JP5962439B2 - Oxygen-absorbing injection molded body - Google Patents

Description

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

  Injection molding (injection molding) is widely used in mechanical parts, automobile parts, electrical / electronic parts, food / pharmaceutical containers, etc., because it can produce molded bodies having complicated shapes and has high productivity. In recent years, various plastic containers have been used as packaging containers because they have advantages such as light weight, transparency and easy moldability. As a typical plastic container, for example, for a beverage container or the like, 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, the injection molded body mainly composed of thermoplastic resin is excellent as a packaging material, but unlike glass bottles and metal containers, it has the property of allowing oxygen to permeate from the outside. There remains a problem with shelf life. In order to impart gas barrier properties to such an injection-molded product made of a general-purpose resin, an injection-molded product having a gas barrier layer as an intermediate layer has been put into practical use.

  On the other hand, oxygen in the package that stores these products for the purpose of preventing oxygen oxidation and preserving them for a long time, such as foods, beverages, pharmaceuticals, and cosmetics, which are easily changed or deteriorated under the influence of oxygen. An oxygen absorber that performs the removal 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 iron is required for the oxidation reaction of the iron powder, the effect of oxygen absorption could only be expressed if the material to be stored is a high moisture system.

  In addition, the container is made of a multilayer material in which an oxygen absorbing layer made of an oxygen absorbing resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. Development of packaging containers having an oxygen absorbing function has been carried out (see Patent Document 1). However, this also has the problems that it cannot be used in a metal detector, cannot be heated by a microwave oven, and the object to be preserved exhibits only high moisture content. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity.

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

  On the other hand, an oxygen-absorbing resin composition comprising a resin and a transition metal catalyst and having oxygen scavenging properties is known. For example, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal catalyst, is known as an oxidizable organic component, and further a resin composition having an oxygen scavenging function and oxygen obtained by molding the resin composition There are also examples of absorbents, packaging materials, and multilayer laminated films for packaging (see Patent Document 3).

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

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

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

  However, the oxygen absorbent composition 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. Yes.

  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, strength reduction due to oxidative degradation of the resin occurs, and packaging There is a problem that the strength of the container itself is lowered. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture.

  Furthermore, the oxygen-absorbing resin composition of Patent Document 4 has a problem in that a low molecular weight organic compound that becomes an odor component is generated by the cleavage of a polymer chain accompanying the oxidation of the resin, and the strength of the odor increases after oxygen absorption. .

  On the other hand, the composition of Patent Document 5 requires the use of a special material containing a cyclohexene functional group, and this material has a problem that it is relatively easy to generate an odor.

  The present invention has been made in view of the above problems, and its object is to provide a novel oxygen-absorbing property that is insensitive to metal detectors, suppresses odor generation after oxygen absorption, and has excellent oxygen-absorbing 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 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. It is in.

  As a result of studying the oxygen-absorbing injection molded article, the present inventors have found that the above problem can be solved by using a polyester compound having a tetralin ring, a transition metal catalyst, and a thermoplastic resin. Was completed.

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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、ｎは０〜７の整数を表し、テトラリン環のベンジル位に少なくとも１つ以上の水素原子が結合している。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及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価の基を表す。）
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＞記載の酸素吸収性インジェクション成形体。
＜３＞ 前記遷移金属触媒が、前記酸素吸収層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（５）〜（７）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インジェクション成形体。

＜５＞ 前記ポリエステル化合物が、前記ポリエステル化合物と前記熱可塑性樹脂（ａ）の合計量１００質量部に対し、５〜９５質量部含まれる、上記＜１＞〜＜４＞のいずれかに記載の酸素吸収性インジェクション成形体。
＜６＞ 上記＜１＞〜＜５＞のいずれかに記載の酸素吸収性インジェクション成形体を、更に加工して得られる酸素吸収性容器。
＜７＞ 延伸ブロー成形により得られる、上記＜６＞に記載の酸素吸収性容器。 That is, the present invention provides the following <1> to <7>.
<1> An oxygen-absorbing injection molded article comprising an oxygen-absorbing resin composition containing a polyester compound, a transition metal catalyst, and a thermoplastic resin,
The polyester compound is represented by the following general formulas (1) to (4).

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group At least one selected from the above, 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 hydrogen atom at the benzyl position of the tetralin ring. X is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic ring. It represents a divalent group containing at least one group selected from the group consisting of.)
An oxygen-absorbing injection molded article containing a structural unit having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing 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 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 oxygen absorption layer. .
<4> Any of the above <1> to <3>, wherein the structural unit represented by the general formula (1) is at least one selected from the group consisting of the following formulas (5) to (7): 2. An oxygen-absorbing injection molded article as described in 1.

<5> The polyester compound according to any one of <1> to <4>, wherein the polyester compound is included in an amount of 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the polyester compound and the thermoplastic resin (a). Oxygen-absorbing injection molding.
<6> An oxygen-absorbing container obtained by further processing the oxygen-absorbing injection-molded article according to any one of <1> to <5>.
<7> The oxygen-absorbing container according to <6>, obtained by stretch blow molding.

  ADVANTAGE OF THE INVENTION According to this invention, the oxygen absorptive injection molding which has the outstanding oxygen absorption performance on the wide humidity conditions from low humidity to high humidity, and an oxygen absorptive container using the same are realizable. The oxygen-absorbing injection molded body and the oxygen-absorbing container using the oxygen-absorbing injection molded body can absorb oxygen regardless of the presence or absence of moisture in the object to be stored, and the odor generation after oxygen absorption is suppressed. For example, it can be used in a wide range of applications such as foods, cooked foods, beverages, pharmaceuticals, and health foods, regardless of the object. It is also possible to realize an oxygen-absorbing injection molded body that is not sensitive to a metal detector and an oxygen-absorbing container using the same. Furthermore, the decrease in strength of the polyester compound due to oxidation after oxygen absorption is extremely small, and the strength of the oxygen absorbing layer is maintained even in long-term use, so that an oxygen-absorbing injection molded article that hardly causes delamination and oxygen using the same Absorbent containers 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.

[Injection molded body]
The oxygen-absorbing injection molded article of this embodiment includes at least a polyester compound, a transition metal catalyst, and a thermoplastic resin.

  In this embodiment, the resin composition can exhibit oxygen absorption performance and oxygen barrier performance by containing a polyester compound, a transition metal catalyst, and a thermoplastic resin. 1 type may be sufficient as the polyester compound contained in a resin composition, and the combination of 2 or more types may be sufficient as it. Further, the thermoplastic resin contained in the resin composition may be one kind or a combination of two or more kinds.

[Polyester compound]
The polyester compound of this embodiment contains the structural unit which has at least 1 type of tetralin ring represented by either of the said general formula (1)-(4).

  In the general formulas (1) to (4) and (8) to (15) of the present application, examples of the monovalent substituent represented by R include a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), and 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 methyl group, ethyl group, n-propyl group, isopropyl group, t- A butyl group, an n-octyl group, a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group), an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 linear, branched or branched) Cyclic alkenyl groups such as vinyl and allyl groups, alkynyl groups (preferably alkynyl groups having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms such as ethynyl groups and propargyl groups), 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 A monovalent group obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound having 2 to 6 carbon atoms, 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. 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, for example, an alkyl group substituted with a hydroxy group (for example, hydroxyethyl group), an alkyl group substituted with an alkoxy group (for example, methoxyethyl group), and an alkyl group substituted with an aryl group (for example, Benzyl group), alkyl groups substituted with primary or secondary amino groups (eg aminoethyl group), aryl groups substituted with alkyl groups (eg p-tolyl group), substituted with alkyl groups Aryloxy groups (for example, 2-methylphenoxy group) and the like, but are not particularly limited thereto. 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.

  X is at least one selected from the group consisting of an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. Represents a divalent group containing one group. The 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, and may contain an ether group, sulfide group, carbonyl group, hydroxy group, amino group, sulfoxide group, sulfone group, and 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 polyester compound containing the structural unit represented by the general formula (1) can be obtained by polycondensation of a dicarboxylic acid having a tetralin ring or a derivative (I) thereof and a diol or a derivative (II) thereof.

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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、ｎは０〜７の整数を表し、テトラリン環のベンジル位に少なくとも１つ以上の水素原子が結合している。Ｙは水素原子又はアルキル基を表す。） The dicarboxylic acid having a tetralin ring or its derivative (I) used in the present embodiment is represented by the following general formula (8). These can be used alone or in combination of two or more.

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group At least one selected from the above, 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 hydrogen atom at the benzyl position of the tetralin ring. Atoms are bonded. Y represents a hydrogen atom or an alkyl group.)

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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の整数を表す。Ｙは水素原子又はアルキル基を表す。） The compound represented by the general formula (8) can be obtained by reacting a dicarboxylic acid having a naphthalene ring represented by the following general formula (9) or a derivative thereof with hydrogen.

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group These are at least one selected, and may further have a substituent, each m independently represents an integer of 0 to 3, and Y represents a hydrogen atom or an alkyl group.)

  Examples of the diol or derivative (II) used in the present embodiment include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3-propanediol, 2-methyl- 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1 , 9-nonanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, 2-phenylpropanediol, 2- (4-hydroxyphenyl) ethyl alcohol, α, α-dihydroxy-1,3-diisopropylbenzene, α, α Dihydroxy-1,4-diisopropylbenzene, o- xylene glycol, m- xylene glycol, p- xylene glycol, hydroquinone, 4,4-dihydroxyphenyl, naphthalene diol or derivatives thereof,. These can be used alone or in combination of two or more.

  The polyester compound containing the structural unit represented by the general formula (2) is obtained by polycondensation of a diol having a tetralin ring or a derivative (III) thereof and a dicarboxylic acid or a derivative (IV) thereof. It is done.

（式中、それぞれ独立して、水素原子または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、複素環チオ基及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、ｎは０〜７の整数を表し、テトラリン環のベンジル位に少なくとも１つ以上の水素原子が結合している。） A diol having a tetralin ring or a derivative (III) thereof used in the present embodiment is represented by the following general formula (10). These can be used alone or in combination of two or more.

(In the formula, each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent 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 hydrogen atom is bonded to the benzyl position of the tetralin ring. doing.)

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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の整数を表す。） The compound represented by the general formula (10) can be obtained by reacting a diol having a naphthalene ring represented by the following general formula (11) or a derivative thereof with hydrogen.

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group These are at least one selected, and may further have a substituent, each m independently represents an integer of 0 to 3.)

  Examples of the dicarboxylic acid or derivative (IV) used in the present embodiment include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid. Benzenedicarboxylic acid such as 3,3-dimethylpentanedioic acid, phthalic acid, isophthalic acid and terephthalic acid, naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, phenylmalonic acid, phenylenediacetic acid, pheny Examples include dibutyric acid, 4,4-diphenyl ether dicarboxylic acid, p-phenylene dicarboxylic acid, and derivatives thereof. These can be used alone or in combination of two or more.

  The polyester compound containing the structural unit represented by the general formula (3) or (4) can be obtained by polycondensation of a hydroxycarboxylic acid having a tetralin ring or a derivative (V) thereof.

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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、ｎは０〜７の整数を表し、テトラリン環のベンジル位に少なくとも１つ以上の水素原子が結合している。Ｙは水素原子又はアルキル基を表す。） The hydroxycarboxylic acid having a tetralin ring or its derivative (V) used in the present embodiment is represented by the following general formula (12) or (13). These can be used alone or in combination of two or more.

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group At least one selected from the above, 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 hydrogen atom at the benzyl position of the tetralin ring. Atoms are bonded. Y represents a hydrogen atom or an alkyl group.)

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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の整数を表す。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及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価の基を表す。）

（式中、Ｒは、それぞれ独立して、水素原子または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、複素環チオ基及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の整数を表す。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及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価の基を表す。） The polyester compound containing the structural unit represented by the general formula (1) or (2) is obtained by hydrogenation reaction of the polyester compound containing the structural unit represented by the following general formula (14) or (15). You can also

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group At least one selected from the above, 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 fat. Represents a divalent group containing at least one group selected from the group consisting of a cyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group. )

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group At least one selected from the above, 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 fat. Represents a divalent group containing at least one group selected from the group consisting of a cyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group. )

  In the polyester compound of the present embodiment, a constitutional unit having no tetralin ring may be incorporated as a copolymer component to the extent that it does not affect the performance. Specifically, the diol or its derivative (II) or the compound shown in the dicarboxylic acid or its derivative (IV) can be used as a copolymerization component.

Preferred specific examples of the polyester compound containing the structural unit represented by the general formula (1) include the above formulas (5) to (7) and the following formulas (16) to (18). It is not limited to.

  There is no restriction | limiting in particular in the method of manufacturing the polyester compound used for this embodiment, All the manufacturing methods of conventionally well-known polyester can be applied. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method. Among the above-described methods for producing a polyester compound, a transesterification method is preferably used from the viewpoint of easy availability of raw materials.

  Various known catalysts such as transesterification catalysts, esterification catalysts, polycondensation catalysts, etc., etherification inhibitors, heat stabilizers, light stabilizers, polymerization regulators, etc., used in the production of polyester compounds Any of these can be used, and these are appropriately selected according to the reaction rate, the color tone of the polyester compound, safety, thermal stability, weather resistance, self-elution, and the like. For example, the above-mentioned various catalysts include zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, antimony, tin, and other metal compounds (for example, fatty acid salts , Carbonates, phosphates, hydroxides, chlorides, oxides, alkoxides), magnesium metal, and the like. These can be used alone or in combination.

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

  Moreover, the oxygen absorption layer of the present embodiment is one in which odor generation after oxygen absorption is suppressed. Although the reason is not clear, for example, the following oxidation reaction mechanism is assumed. That is, in the polyester compound, first, hydrogen at the benzylic position of the tetralin ring is extracted to generate a radical, and then the benzylic carbon is oxidized by the reaction between the radical and oxygen to generate a hydroxy group or a ketone group. Conceivable. Therefore, in the oxygen-absorbing layer of this 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 polyester compound is maintained, so that the low-molecular weight that causes odor is lost. It is presumed that the organic compound is hardly generated after oxygen absorption, and as a result, the increase in odor intensity after oxygen absorption is suppressed.

  The intrinsic viscosity of the polyester compound of the present embodiment (measured value at 25 ° C. using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a mass ratio of 6: 4) is not particularly limited. From the viewpoint of moldability, 0.1 to 2.0 dL / g is preferable, and 0.5 to 1.5 dL / g is more preferable.

  The transition metal catalyst used in the present embodiment is not particularly limited as long as it can function as a catalyst for the oxidation reaction of the polyester compound and can be appropriately selected from known ones.

  Specific examples of the transition metal catalyst include, for example, 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, Although capric acid and naphthenic acid are mentioned, it is not limited to these. The transition metal catalyst is preferably a combination of these transition metals 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 compounding quantity of a transition metal catalyst can be suitably set according to the kind and desired performance of the said polyester compound and transition metal catalyst to be used, and is not specifically limited. From the viewpoint of the oxygen absorption amount of the oxygen absorption layer (A), the blending amount of the transition metal catalyst is preferably 0.001 to 10 parts by mass as the transition metal amount, more preferably 100 parts by mass of the polyester compound. Is 0.002 to 2 parts by mass, more preferably 0.005 to 1 part by mass.

[Thermoplastic resin]
In the present embodiment, a conventionally known resin can be used as the thermoplastic resin, and is not particularly limited. Examples of the thermoplastic resin include polyolefins, polyesters, polyamides, ethylene-vinyl alcohol copolymers, and plant-derived resins. In the present embodiment, the oxygen absorption layer includes at least one selected from the group consisting of these resins. It is preferable to include.
Among these, a resin having high oxygen barrier properties such as polyester, polyamide, and ethylene-vinyl alcohol copolymer is more preferable in order to effectively exhibit the oxygen absorption effect.

[Polyolefin]
Specific examples of polyolefin include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, and the like, such as polypropylene, polybutene-1, poly-4-methylpentene-1, and the like. Olefin homopolymer; ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cyclic olefin copolymer, etc. Copolymer of ethylene and α-olefin Copolymer; Ethylene-α, β-unsaturated carboxylic acid copolymer such as ethylene- (meth) acrylic acid copolymer, ethylene-α, β-unsaturated carboxylic acid such as ethylene- (meth) acrylic acid ethyl copolymer Acid ester copolymer, ionic cross-linked product of ethylene-α, β-unsaturated carboxylic acid copolymer, Other ethylene copolymers such as tylene-vinyl acetate copolymers; ring-opening polymers of cyclic olefins and hydrogenated products thereof; cyclic olefins-ethylene copolymers; and these polyolefins with acid anhydrides such as maleic anhydride Examples thereof include graft-modified polyolefins graft-modified with products.

[polyester]
The polyester described here is a polyester that can be used as a thermoplastic resin, and is not a polyester compound of the present embodiment. In the present embodiment, the polyester is composed of one or more selected from polycarboxylic acids containing dicarboxylic acids and ester-forming derivatives thereof, and one or more selected from polyhydric alcohols containing glycol. Or those composed of hydroxycarboxylic acids and their ester-forming derivatives, or those composed of cyclic esters. 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. Polyethylene terephthalate is particularly excellent as an ethylene terephthalate thermoplastic polyester in terms of pressure resistance, heat resistance, heat pressure resistance, etc. In addition to ethylene terephthalate units, dibasic acids such as isophthalic acid and naphthalenedicarboxylic acid and diols such as propylene glycol Copolyesters containing a small amount of ester units consisting of can also be used.

  Examples of dicarboxylic acids 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- Exemplified as cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,5-norbornanedicarboxylic acid, dimer acid, etc. Saturated aliphatic dicarboxylic acids or ester-forming derivatives thereof, unsaturated aliphatic dicarboxylic acids exemplified by fumaric acid, maleic acid, itaconic acid or the like, or ester-forming derivatives thereof, orthophthalic acid, isophthalic acid, terephthalic acid 1,3-na Taleenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′- Aromatic dicarboxylic acids exemplified by biphenylsulfone dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic acid, etc. or ester formation thereof Metal, exemplified by 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 5-lithium sulfoisophthalic acid, 2-lithium sulfoterephthalic acid, 5-potassium sulfoisophthalic acid, 2-potassium sulfoterephthalic acid, etc. Sulfonate group-containing aromatic dicarboxylic acid or Such lower alkyl esters thereof derivative.

  Among the above dicarboxylic acids, the use of terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid is particularly preferable in terms of the physical properties of the resulting polyester, and other dicarboxylic acids may be copolymerized as necessary. .

  As polyvalent carboxylic acids other than these dicarboxylic acids, ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarboxylic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ′, 4′-biphenyltetracarboxylic acid, And ester-forming derivatives thereof.

  As glycols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 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, polytrimethyl Aliphatic glycols exemplified by tylene 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 Examples thereof include aromatic glycols exemplified by C, 2,5-naphthalenediol, glycols obtained by adding ethylene oxide to these glycols, and the like.

  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. Examples of polyhydric alcohols other than these glycols include trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol, and the like. Examples of hydroxycarboxylic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, or these And ester-forming derivatives thereof.

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

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

  The polyester used in this embodiment is preferably 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.

  The polyester in which the 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. A polyester containing 80 mol% or more is preferable, and a polyester containing 90 mol% or more is more preferable. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is also preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acid or an ester-forming derivative thereof, more preferably 80 Polyesters containing at least mol%, more preferably polyesters containing at least 90 mol%.

  Examples of the naphthalenedicarboxylic acid or ester-forming derivative thereof used in the present embodiment include 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like exemplified in the above dicarboxylic acids. 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, or ester-forming derivatives thereof are preferred.

  The polyester whose main glycol component is an alkylene glycol is preferably a polyester containing 70 mol% or more of the total amount of alkylene glycol with respect to all glycol components, more preferably a polyester containing 80 mol% or more, More preferably, it is a polyester containing 90 mol% or more. The alkylene glycol here may contain a substituent or an 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, 1,2-propanediol, 1,3-propane. It is preferably at least one selected from the group consisting of diol and 2-methyl-1,3-propanediol in order to achieve both transparency and moldability, particularly isophthalic acid, diethylene glycol, neopentyl glycol, More preferably, it is at least one selected from the group consisting of 1,4-cyclohexanedimethanol.

  A preferred example of the polyester used in this embodiment is a polyester in which the main repeating unit is composed of ethylene terephthalate, more preferably a linear polyester containing 70 mol% or more of ethylene terephthalate units, and still more preferably an ethylene terephthalate unit. Is a linear polyester containing 80 mol% or more, and particularly preferred is a linear polyester containing 90 mol% or more of ethylene terephthalate units.

  Another preferred example of the polyester used in this embodiment is a polyester in which the main repeating unit is composed of ethylene-2,6-naphthalate, and more preferably 70 mol% or more of ethylene-2,6-naphthalate unit. A linear polyester containing 80 mol% or more of ethylene-2,6-naphthalate units, particularly preferably a linear polyester containing 90 mol% or more of ethylene-2,6-naphthalate units. Polyester.

  Other preferred examples of the polyester used in this embodiment include linear polyesters containing 70 mol% or more of propylene terephthalate units, linear polyesters containing 70 mol% or more of propylene naphthalate units, and 1,4-cyclohexanedimethylene. A linear polyester containing 70 mol% or more of terephthalate units, a linear polyester containing 70 mol% or more of butylene naphthalate units, or a linear polyester containing 70 mol% or more of butylene terephthalate units.

  In particular, the composition of the whole polyester is a combination of terephthalic acid / isophthalic acid // ethylene glycol, terephthalic acid // ethylene glycol / 1,4-cyclohexanedimethanol, and terephthalic acid // ethylene glycol / neopentyl glycol. This is preferable in order to satisfy both the moldability and the moldability. Needless to say, a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol may be included in the esterification (transesterification) reaction or polycondensation reaction.

  Other preferred examples of the polyester used in this embodiment include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. This polyglycolic acid may be copolymerized with other components such as lactide.

[polyamide]
The polyamide used in the present embodiment is a polyamide having a unit derived from a lactam or an aminocarboxylic acid as a main constituent unit, or an aliphatic having a unit derived from an aliphatic diamine and an aliphatic dicarboxylic acid as a main constituent unit. Polyamide, Partially aromatic polyamide whose main constituent unit is a unit derived from aliphatic diamine and aromatic dicarboxylic acid, Partially aromatic whose main constituent unit is a unit derived from aromatic diamine and aliphatic dicarboxylic acid Examples thereof include polyamide, and a monomer unit other than the main structural unit may be copolymerized as necessary.

  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. .

  As the aliphatic diamine, an aliphatic diamine having 2 to 12 carbon atoms or a functional derivative thereof can be used. Furthermore, an alicyclic diamine may be used. 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 include aliphatic diamines such as nonamethylenediamine, decamethylenediamine, undecamethylenediamine, and dodecamethylenediamine. Specific examples of the alicyclic diamine include cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, and the like.

  Moreover, as said aliphatic dicarboxylic acid, linear aliphatic dicarboxylic acid and alicyclic dicarboxylic acid are preferable, and also linear aliphatic dicarboxylic acid which has a C4-C12 alkylene group is especially preferable. Examples of such linear aliphatic dicarboxylic acids include adipic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, dimer acid and their functionalities. Derivatives and the like can be mentioned. Examples of the alicyclic dicarboxylic acid include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid.

  Examples of the aromatic diamine include metaxylylenediamine, paraxylylenediamine, para-bis (2-aminoethyl) benzene, and the like.

  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. It is done.

  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.

  Further, as a copolymerization component of the polyamide, a polyether having at least one terminal amino group or a terminal carboxyl group and a number average molecular weight of 2000 to 20000, or an organic carboxylate of the polyether having the terminal amino group, or An amino salt of a polyether having a terminal carboxyl group can also be used. Specific examples 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]
Although it does not specifically limit as an ethylene-vinyl alcohol copolymer used by this embodiment, Preferably it is 15-60 mol%, More preferably, it is 20-55 mol%, More preferably, it is 29-44 mol%. The saponification degree of the vinyl acetate component is preferably 90 mol% or more, more preferably 95 mol% or more.
Further, the ethylene vinyl alcohol copolymer has a smaller amount of α-olefin such as propylene, isobutene, α-octene, α-dodecene, α-octadecene, unsaturated carboxylic acid, etc., as long as the effect of the present embodiment is not adversely affected. A comonomer such as an acid or a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile, an amide, an anhydride, an unsaturated sulfonic acid or a salt thereof may be contained.

  The polyester compound, the transition metal catalyst, and the thermoplastic resin can be mixed by a known method, but can be used as a resin composition with good dispersibility, preferably by kneading with an extruder. Further, the oxygen absorbing layer has additives such as desiccants, pigments, dyes, antioxidants, slip agents, antistatic agents, stabilizers, calcium carbonate, clay, mica as long as the effects of the present embodiment are not impaired. In addition, fillers such as silica, deodorizers and the like may be added, but various materials can be mixed without being limited to those described above.

  In addition, in order to accelerate | stimulate oxygen absorption reaction, the resin composition of this embodiment may contain the radical generator and the photoinitiator further as needed. Specific examples of the radical generator include various N-hydroxyimide compounds such as N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxyhexahydrophthalimide, 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-hydroxyhexahydrophthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide , N, N-dihydroxypyromellitic acid diimide and the like, but are not particularly limited thereto. 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. In addition, these radical generators and photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  The thickness of the oxygen-absorbing injection molded body of the present embodiment is preferably 3 to 5000 μm from the viewpoint of having oxygen absorption performance and ensuring various physical properties such as flexibility required for the injection molded body. More preferably, it is 5-4500 micrometers, More preferably, it is 10-4000 micrometers.

  The method for producing the oxygen-absorbing injection molded article of the present embodiment is not particularly limited, and can be produced by a normal injection molding method. For example, using a molding machine equipped with an injection machine and an injection mold, the resin composition is injected from the injection cylinder into the cavity through the mold hot runner, and injection molding corresponding to the shape of the injection mold The body can be manufactured. In order to give heat resistance to the mouth and neck of the obtained molded body, the mouth and neck may be crystallized by heat treatment at this stage. The degree of crystallinity is preferably 30 to 50%, more preferably 35 to 45%. In addition, you may implement crystallization, after giving the secondary process mentioned later.

  In the case where the injection molded product itself of the present embodiment is a container, in addition to oxygen that slightly enters from the outside of the container, oxygen in the container can be absorbed and alteration of the stored content article due to oxygen can be prevented.

  The shape of the oxygen-absorbing injection molded body of the present embodiment is not particularly limited, and can be any shape depending on the mold. Considering that the oxygen-absorbing injection molded article of the present embodiment can exhibit oxygen absorption performance, the oxygen-absorbing injection molded article of the present embodiment can be stored in cup-shaped containers (injection cups), bottle-shaped containers, and the like. A container is preferred. Moreover, it is also preferable that the injection molded body of the present embodiment is a test tubular preform (parison) for secondary processing such as blow molding as will be described later, such as a PET bottle.

  The container obtained by secondary processing of the oxygen-absorbing injection molded article of the present embodiment absorbs oxygen in the container in addition to oxygen that slightly enters from the outside of the container, and changes the contents of the stored article due to oxygen. Can be prevented. Examples of secondary processing include blow molding and stretch blow molding, and examples of containers obtained by secondary processing include bottles.

In the injection blow molding, first, a test tubular preform (parison) is molded as the oxygen-absorbing injection molded body of the present embodiment, and then the mouth of the heated preform is fixed with a jig, and the preform is formed into a final shape. It can be molded into a bottle shape by fitting into a mold, blowing air from the mouth, inflating the preform, closely contacting the mold, and solidifying by cooling.
In injection stretch blow molding, the mouth of a heated preform is fixed with a jig, the preform is fitted into a final shape mold, and air is blown from the mouth while stretching with a stretching rod. It can be formed into a bottle by blow-stretching, closely adhering to a mold, and solidifying by cooling.
The injection stretch blow molding method is roughly classified into a hot parison method and a cold parison method. The former blow-molds in a softened state without completely cooling the preform. On the other hand, in the latter cold parison method, the preform is formed as a supercooled bottomed preform that is considerably smaller than the dimensions of the final shape and the resin is amorphous, and this preform is preheated to its stretching temperature to obtain the final shape. It is suitable for mass production by drawing in the mold in the axial direction and blow-drawing in the circumferential direction. In either method, the preform is heated to a stretching temperature equal to or higher than the glass transition point (Tg), and then stretched by a stretching rod in a final shape mold heated to a heat treatment (heat set) temperature by a stretch blow molding method. Stretching in the direction and stretching in the transverse direction by blow air. The draw ratio of the final blow molded article is preferably 1.2 to 6 times in the longitudinal direction and 1.2 to 4.5 times in the transverse direction.

  The above-described final shape mold is heated to a temperature at which resin crystallization is promoted, for example, 120 to 230 ° C., preferably 130 to 210 ° C. for PET resin, and the outer side of the wall of the molded body is molded at the time of blowing. Heat treatment is performed by contacting the inner surface for a predetermined time. After the heat treatment for a predetermined time, the inner layer is cooled by switching the blowing fluid to the internal cooling fluid. The heat treatment 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.

  As the cooling fluid, in addition to air at normal temperature, various gases cooled, for example, nitrogen at −40 ° C. to + 10 ° C., air, carbon dioxide, 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 gases, and the like can be used. In this cooling fluid, a liquid mist having a large heat of vaporization such as water can coexist. By using the cooling fluid described above, a remarkably high cooling temperature can be obtained. In addition, two molds are used for stretch blow molding, and after heat treatment within a predetermined temperature and time range in the first mold, the blow molded body is transferred to the second mold for cooling, and again. You may cool a blow molded object simultaneously with blowing. The outer layer of the blow molded article taken out from the mold is cooled by cooling or by blowing cold air.

  As another method for producing a blow molded article, the preform was formed into a primary blow molded article having a size larger than that of the final blow molded article using a primary stretch blow mold, and then the primary blow molded article was heated and shrunk. Thereafter, two-stage blow molding may be employed in which a final blow molded article is formed by performing stretch blow molding using a secondary mold. According to this method for producing a blow molded article, the bottom of the blow molded article is sufficiently stretched and thinned to obtain a blow molded article excellent in hot filling, deformation of the bottom during heat sterilization, and impact resistance. .

The injection molded body of this embodiment and the container obtained by secondary processing thereof may be coated with an inorganic or inorganic oxide vapor deposition film or an amorphous carbon film.
Examples of the inorganic substance or inorganic oxide include aluminum, alumina, and silicon oxide. The vapor deposition film of an inorganic substance or an inorganic oxide can shield eluents, such as acetaldehyde and formaldehyde, from the injection molded object of this embodiment and the container obtained by carrying out a secondary process. The formation method of a vapor deposition film is not specifically limited, For example, physical vapor deposition methods, such as a vacuum evaporation method, sputtering method, and an ion plating method, Chemical vapor deposition methods, such as PECVD, etc. are mentioned. The thickness of the deposited film is preferably 5 to 500 nm, more preferably 5 to 200 nm, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.
The amorphous carbon film is a diamond-like carbon film, which is a hard carbon film also called i-carbon film or hydrogenated amorphous carbon film. Examples of the method for forming the film include a method in which the inside of the hollow molded body is evacuated by evacuation, a carbon source gas is supplied thereto, and plasma generating energy is supplied by supplying plasma generating energy, Thereby, an amorphous carbon film can be formed on the inner surface of the container. The amorphous carbon film not only can remarkably reduce the permeability of low-molecular inorganic gases such as oxygen and carbon dioxide, but can also suppress the sorption of various low-molecular organic compounds having an odor. The thickness of the amorphous carbon film is preferably 50 to 5000 nm from the viewpoint of the effect of suppressing the sorption of the low molecular organic compound, the effect of improving the gas barrier property, the adhesion to the plastic, the durability and the transparency.

The oxygen-absorbing injection molded body of this embodiment and the container obtained by secondary processing thereof do not require moisture for oxygen absorption, so oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity In addition, it is suitable for packaging of various articles because of its excellent flavor retention of contents.
Specific examples of stored items include beverages such as milk, juice, coffee, tea, alcoholic beverages; liquid seasonings such as sauces, soy sauce, dressings, etc .; cooked foods such as soups, stews, curries; jams, mayonnaise, etc. Pasty foods; fishery products such as tuna and shellfish; dairy products such as cheese and butter; processed meat products such as meat, salami, sausage and ham; vegetables such as carrots and potatoes; eggs; noodles; Processed rice products such as rice, cooked cooked rice and rice bran; powdered seasonings, powdered coffee, infant milk powder, infant cooked food, powdered diet food, nursing food, dried vegetables, rice crackers and other dried food Chemicals such as agricultural chemicals and insecticides; pharmaceuticals; pet foods; detergents and the like. In particular, content that easily deteriorates in the presence of oxygen, such as beer, wine, fruit juice, carbonated soft drink, etc. for beverages, fruits, nuts, vegetables, meat products, infant foods, coffee, jam, mayonnaise, ketchup It is suitable for packaging materials such as edible oils, dressings, sauces, boiled foods, dairy products, etc., and other medicines and cosmetics.

  In addition, before and after the filling of these objects to be preserved, the oxygen-absorbing injection molded body of this embodiment and the container or the object to be preserved obtained by secondary processing thereof are sterilized in a form suitable for the objects to be preserved. be able to. Sterilization methods include hot water treatment at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultra-high temperature heat treatment at 130 ° C. or higher, electromagnetic wave sterilization of ultraviolet rays, microwaves, gamma rays, etc., ethylene oxide And gas 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]
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 make the pressure 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 ).

[Polymer production example]
(Production Example 1)
Tetralin-2,6-dicarboxylic acid obtained in the monomer synthesis example in a polyester resin production apparatus equipped with a fractionator, a total condenser, a cold trap, a stirrer, a heating device, and a nitrogen introduction pipe, etc. Dimethyl 543 g, 1,4-butanediol 315 g, and tetrabutyl titanate 0.050 g were charged, and the temperature was raised to 230 ° C. in a nitrogen atmosphere to conduct a transesterification reaction. After setting the reaction conversion rate of the dicarboxylic acid component to 85% or more, 0.050 g of tetrabutyl titanate is added, the temperature is increased and the pressure is gradually reduced, polycondensation is performed at 245 ° C. and 133 Pa or less, and the polyester compound (1) Got.

As a result of measuring the weight average molecular weight and number average molecular weight of the obtained polyester compound (1) by GPC (gel permeation chromatography), the weight average molecular weight in terms of polystyrene was 8.7 × 10 ⁴ , and the number average molecular weight was It was 3.1 × 10 ⁴ . As a result of measuring the glass transition temperature and the melting point by DSC, the glass transition temperature was 36 ° C. and the melting point was 145 ° C.

(Production Example 2)
In the same manner as in Production Example 1, 543 g of dimethyl tetralin-2,6-dicarboxylate, 217 g of ethylene glycol, 0.268 g of magnesium acetate tetrahydrate and 0.085 g of calcium acetate monohydrate were charged up to 230 ° C. under a nitrogen atmosphere. The ester exchange reaction was carried out at an elevated temperature. After setting the reaction conversion rate of the dicarboxylic acid component to 90% or more, add 0.080 g of triethyl phosphate and 0.108 g of antimony trioxide, gradually increase the temperature and reduce the pressure, and perform polycondensation at 250 ° C. and 133 Pa or less. And polyester compound (2) was obtained. The weight average molecular weight in terms of polystyrene of the polyester compound (2) was 8.5 × 10 ⁴ , the number average molecular weight was 3.0 × 10 ⁴ , the glass transition temperature was 68 ° C., and the melting point was not recognized.

(Production Example 3)
A polyester compound (3) was synthesized in the same manner as in Production Example 1 except that 1,4-butanediol in Production Example 1 was changed to 1,6-hexanediol and its weight was changed to 413 g. The weight average molecular weight of the polyester compound (3) was 8.9 × 10 ⁴ , the number average molecular weight was 3.3 × 10 ⁴ , the glass transition temperature was 16 ° C., and the melting point was 137 ° C.

(Production Example 4)
As in Production Example 1, 554 g of dimethyl tetralin-2,6-dicarboxylate, 44.3 g of ethylene glycol, 258 g of 1,4-butanediol, and 0.050 g of tetrabutyl titanate were added, and the temperature was raised to 220 ° C. in a nitrogen atmosphere. The transesterification reaction was performed. After the reaction conversion rate of the dicarboxylic acid component is 85% or more, 0.050 g of tetrabutyl titanate is added, the temperature is increased and the pressure is gradually reduced, polycondensation is performed at 250 ° C. and 133 Pa or less, ethylene glycol and 1, A polyester compound (4) having a molar ratio of 4-butanediol of 8:92 was obtained. Polyester compound (4) had a polystyrene equivalent weight average molecular weight of 1.1 × 10 ⁵ , a number average molecular weight of 4.0 × 10 ⁴ , a glass transition temperature of 38 ° C., and a melting point of 135 ° C.

Example 1
20 parts by mass of polyester compound (1), cobalt stearate (II) is 0.02 parts by mass of cobalt, 80 parts by mass of polyethylene terephthalate (manufactured by Nippon Unipet Co., Ltd., trade name: BK-2180), The above materials are supplied to a twin screw extruder having two screws with a diameter of 37 mm at a speed of 15 kg / h, melt kneading is performed at a cylinder temperature of 260 ° C., a strand is extruded from the extruder head, cooled, and pelletized. As a result, an oxygen-absorbing resin composition was obtained.

  Next, 25 g of an injection molded body (parison) was obtained by injecting a necessary amount of the oxygen-absorbing resin composition from an injection cylinder under the following conditions to fill the cavity. After cooling the obtained parison, as a secondary process, the parison was heated and biaxial stretch blow molding was performed to produce a bottle.

(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: 280 ° C
Resin channel temperature in mold: 280 ° C
Mold cooling water temperature: 20 ° C

(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 0.40 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: 0.30 sec
Primary blow time: 0.30 sec
Secondary blow time: 2.0 sec
Blow exhaust time: 0.6 sec
Mold temperature: 30 ° C.

  Subsequently, the oxygen permeability of the container obtained in an atmosphere of 23 ° C., 50% relative humidity outside the container, and 100% relative humidity inside was measured. For the measurement, an oxygen permeability measuring device (manufactured by MOCON, trade name: OX-TRAN 2-61) was used. The lower the measured value, the better the oxygen barrier property. Table 1 shows the oxygen permeability after 30 days from the start of measurement.

(Example 2)
A single-layer bottle was produced in the same manner as in Example 1 except that 50 parts by mass of the polyester compound (1) and 50 parts by mass of polyethylene terephthalate were measured, and the oxygen transmission rate was measured. The evaluation results are shown in Table 1.

(Example 3)
A single-layer bottle was produced in the same manner as in Example 1 except that the polyester compound (1) was changed to the polyester compound (2), and the oxygen transmission rate was measured. The evaluation results are shown in Table 1.

Example 4
A single-layer bottle was produced in the same manner as in Example 1 except that the polyester compound (1) was changed to the polyester compound (3), and the oxygen transmission rate was measured. The evaluation results are shown in Table 1.

(Example 5)
A single-layer bottle was prepared and the oxygen transmission rate was measured in the same manner as in Example 1 except that the polyester compound (1) was changed to the polyester compound (4). The evaluation results are shown in Table 1.

(Example 6)
A single layer bottle was produced in the same manner as in Example 1 except that 18 parts by mass of the polyester compound (1) and 2 parts by mass of the polyester compound (2) were used instead of 20 parts by mass of the polyester compound (1). The oxygen transmission rate was measured. The evaluation results are shown in Table 1.

(Comparative Example 1)
A single-layer bottle having the same shape as in Example 1 was prepared using polyethylene terephthalate (trade name: BK-2180, manufactured by Nippon Unipet Co., Ltd.), and the oxygen transmission rate was measured. The evaluation results are shown in Table 1.

  In the containers of Examples 1 to 6, since oxygen was absorbed by the oxygen absorbing layer, the oxygen permeability was small and the oxygen barrier property was excellent compared to a normal PET bottle (Comparative Example 1).

Claims (7)

An oxygen-absorbing injection-molded article comprising an oxygen-absorbing resin composition containing a polyester compound, a transition metal catalyst and a thermoplastic resin,
The polyester compound is represented by the following general formulas (1) to (4).

(In the formula, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, A group consisting of a group, a hydroxy group, a carboxyl group, an ester group, an amide group, a nitro group, an alkoxy group, an aryloxy group, an acyl group, an amino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, and an imide group At least one selected from the above, 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 hydrogen atom at the benzyl position of the tetralin ring. X is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic ring. It represents a divalent group containing at least one group selected from the group consisting of.)
An oxygen-absorbing injection molded article containing a structural unit having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing 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 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 polyester compound. The oxygen absorptivity according to any one of claims 1 to 3, wherein the structural unit represented by the general formula (1) is at least one selected from the group consisting of the following formulas (5) to (7). Injection molded body.

  The oxygen-absorbing injection molded article according to any one of claims 1 to 4, wherein the polyester compound is contained in an amount of 5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the polyester compound and the thermoplastic resin (a). .   The oxygen absorptive container obtained by further processing the oxygen absorptive injection molded object according to any one of claims 1 to 5.   The oxygen-absorbing container according to claim 6 obtained by stretch blow molding.