoplastic resin. It has been used as an oxygen absorbing layer that is a thermoplastic resin layer that has been added to provide a function to absorb oxygen in the container in addition to the function of preventing oxygen permeation from the outside, such as extrusion lamination, co-extrusion lamination, and dry lamination. It is manufactured using a known manufacturing method. However, this is also a problem that it can not be detected by metal detectors used for detecting foreign substances such as food, it can not be heated with a microwave oven, and the object to be stored only exhibits high moisture content have. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity. Those using oxygen absorbers such as iron powder are detected by metal detectors used to detect foreign objects such as food, when internal visibility is insufficient due to opacity problems, and the contents are alcoholic drinks There was a problem that aldehyde was generated by the reaction of iron and alcohol, and the flavor was lowered.

  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 Documents 3 and 4). Further, Patent Documents 3 and 4 also exemplify 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 5). .

  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 ring is bonded and a transition metal is known (see Patent Document 6).

  On the other hand, injection molding (injection molding) is widely used in machine parts, automobile parts, electrical / electronic parts, food / medicine containers, etc. because it can produce molded bodies having complicated shapes and has high productivity. . In recent years, various plastic containers have been widely used as packaging containers because they have advantages such as light weight, transparency and easy moldability. As a typical plastic container, for example, in a container such as a beverage, an injection molded body in which a screw shape is formed on a cap so that a lid can be sufficiently tightened is frequently used.

  Examples of the material used for the injection molded article include general-purpose thermoplastic resins such as polyolefin (polyethylene, polypropylene, etc.), polyester, polystyrene, and the like. In particular, injection molded articles mainly composed of polyester such as polyethylene terephthalate (PET) are widely used as plastic containers for beverages such as tea, fruit juice beverages, carbonated beverages and alcoholic beverages. However, although the injection-molded body mainly composed of thermoplastic resin is excellent as a packaging material, unlike glass bottles and metal containers, it tends to allow oxygen to permeate from the outside. There remains a problem with sex. Therefore, in order to impart gas barrier properties to such an injection-molded product made of a general-purpose resin, multilayer injection-molded products having a gas barrier layer as an intermediate layer have been put into practical use.

Japanese Patent Application Laid-Open No. 09-234832 JP-A-51-136845 JP 2001-252560 A JP 2009-108153 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. Further, Patent Document 4 describes a method for improving delamination, but the effect is limited. 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 5 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 6 needs to use a special material containing a cyclohexene functional group, and this material still has a problem that it is relatively easy to generate an odor.

  On the other hand, the above-mentioned conventional gas barrier multilayer containers and medical multilayer containers have insufficient basic performance such as oxygen barrier property, water vapor barrier property, chemical solution adsorption property, container durability, etc. Improvement is required from the viewpoint of storage stability.

  The present invention has been made in view of the above problems, and its object is to provide a novel oxygen-absorbing multilayer that is not sensitive to metal detectors, has no odor generation after oxygen absorption, and has excellent oxygen absorption performance. An object of the present invention is to provide an injection molded article and an oxygen-absorbing container using the same. Another object of the present invention is to provide an oxygen-absorbing multilayer injection molded article having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and an oxygen-absorbing container using the same. There is.

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。各式中、ｍは、それぞれ独立して、０〜３の整数を示し、各式中、ｎは、それぞれ独立して、０〜７の整数を示し、テトラリン環のベンジル位には少なくとも１つ以上の水素原子が結合している。各式中、Ｘは、それぞれ独立して、芳香族炭化水素基、飽和または不飽和の脂環式炭化水素基、直鎖状または分岐状の飽和または不飽和の脂肪族炭化水素基および複素環基からなる群から選ばれる少なくとも１つの基を含有する２価の基を示す。）
からなる群より選択される少なくとも１つのテトラリン環を有する構成単位を含有する、酸素吸収性多層インジェクション成形体。
＜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＞に記載の酸素吸収性多層インジェクション成形体。
＜３＞ 前記遷移金属触媒が、前記ポリアミド化合物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多層インジェクション成形体。
＜４＞ 前記一般式（１）で表される構成単位が、下記式（３）〜（６）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つである、上記＜１＞〜＜３＞のいずれかに記載の酸素吸収性多層インジェクション成形体。
＜５＞ 上記＜１＞〜＜４＞のいずれか一項に記載の酸素吸収性多層インジェクション成形体を、カップ状またはボトル状に成形加工して得られる、酸素吸収性多層容器。
＜６＞ 前記成形加工が、延伸ブロー成形である、上記＜５＞に記載の酸素吸収性多層容器。 As a result of earnest studies on the oxygen-absorbing multilayer injection molded article, the present inventors have found that the above problems can be solved by using a polyamide compound having a predetermined tetralin ring and a transition metal catalyst. Completed the invention.
That is, the present invention provides the following <1> to <6>.
<1> Oxygen-absorbing multilayer injection molding comprising an oxygen-absorbing layer (layer A) comprising an oxygen-absorbing resin composition containing a polyamide compound and a transition metal catalyst, and a resin layer (layer B) containing a thermoplastic resin Body,
The polyamide compound is a structural unit represented by the following general formulas (1) to (2);

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group And each of them may further have a substituent, wherein each m independently represents an integer of 0 to 3, and in each formula, n is each independently Represents an integer of 0 to 7, and at least one hydrogen atom is bonded to the benzylic position of the tetralin ring, wherein each X is independently an aromatic hydrocarbon group, saturated or unsaturated. Sat It shows the alicyclic hydrocarbon group, a divalent group containing at least one group selected from the group consisting of aliphatic hydrocarbon group and the heterocyclic group of linear or branched, saturated or unsaturated.)
An oxygen-absorbing multilayer injection molded article containing a structural unit having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing multilayer injection molded article 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 multilayer injection molded article 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 polyamide compound. .
<4> The structural unit represented by the general formula (1) is represented by the following formulas (3) to (6);

The oxygen-absorbing multilayer injection molded article according to any one of <1> to <3>, which is at least one selected from the group consisting of:
<5> An oxygen-absorbing multilayer container obtained by molding the oxygen-absorbing multilayer injection molded article according to any one of <1> to <4> into a cup shape or a bottle shape.
<6> The oxygen-absorbing multilayer container according to <5>, wherein the molding process is stretch blow molding.

  According to the present invention, an oxygen-absorbing multilayer injection molded article having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity, and an oxygen-absorbing multilayer container using the same can be realized. . And these oxygen-absorbing multilayer injection molded articles and oxygen-absorbing multilayer containers can absorb oxygen regardless of the presence or absence of moisture in the object to be stored, and there is no odor generation after oxygen absorption. It can be used in a wide range of applications, including foods, cooked foods, beverages, pharmaceuticals, and health foods, regardless of the object. In addition, an oxygen-absorbing multilayer injection molded body and an oxygen-absorbing multilayer container that are not sensitive to metal detectors can be realized. Furthermore, according to a preferred embodiment of the present invention, the strength of the polyamide compound due to oxidation is very small even after oxygen absorption, and the oxygen absorption layer is maintained in strength even in long-term use. An absorptive multilayer injection molded article, an oxygen-absorbing multilayer container, and the like can also be realized.

  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 injection molded product]
The oxygen-absorbing multilayer injection molded article of this embodiment includes at least an oxygen-absorbing layer (layer A) made of an oxygen-absorbing resin composition and a resin layer (layer B) containing a thermoplastic resin.

  By using the oxygen-absorbing multilayer injection molded article of this embodiment as a part of the components of the container for sealing, oxygen in the container is absorbed and little oxygen penetrates or penetrates from the outside of the container. However, in some cases, this permeating or penetrating oxygen can also be absorbed to prevent alteration of the stored content item (stored object) due to oxygen. At this time, the injection molded body of the present embodiment may itself be molded into a container shape. Considering that the oxygen-absorbing multilayer injection molded article of the present embodiment exhibits oxygen absorption performance, it is preferably a storage container such as a cup-shaped container (injection cup) or a bottle-shaped container.

  The layer structure in the oxygen-absorbing multilayer injection molded article of the present embodiment is not particularly limited, and the number and types of oxygen-absorbing layers (layer A) and resin layers (layer B) are not particularly limited. For example, an A / B configuration composed of one layer A and one layer B may be employed, or a three-layer configuration of B / A / B composed of one layer A and two layers B may be employed. Further, a five-layer configuration of B1 / B2 / A / B2 / B1 including one layer A, two layers B1, and two layers B2 may be used. Furthermore, the multilayer injection molded article of the present embodiment may include an arbitrary layer such as an adhesive layer (layer AD) as necessary, for example, seven layers of B1 / AD / B2 / A / B2 / AD / B1. It may be a configuration.

[Oxygen absorbing layer (layer A)]
In the oxygen-absorbing multilayer injection molded article of this embodiment, the oxygen-absorbing layer (layer A) is at least one tetralin selected from the group consisting of the structural units represented by the general formulas (1) to (2). It consists of an oxygen-absorbing resin composition containing a polyamide compound containing a structural unit having a ring (hereinafter also simply referred to as “tetralin ring-containing polyamide compound”) and a transition metal catalyst.

<Tetralin ring-containing polyamide compound>
The tetralin ring-containing polyamide compound used in the oxygen-absorbing resin composition of the present embodiment contains at least one of the structural units represented by the general formulas (1) to (2). The structural unit represented by the general formula (1) is preferably at least one selected from the group consisting of structural units represented by the above formulas (3) to (6). 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 polyamide compound. Thus, when the tetralin ring-containing polyamide compound is a polymer, any one of the homopolymer of the structural unit, a random copolymer of the structural unit and other structural units, and a block copolymer of the structural unit and other structural units. It does not matter.

  In the structural units represented by the general formulas (1) to (2), examples of the monovalent substituent represented by R include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably A linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, more preferably 1 to 6 carbon atoms, such as a 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 a linear, branched or cyclic alkenyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, For example, vinyl group, allyl group), alkynyl group (preferably alkynyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, such as ethynyl group, propargyl group), aryl A group (preferably 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), a heterocyclic group (preferably having a carbon number of 1 to 12, more preferably carbon A monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound having a number of 2 to 6, such as a 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 1 to 6 carbon atoms). A linear, branched or cyclic alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, eg 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 carbon atoms. An arylcarbonyl group having 7 to 9 carbon atoms, for example, an acetyl group, a pivaloyl group, a benzoyl group), an amino group (preferably having 1 to 10 carbon atoms, more preferably an alkylamino group having 1 to 6 carbon atoms, preferably An anilino group having 6 to 12 carbon atoms, 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, such as an amino group, methyl Amino 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, ethyl Luthio group), an arylthio 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, and more). Preferably a heterocyclic thio group having 1 to 6 carbon atoms, such as a 2-benzothiazolylthio group, an imide group (preferably an imide group having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, Examples thereof include N-succinimide group and N-phthalimide group), but are not particularly limited thereto.

  In addition, when said monovalent substituent R has a hydrogen atom, the hydrogen atom is a substituent T (Here, the substituent T is synonymous with what was demonstrated by said monovalent substituent R.). ) May be further substituted. 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. When the monovalent substituent R has a monovalent substituent T, the carbon number described above does 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. When the monovalent substituent R has a substituent T, there may be a plurality of the substituents T.

In the structural units represented by the general formulas (1) to (2), X is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. And a divalent group containing at least one group selected from the group consisting of an aliphatic hydrocarbon group and a heterocyclic group. Aromatic hydrocarbon group, saturated or unsaturated alicyclic hydrocarbon group, linear or branched saturated or unsaturated aliphatic hydrocarbon group and heterocyclic group may be substituted or unsubstituted . X may contain a hetero atom, or may contain an ether group, sulfide group, carbonyl group, hydroxy group, amino group, sulfoxide group, sulfone group or the like.
Here, as the aromatic hydrocarbon group, for example, o-phenylene group, m-phenylene group, p-phenylene group, methylphenylene group, o-xylylene group, m-xylylene group, p-xylylene group, naphthylene group, Anthracenylene group, phenanthrylene group, biphenylene group, fluoronylene group and the like can be mentioned, but not limited thereto. Examples of the alicyclic hydrocarbon group include a cycloalkylene group such as a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group, and a cyclooctylene group, and a cycloalkenylene group such as a cyclohexenylene group. Although it is mentioned, it is not specifically limited to these. Examples of the aliphatic hydrocarbon group include methylene group, ethylene group, trimethylene group, propylene group, isopropylidene group, tetramethylene group, isobutylidene group, sec-butylidene group, pentamethylene group, hexamethylene group, heptamethylene group, Linear or branched alkylene groups such as octamethylene group, nonamethylene group, decamethylene group, vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, 1,3-butadienylene group, 1-pentenylene group Alkenylene groups such as 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 3-hexenylene group and the like, but are not particularly limited thereto. These may further have a substituent, and specific examples thereof include, for example, halogen, alkoxy group, hydroxy group, carboxyl group, carboalkoxy group, amino group, acyl group, thio group (for example, alkylthio group, Phenylthio group, tolylthio group, pyridylthio group, etc.), amino group (for example, unsubstituted amino group, methylamino group, dimethylamino group, phenylamino group, etc.), cyano group, nitro group and the like, but not limited thereto .

  The tetralin ring-containing polyamide compound containing the structural unit represented by the general formula (1) is, for example, polycondensation of a dicarboxylic acid having a tetralin ring or a derivative (I) thereof with a diamine or a derivative (II) thereof. Can be obtained.

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。ｍは０〜３の整数を示し、ｎは０〜７の整数を示し、テトラリン環のベンジル位には少なくとも１つ以上の水素原子が結合している。） Examples of the dicarboxylic acid having a tetralin ring or its derivative (I) include compounds represented by the following general formula (7). The dicarboxylic acid having a tetralin ring or its derivative (I) can be used alone or in combination of two or more.

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group At least one kind, which may further have a substituent, m represents an integer of 0 to 3, n represents an integer of 0 to 7, and at least one or more at the benzylic position of the tetralin ring Of hydrogen atoms are bonded.)

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。ｍは、それぞれ独立して０〜３の整数を示す。） The compound represented by the general formula (7) can be obtained, for example, by reacting a dicarboxylic acid having a naphthalene ring represented by the following general formula (8) or a derivative thereof with hydrogen.

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group These are at least one kind, and these may further have a substituent, each m independently represents an integer of 0 to 3.)

  Examples of the diamine or its derivative (II) include ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, and undecamethylene diamine. , Straight-chain saturated aliphatic diamines such as dodecamethylenediamine and tridecamethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, 2,4-dimethyloctamethylene Branched saturated aliphatic amines such as diamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) Alicyclic amines such as cyclohexane, meta-xylylenediamine, para-xylylenediamine amine, meta-phenylenediamine, aromatic amines paraphenylenediamine, etc. or their derivatives, and the like. Diamine or its derivative (II) can be used individually by 1 type or in combination of 2 or more types.

  The tetralin ring-containing polyamide compound containing the structural unit represented by the general formula (2) is, for example, polycondensation of a diamine having a tetralin ring or a derivative (III) thereof and a dicarboxylic acid or a derivative (IV) thereof. Can be obtained.

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。ｍは０〜３の整数を示し、ｎは０〜７の整数を示し、テトラリン環のベンジル位には少なくとも１つ以上の水素原子が結合している。） Examples of the diamine having a tetralin ring or a derivative (III) thereof include compounds represented by the following general formula (9). A diamine having a tetralin ring or a derivative (III) thereof can be used alone or in combination of two or more.

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group At least one kind, which may further have a substituent, m represents an integer of 0 to 3, n represents an integer of 0 to 7, and at least one or more at the benzylic position of the tetralin ring Of hydrogen atoms are bonded.)

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。ｍは、それぞれ独立して０〜３の整数を示す。） The compound represented by the general formula (9) can be obtained, for example, by reacting a diamine having a naphthalene ring represented by the following general formula (10) or a derivative thereof with hydrogen.

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group These are at least one kind, and these may further have a substituent, each m independently represents an integer of 0 to 3.)

  Examples of the dicarboxylic acid or its derivative (IV) include oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and 3,3-dimethylpentanedioic acid. Benzene dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, phenylmalonic acid, phenylenediacetic acid, phenylenedibutyric acid, 4,4-diphenyletherdicarboxylic acid And acid, p-phenylenedicarboxylic acid, or derivatives thereof. Dicarboxylic acid or its derivative (IV) can be used individually by 1 type or in combination of 2 or more types.

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。ｍは、それぞれ独立して０〜３の整数を示す。Ｘは芳香族炭化水素基、飽和または不飽和の脂環式炭化水素基、直鎖状または分岐状の飽和または不飽和の脂肪族炭化水素基および複素環基からなる群から選ばれる少なくとも１つの基を含有する２価の基を示す。）

（式中、Ｒは、それぞれ独立して、一価の置換基を示し、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。ｍは、それぞれ独立して０〜３の整数を示す。Ｘは芳香族炭化水素基、飽和または不飽和の脂環式炭化水素基、直鎖状または分岐状の飽和または不飽和の脂肪族炭化水素基および複素環基からなる群から選ばれる少なくとも１つの基を含有する２価の基を示す。） Moreover, the tetralin ring containing polyamide compound containing the structural unit represented by the said general formula (1) or (2) is a polyamide containing the structural unit represented by the following general formula (11) or (12), for example It can be obtained by reacting the compound with hydrogen.

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group At least one kind, which may further have a substituent, each m independently represents an integer of 0 to 3. X is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic group. And a divalent group containing at least one group selected from the group consisting of a hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group.)

(In the formula, each R independently represents a monovalent substituent, which is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, Selected from the group consisting of a 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 imide group At least one kind, which may further have a substituent, each m independently represents an integer of 0 to 3. X is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic group. And a divalent group containing at least one group selected from the group consisting of a hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group.)

  Specific examples of the monovalent substituent represented by R and the divalent group represented by X in the structural units represented by the general formulas (7) to (12) include the general formulas (1) to (2). It is the same as that described in the structural unit represented by Therefore, the duplicate description here is omitted.

（式中、ｌは、２〜１８の整数を表す。） The tetralin ring-containing polyamide compound used in the oxygen-absorbing resin composition of the present embodiment is a structural unit having another tetralin ring other than the structural units represented by the general formulas (1) to (2), and / or Or the structural unit which does not have a tetralin ring may be included as a copolymerization component. Specifically, the compounds shown in the aforementioned diamine or its derivative (II) or dicarboxylic acid or its derivative (IV) can be used as a copolymerization component. Moreover, you may further contain the omega-aminocarboxylic acid unit represented by the following general formula (13).

(In the formula, l represents an integer of 2 to 18.)

  Examples of the compound that can constitute the ω-aminocarboxylic acid unit represented by the general formula (13) include ω-aminocarboxylic acid having 3 to 19 carbon atoms and lactam having 3 to 19 carbon atoms. Examples of the ω-aminocarboxylic acid having 3 to 19 carbon atoms include 6-aminohexanoic acid and 12-aminododecanoic acid. Examples of the lactam having 3 to 19 carbon atoms include ε-caprolactam and laurolactam. However, it is not limited to these. These can be used alone or in combination of two or more.

  Among the tetralin ring-containing polyamide compounds containing the structural unit represented by the general formula (1), a tetralin ring containing the structural units represented by the above formulas (3) to (6) is more preferable. And a containing polyamide compound.

The molecular weight of the tetralin ring-containing polyamide 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 ⁶ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁶ . 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} 5.0 × 10 ⁴ . In addition, all the molecular weights here mean the value of polystyrene conversion. In addition, said tetralin ring containing polyamide compound can be used individually by 1 type or in combination of 2 or more types.

  Moreover, although the glass transition temperature (Tg) of said tetralin ring containing polyamide compound is not specifically limited, It is preferable that it is 0-150 degreeC, More preferably, it is 10-130 degreeC. The glass transition temperature here means a value measured by differential scanning calorimetry.

  The method for producing the tetralin ring-containing polyamide compound is not particularly limited, and any conventionally known method for producing polyamide can be applied. Examples of the method for producing polyamide include a pressurized salt method, a normal pressure dropping method, and a pressure dropping method. Among these, the pressurized salt method is preferable.

  The pressurized salt method is a method of performing polycondensation under pressure using a salt of dicarboxylic acid and diamine as raw materials. Specifically, after preparing an aqueous solution containing a salt of a dicarboxylic acid and a diamine in a set molar ratio composed of a dicarboxylic acid and a diamine, the aqueous solution is concentrated and then heated under pressure to remove condensed water. This is a method of polycondensation.

  The normal pressure dropping method is a method in which after dicarboxylic acid is heated and melted, a diamine component is continuously dropped under normal pressure to perform polycondensation while removing condensed water. At this time, the polycondensation reaction is performed while raising the temperature so that the reaction temperature does not fall below the melting point of the polyamide to be produced. When the set molar ratio is reached, the dropwise addition of the diamine is terminated, the temperature is raised to a temperature about 10 ° C. higher than the melting point of the polyamide, and the polycondensation is continued.

  In the pressure dropping method, after the dicarboxylic acid component is heated and melted, the pressure is preferably increased to about 0.3 to 0.4 MPaG, the diamine component is continuously dropped, and the condensed water is removed. This is a method of polycondensation. At this time, the polycondensation reaction is performed while raising the temperature so that the reaction temperature does not fall below the melting point of the polyamide to be produced. When the set molar ratio is reached, the dropping of the diamine component is terminated, and while gradually returning to normal pressure, the temperature is raised to a temperature about 10 ° C. higher than the melting point of the polyamide and maintained for a predetermined time to continue polycondensation.

  The polyamide produced by the polycondensation method can be used as it is, but may be subjected to a step for further increasing the degree of polymerization. Further examples of the step of increasing the degree of polymerization include reactive extrusion in an extruder and solid phase polymerization. As a heating device used in solid phase polymerization, a continuous heating drying device, a tumble dryer, a conical dryer, a rotary drum heating device called a rotary dryer, etc., and a rotary blade inside a nauta mixer are provided. A conical heating device can be preferably used, but a known method and device can be used without being limited thereto. Especially in the case of solid-phase polymerization of polyamide, the rotary drum type heating device in the above-mentioned device can seal the inside of the system, and it is easy to proceed with polycondensation in a state where oxygen that causes coloring is removed. Preferably used.

  In the production of the tetralin ring-containing polyamide compound, any conventionally known ones such as various stabilizers such as a heat stabilizer and a light stabilizer, and a polymerization regulator can be used. These types and amounts used may be appropriately selected according to the reaction rate, the molecular weight of the tetralin ring-containing polyamide compound, the glass transition temperature, the viscosity, the color tone, the safety, the thermal stability, the weather resistance, and the elution property of itself. There is no particular limitation.

The preferred relative viscosity of the tetralin ring-containing polyamide compound is preferably 1.8 to 4.2, more preferably 1.9 to 4.0, and still more preferably, from the viewpoints of strength and appearance of the molded product and molding processability. Is 2.0 to 3.8.
The relative viscosity here refers to 96% measured in the same manner as the dropping time (t) measured at 25 ° C. with a Cannon Fenceke viscometer by dissolving 1 g of a tetralin ring-containing polyamide compound in 100 mL of 96% sulfuric acid. It is the ratio of the drop time (t ₀ ) of sulfuric acid itself, and is represented by the following formula.
Relative viscosity = t / t ₀

  All of the above-mentioned tetralin ring-containing polyamide compounds have hydrogen at the benzylic position of the tetralin ring, and when used in combination with the above-described transition metal catalyst, hydrogen at the benzylic position is extracted, thereby providing an excellent oxygen absorption capacity. Is expressed.

  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 polyamide 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 to produce a hydroxy group or It is thought that a ketone group is 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, and the structure of the tetralin ring-containing polyamide compound is maintained, causing odor. This is presumably because the low molecular weight organic compound is hardly 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 polyamide compound. There is no particular limitation.

  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 transition metal and an organic acid, the transition metal is manganese, iron, cobalt, nickel or copper, and the organic acid is acetic acid, stearic acid, 2-ethylhexanoic acid, olein. A combination that is an acid or naphthenic acid is more preferred. 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 polyamide compound and the transition metal catalyst in the oxygen-absorbing resin composition of the present embodiment can be appropriately set according to the type and desired performance of the tetralin ring-containing polyamide compound and the transition metal catalyst to be used. Yes, it 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 preferably 0.001 to 10 parts by mass as a transition metal amount with respect to 100 parts by mass of the tetralin ring-containing polyamide compound. More preferably, it is 0.002-2 mass part, More preferably, it is 0.005-1 mass part.

<Other thermoplastic resins>
Moreover, the oxygen-absorbing resin composition of this embodiment may further contain other thermoplastic resins other than the said tetralin ring containing polyamide compound as needed. 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 polyamide compound, the transition metal catalyst, and the thermoplastic resin 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. Examples of such optional components include additives such as desiccants, pigments, dyes, antioxidants, slip agents, antistatic agents, stabilizers, fillers such as calcium carbonate, clay, mica, silica, and deodorants. However, it is not particularly limited 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 1 to 1000 μm, more preferably 2 to 2 μm. It is 800 micrometers, More preferably, it is 5-700 micrometers. 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.

[Resin layer containing thermoplastic resin (layer B)]
The resin layer (layer B) of the oxygen-absorbing multilayer body of the present embodiment is a layer containing a thermoplastic resin. The content ratio of the thermoplastic resin in the layer B 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 B. Is 90 to 100% by mass.

  The oxygen-absorbing multilayer body of this embodiment may have a plurality of layers B, and the configurations of the plurality of layers B may be the same or different from each other. Further, in the oxygen-absorbing multilayer body of the present embodiment, the thickness of the layer B can be appropriately determined according to the application and desired performance, and is not particularly limited, but strength such as drop resistance required for the multilayer body. From the viewpoint of securing various physical properties such as flexibility and flexibility, the thickness is preferably 5 to 1000 μm, more preferably 10 to 800 μm, and still more preferably 20 to 500 μm.

  As the thermoplastic resin of the layer B of the oxygen-absorbing multilayer body of the present embodiment, any thermoplastic resin can be used and is not particularly limited. Specifically, the layer B of the present embodiment contains at least one thermoplastic resin selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, plant-derived resin, and chlorine-based resin. preferable. In addition, the thermoplastic resin used for the layer B of the present embodiment preferably contains 50 to 100% by mass, more preferably 70 to 100% by mass, of the thermoplastic resin other than the tetralin ring-containing polyamide compound with respect to the total amount. More preferably, it is 90-100 mass%.

Hereinafter, the thermoplastic resin suitably used in the layer B of the oxygen-absorbing multilayer body of the present embodiment will be exemplified.
<Polyolefin>
Specific examples of the polyolefin used in the layer B of the oxygen-absorbing multilayer body of the present embodiment include polyethylenes such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene Olefin homopolymers such as polybutene-1, poly-4-methylpentene-1; ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cyclic Copolymer of ethylene and α-olefin such as olefin copolymer; Ethylene-α, β-unsaturated carboxylic acid copolymer such as ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid Ethylene-α, β-unsaturated carboxylic acid ester copolymer such as ethyl copolymer, ethyl Other α-, β-unsaturated carboxylic acid copolymer ionic cross-linked products, other ethylene copolymers such as ethylene-vinyl acetate copolymer; cyclic olefins ring-opened polymers and hydrogenated products thereof; cyclic olefins An ethylene copolymer; and a graft-modified polyolefin obtained by graft-modifying these polyolefins with an acid anhydride such as maleic anhydride.

<Polyester>
Specific examples of the polyester used in the layer B of the oxygen-absorbing multilayer body of the present embodiment include a polyvalent carboxylic acid containing a dicarboxylic acid and a polyvalent carboxylic acid containing one or more selected from these ester-forming derivatives and a glycol. The thing which consists of 1 type or 2 or more types chosen from alcohol, the thing which consists of hydroxycarboxylic acid and these ester-forming derivatives, or the thing which consists of cyclic ester etc. are mentioned. The ethylene terephthalate-based thermoplastic polyester is composed of an ethylene terephthalate unit in the majority of ester repeating units, generally 70 mol% or more, and has a glass transition point (Tg) of 50 to 90 ° C. and a melting point (Tm) of 200 to 275. Those in the range of ° C. are preferred. As an ethylene terephthalate thermoplastic polyester, polyethylene terephthalate is particularly superior in terms of pressure resistance, heat resistance, heat pressure resistance, etc., but in addition to the ethylene terephthalate unit, from dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid and diols such as propylene glycol Copolyesters containing small amounts of ester units can also be used.

  Specific examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid 3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid Saturated aliphatic dicarboxylic acids exemplified in the above, or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified in fumaric acid, maleic acid, itaconic acid, etc., or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid ,Terephthalic acid 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid such as 2,7-naphthalenedicarboxylic acid, 4,4′- Examples include biphenyl dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic acid, and the like. Aromatic dicarboxylic acids or their ester-forming derivatives, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium Exemplified by sulfoterephthalic acid Genus sulfonate group-containing aromatic dicarboxylic acid or lower alkyl ester derivatives thereof, and the like.

  Among the above dicarboxylic acids, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acids are particularly preferable from the viewpoint of physical properties of the resulting polyester. In addition, you may copolymerize another dicarboxylic acid as needed.

  Specific examples of polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyl. Examples thereof include tetracarboxylic acid and ester-forming derivatives thereof.

  Specific examples of glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol. 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, polyethylene glycol Aliphatic glycols exemplified by polytrimethylene glycol and polytetramethylene glycol, hydroquinone, 4,4′-dihydroxybisphenol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-bis ( β-hydroxyethoxyphenyl) sulfone, bis (p-hydroxyphenyl) ether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, 1,2-bis (p-hydroxyphenyl) ethane, bisphenol A , Bisphenol C, 2,5-naphthalenediol, and aromatic glycols exemplified by glycols obtained by adding ethylene oxide to these glycols.

  Among the above glycols, it is particularly preferable to use ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, and 1,4-cyclohexanedimethanol as the main component.

  Specific examples of polyhydric alcohols other than these glycols include trimethylol methane, trimethylol ethane, trimethylol propane, pentaerythritol, glycerol, hexanetriol, and the like.

  Specific examples of the hydroxycarboxylic acid include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexanecarboxylic acid. Or ester-forming derivatives thereof.

  Specific examples of the cyclic ester include ε-caprolactone, β-propiolactone, β-methyl-β-propiolactone, δ-valerolactone, glycolide, lactide and the like.

  Specific examples of ester-forming derivatives of polyvalent carboxylic acids and hydroxycarboxylic acids include these alkyl esters, acid chlorides, acid anhydrides and the like.

  Among those described above, a polyester in which the main acid component is terephthalic acid or an ester-forming derivative thereof or naphthalenedicarboxylic acid or an ester-forming derivative thereof, and the main glycol component is alkylene glycol is preferable.

  In addition, the polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of terephthalic acid or an ester-forming derivative thereof in total with respect to the total acid component, More preferred is a polyester containing 80 mol% or more, and even more preferred is a polyester containing 90 mol% or more. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is preferably a polyester containing naphthalenedicarboxylic acid or an ester-forming derivative in total of 70 mol% or more, more preferably It is a polyester containing 80 mol% or more, more preferably a polyester containing 90 mol% or more.

  Among the above-mentioned naphthalenedicarboxylic acids or ester-forming derivatives thereof, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid exemplified in dicarboxylic acids 2,7-naphthalenedicarboxylic acid or their ester-forming derivatives are preferred.

  Further, the polyester in which the main glycol component is alkylene glycol is preferably a polyester containing 70 mol% or more of alkylene glycol in total with respect to all glycol components, and more preferably polyester containing 80 mol% or more. More preferably, it is a polyester containing 90 mol% or more. In addition, the alkylene glycol said here may contain the substituent and the alicyclic structure in the molecular chain.

  The copolymer components other than the terephthalic acid / ethylene glycol are isophthalic acid, 2,6-naphthalenedicarboxylic acid, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, from the viewpoint of achieving both transparency and moldability. It is preferably at least one selected from the group consisting of 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propanediol. Isophthalic acid, diethylene glycol, neopentyl glycol and 1 More preferred is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.

  A preferred example of the polyester used for the layer B of the oxygen-absorbing multilayer body of the present embodiment is a polyester whose main repeating unit is composed of ethylene terephthalate. More preferred is a linear polyester containing 70 mol% or more of ethylene terephthalate units, still more preferred is a linear polyester containing 80 mol% or more of ethylene terephthalate units, and particularly preferred is a line containing 90 mol% or more of ethylene terephthalate units. Polyester.

  Another preferred example of the polyester used for the layer B of the oxygen-absorbing multilayer body of the present embodiment is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate. More preferably, it is a linear polyester containing 70 mol% or more of ethylene-2,6-naphthalate units, more preferably a linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, and particularly preferred is , A linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units.

  Further, other preferable examples of the polyester used for the layer B of the oxygen-absorbing multilayer body of the present embodiment include a linear polyester containing 70 mol% or more of propylene terephthalate units, and a linear containing 70 mol% or more of propylene naphthalate units. Polyester, linear polyester containing 70 mol% or more of 1,4-cyclohexanedimethylene terephthalate units, linear polyester containing 70 mol% or more of butylene naphthalate units, or linear polyester containing 70 mol% or more of butylene terephthalate units. .

  From the viewpoint of coexistence of transparency and moldability, particularly suitable polyesters include a combination of terephthalic acid / isophthalic acid / ethylene glycol, terephthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol as a combination of the whole polyester. Combination, terephthalic acid / ethylene glycol / neopentyl glycol combination. Needless to say, the above-mentioned polyester may contain a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol during esterification (transesterification) reaction or polycondensation reaction. .

  Other preferred examples of the polyester used for layer B of the oxygen-absorbing multilayer body of the present embodiment include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. It is done. The polyglycolic acid may be one in which other components such as lactide are copolymerized.

<Polyamide>
The polyamide described below is a polyamide exemplified as the thermoplastic resin of the layer B, and does not include the tetralin ring-containing polyamide compound of this embodiment. Specific examples of the polyamide used in the layer B of the oxygen-absorbing multilayer body of the present embodiment include polyamides whose main constituent units are units derived from lactam or aminocarboxylic acid, and aliphatic diamines and aliphatic dicarboxylic acids. Derived from aliphatic polyamides having derived units as main constituent units, partially aromatic polyamides having units derived from aliphatic diamines and aromatic dicarboxylic acids as main constituent units, aromatic diamines and aliphatic dicarboxylic acids A partially aromatic polyamide having the main unit as the main constituent unit. The polyamide referred to here may be a copolymer of monomer units other than the main structural unit, if necessary.

  Specific examples of the lactam or aminocarboxylic acid include lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, and aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid. Can be mentioned.

  Specific examples of the aliphatic diamine include an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof, an alicyclic diamine, and the like. The aliphatic diamine may be a linear aliphatic diamine or a branched chain aliphatic diamine. Specific examples of such linear aliphatic diamines include ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Examples thereof include aliphatic diamines such as nonamethylene diamine, decamethylene diamine, undecamethylene diamine and dodecamethylene diamine. Specific examples of the alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like.

  Specific examples of the aliphatic dicarboxylic acid include linear aliphatic dicarboxylic acid and alicyclic dicarboxylic acid. In particular, a linear aliphatic dicarboxylic acid having an alkylene group having 4 to 12 carbon atoms is preferable. As the linear aliphatic dicarboxylic acid, adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, dimer acid and their functions And the like. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like.

  Specific examples of aromatic diamines include metaxylylenediamine, paraxylylenediamine, para-bis (2-aminoethyl) benzene, and the like.

  Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, and functional derivatives thereof. Is mentioned.

  Specific polyamides include polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 4, 6, polyamide 6, 6, polyamide 6, 10, polyamide 6T, polyamide 9T, polyamide 6IT, polymetaxylylene azide. Pamide (Polyamide MXD6), Isophthalic acid copolymer polymetaxylylene adipamide (Polyamide MXD6I), Polymetaxylylene sebamide (Polyamide MXD10), Polymetaxylylene decanamide (Polyamide MXD12), Poly 1,3-bis Examples include aminocyclohexane adipamide (polyamide BAC6) and polyparaxylylene sebacamide (polyamide PXD10). More preferable polyamides include polyamide 6, polyamide MXD6, and polyamide MXD6I.

  In addition, as a copolymerization component that may be copolymerized with the polyamide, a polyether having at least one terminal amino group or terminal carboxyl group and a number average molecular weight of 2000 to 20000, or a polymer having the terminal amino group is used. An ether organic carboxylate or an amino salt of a polyether having a terminal carboxyl group can also be used. Specific examples thereof include bis (aminopropyl) poly (ethylene oxide) (polyethylene glycol having a number average molecular weight of 2000 to 20000).

  The partially aromatic polyamide may contain a structural unit derived from a polybasic carboxylic acid having 3 or more bases such as trimellitic acid and pyromellitic acid within a substantially linear range.

<Ethylene-vinyl alcohol copolymer>
The ethylene vinyl alcohol copolymer used in layer B of the oxygen-absorbing multilayer body of this embodiment has an ethylene content of 15 to 60 mol% and a vinyl acetate component saponification degree of 90 mol% or more. Is preferred. The ethylene content is preferably 20 to 55 mol%, more preferably 29 to 44 mol%. The saponification degree of the vinyl acetate component is preferably 95 mol% or more. The ethylene vinyl alcohol copolymer is composed of α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, unsaturated carboxylic acid or salt thereof, partial alkyl ester, complete alkyl ester, nitrile, amide. Further, a small amount of a comonomer such as an anhydride, an unsaturated sulfonic acid or a salt thereof may be further contained.

<Plant-derived resin>
The plant-derived resin used in the layer B of the oxygen-absorbing multilayer body of the present embodiment is not particularly limited as long as it is a resin containing a plant-derived substance as a raw material. Specific examples of plant-derived resins include aliphatic polyester-based biodegradable resins. Examples of the aliphatic polyester biodegradable resin include poly (α-hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES). And polyalkylene alkanoates.

<Chlorine-based resin>
The chlorine-based resin used in the layer B of the oxygen-absorbing multilayer body of the present embodiment may be a resin containing chlorine as a structural unit, and a known resin can be used. Specific examples of the chlorine-based resin include polyvinyl chloride, polyvinylidene chloride, and copolymers of these with vinyl acetate, maleic acid derivatives, higher alkyl vinyl ethers, and the like.

  Further, the layer B 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 B from the viewpoint of recycling and reworking offcuts generated during production.

  The oxygen-absorbing multilayer injection molded article of the present embodiment may contain an arbitrary layer in addition to the above-described oxygen-absorbing layer (layer A) and resin layer (layer B) depending on the desired performance and the like. . Examples of such an arbitrary layer include an adhesive layer.

  For example, from the viewpoint of further increasing the interlayer adhesive strength between two adjacent layers, it is preferable to provide an adhesive layer (layer AD) between the two layers. The adhesive layer preferably contains a thermoplastic resin having adhesiveness. As the thermoplastic resin having adhesiveness, for example, an acid modification obtained by modifying a polyolefin resin such as polyethylene or polypropylene with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid Polyolefin resin; polyester-based thermoplastic elastomer mainly composed of a polyester-based block copolymer. Further, from the viewpoint of enhancing the adhesiveness with the resin layer (layer B) described above, a resin obtained by modifying the same type of resin as the thermoplastic resin used for the layer B is preferable. The thickness of the adhesive layer is not particularly limited, but is preferably 2 to 100 μm, more preferably 5 to 90 μm, and still more preferably from the viewpoint of ensuring molding processability while exhibiting practical adhesive strength. Is 10-80 μm.

  The method for producing the oxygen-absorbing multilayer injection molded article of the present embodiment is not particularly limited, and a known method can be applied depending on the properties of various materials, the target shape, and the like. Various injection molding methods can be applied to produce an injection molded body. Using a molding machine equipped with two or more injection machines and an injection mold, the material constituting layer A and the material constituting layer B are injected into the cavity from the respective injection cylinders through the mold hot runner. By doing so, a multilayer injection molded article having a two-layer structure A / B having a shape corresponding to the cavity shape of the injection mold can be manufactured. First, the material constituting the layer B is injected from the injection cylinder, then the material constituting the layer A is injected from another injection cylinder simultaneously with the resin constituting the layer B, and then the resin constituting the layer B By injecting a necessary amount of the solution to fill the cavity, a multilayer injection molded body having a three-layer structure B / A / B can be manufactured. Further, first, the material constituting the layer B is injected, then the material constituting the layer A is injected alone, and finally the necessary amount of the material constituting the layer B is injected to fill the cavity. A multilayer injection molded article having the structure B / A / B / A / B can be produced. Still further, first, the material constituting the layer B1 is injected from the injection cylinder, then the material constituting the layer B2 is injected from another injection cylinder simultaneously with the resin constituting the layer B1, and then the layer A is constituted. By injecting the resin simultaneously with the resins constituting the layers B1 and B2, and then injecting a necessary amount of the resin constituting the layer B1 to fill the cavity, the five-layer structure B1 / B2 / A / B2 / B1 A multilayer injection molded article can be produced. In addition, in order to give heat resistance to the mouth and neck of the obtained molded body, the mouth and neck may be heat-treated at this stage for crystallization. The crystallinity in this case may be appropriately set according to the type of resin to be used and the desired performance, and is not particularly limited, but is generally preferably about 30 to 50%, more preferably 35 to 45. %. In addition, you may implement after crystallizing the mouth neck part of a molded object after performing the secondary process mentioned later.

  The shape of the oxygen-absorbing multilayer injection molded article of the present embodiment is not particularly limited as long as it is appropriately set according to the intended use. In the case of performing injection molding using a mold as described above, it can have an arbitrary shape corresponding to the cavity shape of the mold.

  The thickness of the oxygen-absorbing multilayer injection molded article of the present embodiment is not particularly limited, but is 3 to 5000 μm from the viewpoint of enhancing the oxygen absorption performance and ensuring various physical properties such as flexibility required for the injection molded article. More preferably, it is 5-4500 micrometers, More preferably, it is 10-4000 micrometers.

  By using the oxygen-absorbing multilayer injection molded article of this embodiment as a part of the components of the container for sealing, oxygen in the container is absorbed and little oxygen penetrates or penetrates from the outside of the container. However, in some cases, this permeating or penetrating oxygen can also be absorbed to prevent alteration of the stored content item (stored object) due to oxygen. At this time, the injection molded body of the present embodiment may itself be molded into a container shape. Considering that the oxygen-absorbing multilayer injection molded article of the present embodiment exhibits oxygen absorption performance, it is preferably a storage container such as a cup-shaped container (injection cup) or a bottle-shaped container.

  On the other hand, the injection molded body of the present embodiment can be formed into a container by performing secondary processing described later. For example, when secondary processing is performed like a PET bottle, the injection molded article of the present embodiment is preferably a test tubular preform (parison). The container obtained by secondary processing of the oxygen-absorbing multilayer injection molded article of this embodiment also absorbs oxygen in the container, and there is little oxygen that penetrates or penetrates the container wall surface from the outside of the container. Can also absorb this permeating or penetrating oxygen and prevent alteration of the stored content item (stored object) due to oxygen. In addition, as a shape of the container after secondary processing, a bottle, a cup, etc. are mentioned, for example.

  Examples of the method of secondary processing the oxygen-absorbing multilayer injection molded article of the present embodiment include blow molding and stretch blow molding, but are not particularly limited thereto, and a known molding method can be applied. it can.

  For example, in injection blow molding, first, a test tubular preform (parison) is molded as the oxygen-absorbing multilayer injection molded body of the present embodiment, and then the mouth of the heated preform is fixed with a jig, and the preform Can be formed into a bottle shape by fitting air to the final shape mold, and then blowing air from the mouth, inflating the preform, bringing it into close contact with the mold, and solidifying by cooling.

  Further, for example, in injection stretch blow molding, first, a test tubular preform (parison) is molded as the oxygen-absorbing multilayer injection molded body of the present embodiment, and then the mouth portion of the heated preform is fixed with a jig, The preform is fitted into the final shape mold, and then blown with air while stretching with a stretching rod from the mouth, blow-stretched the preform to adhere to the mold, and cooled and solidified to form a bottle shape can do.

  Here, the injection stretch blow molding method is generally roughly classified into a hot parison method and a cold parison method. In the former, the preform is blow-molded in a softened state without being completely cooled. On the other hand, in the latter, a bottomed preform in a supercooled state is formed which is considerably smaller than the dimensions of the final shape and the resin is amorphous, and the preform is preheated to its stretching temperature, and the final shape mold Inside, it is stretched in the axial direction and blow-drawn in the circumferential direction. Therefore, the latter is suitable for mass production. In either method, the preform is heated to a stretching temperature equal to or higher than the glass transition point (Tg), and then stretched in the longitudinal direction by a stretching rod in a final shape mold heated to a heat treatment (heat set) temperature. Stretch in the transverse direction by blow air. Here, the draw ratio of the final blow molded article is not particularly limited, but is preferably 1.2 to 6 times in the longitudinal direction and 1.2 to 4.5 times in the transverse direction.

  In injection blow molding, as a general technique, the above-described final shape mold is heated to a temperature at which crystallization of the resin is promoted, for example, 120 to 230 ° C., preferably 130 to 210 ° C. for PET resin. Further, at the time of subsequent blow, heat treatment is performed by bringing the outer wall of the molded body into contact with the inner surface of the mold for a predetermined time. After the heat treatment for a predetermined time, the blowing fluid is switched to the internal cooling fluid to cool the inner layer. The heat treatment time at this time varies depending on the thickness and temperature of the blow molded article, but is generally 1.5 to 30 seconds, preferably 2 to 20 seconds in the case of a PET resin. On the other hand, the cooling time varies depending on the heat treatment temperature and the type of cooling fluid, but is generally 0.1 to 30 seconds, preferably 0.2 to 20 seconds. Each part of the compact is crystallized by this heat treatment.

  Here, as a cooling fluid, in addition to air at normal temperature, various cooled gases, for example, nitrogen at −40 ° C. to + 10 ° C., air, carbon dioxide gas, etc., a chemically inert liquefied gas such as liquefied nitrogen Gas, liquefied carbon dioxide gas, liquefied trichlorofluoromethane gas, liquefied dichlorodifluoromethane gas, other liquefied aliphatic hydrocarbon gas, etc. can be used. In this cooling fluid, a liquid mist having a large heat of vaporization such as water can coexist. By using these cooling fluids, a significantly high cooling temperature can be provided. Also, in stretch blow molding, two molds are used, and after heat treatment within a predetermined temperature and time range in the first mold, the blow molded body is transferred to a second mold for cooling, You may cool a blow molded object simultaneously with blowing again. Moreover, the outer layer of the blow molded product taken out from the mold can be cooled by cooling or by blowing cold air.

  As another blow molding method, the preform is processed into a primary blow molded body having a size larger than that of the final blow molded body using a primary stretch blow mold, and then the primary blow molded body is heated and contracted. A two-stage blow molding in which a stretch blow molding is performed using a secondary mold to form a final blow molded body is exemplified. According to this blow molding method, it is possible to obtain a blow molded body in which the bottom of the blow molded body is sufficiently stretched and thinned, deformation of the bottom at the time of hot filling and heat sterilization is small, and excellent in impact resistance. Can do.

  The oxygen-absorbing multilayer injection molded article of this embodiment and the multilayer container obtained by secondary processing thereof may be coated with an inorganic or inorganic oxide vapor-deposited film, an amorphous carbon film, or the like.

  Examples of the inorganic material or inorganic oxide of the vapor deposition film include, but are not limited to, aluminum, alumina, silicon oxide, and the like. By coating the vapor deposition film of an inorganic substance or an inorganic oxide, the elution of a low molecular weight organic compound can be shielded from the injection molded article of this embodiment and a container obtained by secondary processing thereof. Examples of the method for forming a vapor deposition film include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition methods such as plasma CVD, but are not particularly limited thereto. A known method can be applied. In addition, although the thickness of a vapor deposition film is not specifically limited, From viewpoints, such as gas-barrier property, light-shielding property, and bending resistance, 5-500 nm is preferable, More preferably, it is 5-200 nm.

  The amorphous carbon film is known as a diamond-like carbon film, and is a hard carbon film also called i-carbon film or hydrogenated amorphous carbon film. As a method for forming this amorphous carbon film, there is a method in which the inside of the hollow molded body is evacuated by exhaust, carbon source gas is supplied thereto, and energy for generating plasma is supplied to convert the carbon source gas into plasma. Although illustrated, it is not specifically limited to this method. Thereby, an amorphous carbon film can be formed on the inner surface of the container. Not only can the permeability of low-molecular inorganic gases such as oxygen and carbon dioxide be significantly reduced by the coating of amorphous carbon film, but also oxygen-absorbing multilayer injection molded articles of various low-molecular organic compounds with odors. Adsorption can be suppressed. The thickness of the amorphous carbon film is not particularly limited, but is preferably 50 to 5000 nm from the viewpoints of the effect of suppressing the adsorption of low molecular organic compounds, the effect of improving gas barrier properties, the adhesion to plastics, the durability and the transparency. .

  In using the oxygen-absorbing resin composition of the present embodiment and various molded articles such as laminates using the same, energy rays are irradiated to accelerate the start of the oxygen-absorbing reaction, or to increase the oxygen absorption rate. can do. 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 multilayer injection molded article of this embodiment and the oxygen-absorbing multilayer container using the same do not require moisture for oxygen absorption, in other words, oxygen is absorbed regardless of the presence or absence of moisture in the object to be stored. Therefore, it can be used in a wide range of applications regardless of the type of the object to be stored. 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 resin composition of the present embodiment and various molded articles such as laminates using the same are oxygen in a wide range of humidity conditions (relative humidity 0% to 100%) from low humidity to high humidity. Since it has excellent absorption performance and excellent flavor retention of contents, 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, fruit juice beverages, fruit juices, vegetable juices, carbonated soft drinks, teas in beverages, fruits, nuts, vegetables, meat products in foods, It is suitable for infant foods, coffee, jam, mayonnaise, ketchup, edible oil, dressing, sauces, boiled foods, dairy products, etc., and for other packaging materials such as pharmaceuticals and cosmetics. 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 sterilization methods, for example, boil treatment at 100 ° C. or lower, semi-retort treatment at 100 ° C. or higher, retort treatment, heat sterilization such as high retort treatment at 130 ° C. or higher, electromagnetic wave sterilization of ultraviolet rays, microwaves, gamma rays, etc., ethylene Examples include gas treatment of oxide and the like, and chemical sterilization such as hydrogen peroxide and hypochlorous acid.

  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. Unless otherwise specified, NMR measurements were performed at room temperature.

[Monomer synthesis example]
(Synthesis Example 1)
An autoclave having an internal volume of 18 L was charged with 2.20 kg of dimethyl naphthalene-2,6-dicarboxylate, 11.0 kg of 2-propanol, and 350 g (50 wt% water-containing product) of 5% palladium supported on activated carbon. Next, after the air in the autoclave was replaced with nitrogen, and further nitrogen was replaced with hydrogen, hydrogen was supplied until the pressure in the autoclave reached 0.8 MPa. Next, the agitator was started, the rotation speed was adjusted to 500 rpm, the internal temperature was raised to 100 ° C. over 30 minutes, and hydrogen was further supplied to a pressure of 1 MPa. Thereafter, the supply of hydrogen was continued to maintain 1 MPa in accordance with the pressure drop due to the progress of the reaction. Since the pressure drop disappeared after 7 hours, the autoclave was cooled, unreacted residual hydrogen was released, and then the reaction solution was taken out from the autoclave. The reaction solution was filtered to remove the catalyst, and then 2-propanol was evaporated from the separated filtrate with an evaporator. To the obtained crude product, 4.40 kg of 2-propanol was added and purified by recrystallization to obtain dimethyl tetralin-2,6-dicarboxylate in a yield of 80%. The NMR analysis results are as follows. 1H-NMR (400 MHz CDCl ₃ ) δ7.76-7.96 (2H m), 7.15 (1H d), 3.89 (3H s), 3.70 (3H s), 2.70-3.09 (5H m), 1.80-1.95 (1H m ).

Next, 1.00 kg of dimethyl tetralin-2,6-dicarboxylate obtained above, 8.0 kg of a 16 wt% aqueous ethanol solution and 360 g of sodium hydroxide were added to a 10 L flask, and the mixture was stirred at 80 ° C. for 4 hours for hydrolysis. . Thereafter, 36% hydrochloric acid was added until the pH reached 7, and the precipitated tetralin-2,6-dicarboxylic acid was separated by filtration and then vacuum-dried to obtain 90% yield. The NMR analysis results are as follows. 1H-NMR (400 MHz ((D ₃ C) ₂ S═O) δ12.41-12.75 (2H br), 7.65 (2H m), 7.23 (1H d), 3.70 (3H s), 2.60-3.45 (5H m ), 2.05-2.13 (1H m), 1.70-1.79 (1H m).

[Polymer production example]
(Production Example 1)
In a 200 mL autoclave equipped with a thermometer, a pressure gauge, a nitrogen inlet, and a pressure outlet, 17.18 g (78.0 mmol) of tetralin-2,6-dicarboxylic acid obtained in Synthesis Example 1 and 15.63 g of dodecamethylenediamine ( 78.0 mmol) and 19 g of distilled water were charged, and the inside of the container was purged with nitrogen. The temperature was raised to 220 ° C. over 2 hours and held at a pressure of 2 MPaG for 2 hours. Thereafter, the temperature is raised to 320 ° C. over 1 hour, the pressure is lowered to normal pressure during the temperature rise, and the tetralin ring-containing polyamide compound (1 is cooled by holding at 320 ° C. and normal pressure for 30 minutes. ) As a result of measuring the glass transition temperature and melting | fusing point of the obtained polyamide compound (1) by DSC, the glass transition temperature was 111 degreeC and melting | fusing point was 262 degreeC. The relative viscosity was 3.74. The charge composition is shown in Table 1.

(Production Example 2)
In the same autoclave as in Production Example 1, 11.64 g (52.9 mmol) of tetralin-2,6-dicarboxylic acid obtained in Synthesis Example 1, 2.48 g (13.2 mmol) of azelaic acid, 13.24 g of dodecamethylenediamine ( 66.1 mmol) and 12 g of distilled water were charged, and a tetralin ring-containing polyamide compound (2) was synthesized in the same manner as in Production Example 1. Polyamide compound (2) had a glass transition temperature of 94 ° C., a melting point of 246 ° C., and a relative viscosity of 3.5. The charge composition is shown in Table 1.

(Production Example 3)
In an autoclave similar to Production Example 1, 15.11 g (68.6 mmol) of tetralin-2,6-dicarboxylic acid obtained in Synthesis Example 1, 13.88 g (68.6 mmol) of sebacic acid, 15.95 g of hexamethylenediamine ( 137.2 mmol) and 12 g of distilled water were charged, and a tetralin ring-containing polyamide compound (3) was synthesized in the same manner as in Production Example 1. Polyamide compound (3) had a glass transition temperature of 87 ° C., a melting point of 250 ° C., and a relative viscosity of 2.6. The charge composition is shown in Table 1.

(Production Example 4)
In the same autoclave as in Production Example 1, 11.22 g (51.0 mmol) of tetralin-2,6-dicarboxylic acid obtained in Synthesis Example 1, 5.93 g (50.9 mmol) of hexamethylenediamine, 11.54 g of ε-caprolactam (102.0 mmol) and 12 g of distilled water were charged, and a tetralin ring-containing polyamide compound (4) was synthesized in the same manner as in Production Example 1. Polyamide compound (4) had a glass transition temperature of 96 ° C., a melting point of 219 ° C., and a relative viscosity of 2.4. The charge composition is shown in Table 1.

Example 1
A biaxial extrusion having two screws with a diameter of 37 mm for a mixture obtained by dry blending cobalt stearate (II) with a cobalt content of 0.03 parts by mass with respect to 100 parts by mass of the polyamide compound (1) The mixture was supplied to the machine at a rate of 15 kg / h, melt kneaded under conditions of a cylinder temperature of 220 ° C., the strand was extruded from the extruder head, cooled and pelletized to obtain an oxygen-absorbing resin composition.

  Next, the thermoplastic resin constituting the layer B is injected from the injection cylinder under the following conditions, and then the resin composition constituting the layer A is simultaneously injected from another injection cylinder with the thermoplastic resin constituting the layer B. Next, a required amount of the thermoplastic resin constituting layer B was injected to fill the cavity, thereby molding a three-layer injection molded body (test tube parison) consisting of layer B / layer A / layer B. . The total mass of the parison was 25 g, and the mass of the layer A was 10% by mass of the total mass of the parison. In addition, as a thermoplastic resin constituting the layer B, polyethylene terephthalate (manufactured by Nippon Unipet Co., Ltd., trade name: BK-2180), as a resin composition constituting the layer A, the above oxygen-absorbing resin composition, Each was used.

(Parison shape)
The total length was 95 mm, the outer diameter was 22 mm, and the wall thickness was 2.7 mm. For the manufacture of the parison, an injection molding machine (manufactured by Meiki Seisakusho Co., Ltd., model: M200, 4 pieces) was used.
(Parison molding conditions)
Injection cylinder temperature for layer A: 250 ° C
Injection cylinder temperature for layer B: 280 ° C
Resin channel temperature in mold: 280 ° C
Mold cooling water temperature: 15 ° C

  After cooling the obtained parison, as a secondary process, the parison was heated and biaxial stretch blow molding was performed to produce a multilayer bottle (oxygen-absorbing multilayer container).

(Bottle shape obtained by secondary processing)
The total length was 160 mm, the outer diameter was 60 mm, the inner volume was 350 mL, and the wall thickness was 0.28 mm. The draw ratio was 1.9 times in length and 2.7 times in width. The bottom shape is a champagne type. The body has dimples. For secondary processing, a blow molding machine (manufactured by Frontier Corporation, model: EFB1000ET) was used.

(Secondary processing conditions)
Parison heating temperature: 100 ° C
Stretching rod pressure: 0.5 MPa
Primary blow pressure: 0.7 MPa
Secondary blow pressure: 2.5 MPa
Primary blow delay time: 0.33 sec
Primary blow time: 0.35 sec
Secondary blow time: 2.0 sec
Blow exhaust time: 0.6 sec
Mold temperature: 30 ℃

  Subsequently, the oxygen permeability of the obtained container was measured in an atmosphere of 23 ° C., a relative humidity of 50% outside the container, and a relative humidity of 100% inside the container. In this measurement, an oxygen permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2-61) was used. It shows that oxygen barrier property is so favorable that a measured value is low. Table 2 shows the oxygen transmission rate after 14 days from the start of measurement.

(Example 2)
An oxygen-absorbing resin composition, a parison and a multilayer bottle were produced in the same manner as in Example 1 except that the polyamide compound (2) was used in place of the polyamide compound (1). Further, the oxygen transmission rate of the multilayer bottle was measured. The evaluation results are shown in Table 2.

(Example 3)
An oxygen-absorbing resin composition, a parison and a multilayer bottle were produced in the same manner as in Example 1 except that the polyamide compound (3) was used instead of the polyamide compound (1). Further, the oxygen transmission rate of the multilayer bottle was measured. The evaluation results are shown in Table 2.

Example 4
An oxygen-absorbing resin composition, a parison and a multilayer bottle were produced in the same manner as in Example 1 except that the polyamide compound (4) was used instead of the polyamide compound (1). Further, the oxygen transmission rate of the multilayer bottle was measured. The evaluation results are shown in Table 2.

(Comparative Example 1)
The blending of the polyamide compound (1) and cobalt stearate (II) is omitted, and 100 parts by mass of polyethylene terephthalate (trade name: BK-2180, manufactured by Nihon Unipet Co., Ltd.) is used as in Example 1. A single-layer bottle having the same shape as in Example 1 was produced. Further, in the same manner as in Example 1, the oxygen transmission rate of the single-layer bottle was measured. The evaluation results are shown in Table 2.

  As is clear from Table 2, the oxygen-absorbing containers of Examples 1 to 4 absorb oxygen in the oxygen-absorbing layer, so that the oxygen permeability is smaller than that of a normal PET bottle (Comparative Example 1). It was confirmed that the barrier property was excellent.

Claims (5)

An oxygen-absorbing multilayer injection molded article comprising an oxygen-absorbing layer comprising an oxygen-absorbing resin composition containing a polyamide compound and a transition metal catalyst, and a resin layer containing a thermoplastic resin,
The polyamide compound is a structural unit represented by the following formulas (3) to (6);

An oxygen-absorbing multilayer injection molded article containing a structural unit having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing multilayer injection molded article 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 multilayer injection molded article 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 polyamide compound. An oxygen-absorbing multilayer container obtained by molding the oxygen-absorbing multilayer injection molded article according to any one of claims 1 to 3 into a cup shape or a bottle shape. The oxygen-absorbing multilayer container according to claim 4 , wherein the molding process is stretch blow molding.