JP2013144782A - Oxygen-absorbing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new oxygen-absorbing resin composition which is not sensitive to a metal detector, generates no odor after absorbing oxygen, and has excellent oxygen-absorbing performance; also to provide an oxygen-absorbing resin composition which has excellent oxygen-absorbing performance in a wide range of humidity conditions from low humidity to high humidity.SOLUTION: This oxygen-absorbing resin composition includes a polyamide compound and a transition metal catalyst, where the polyamide compound contains at least one structural unit having a tetralin ring.

Description

  The present invention relates to an oxygen-absorbing resin composition, and particularly to an oxygen-absorbing resin composition containing a polyamide compound having a tetralin ring and a transition metal catalyst.

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

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

  In addition, the container is made of a multilayer material in which an oxygen absorbing layer made of an oxygen absorbing resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. Development of packaging containers having an oxygen absorbing function has been carried out (see Patent Document 1). However, this also has 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 is known. For example, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal catalyst as an oxidizable organic component is known (see Patent Document 3). Furthermore, Patent Document 3 also exemplifies an oxygen absorbent, a packaging material, and a multilayer laminated film for packaging obtained by molding this resin composition.

  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, the polymer chain is broken due to oxidative degradation of the resin. However, there is a problem that the strength of the packaging 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 generates a low molecular weight organic compound that becomes an odor component due to breakage of the polymer chain accompanying the oxidation of the resin as described above, and the odor is generated after oxygen absorption. There is.

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

  The present invention has been made in view of the above problems, and its object is to provide a novel oxygen-absorbing resin that is not sensitive to metal detectors, does not generate odor after oxygen absorption, and has excellent oxygen-absorbing performance. It is to provide a composition. Another object of the present invention is to provide an oxygen-absorbing resin composition having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity.

  As a result of intensive studies on the oxygen-absorbing resin composition, the present inventors have found that the above-mentioned problems can be solved by using a polyamide compound having a predetermined tetralin ring and a transition metal catalyst. completed.

（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、酸素吸収性樹脂組成物。
＜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樹脂組成物。
＜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樹脂組成物。
＜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樹脂組成物。 That is, the present invention provides the following <1> to <4>.
<1> An oxygen-absorbing resin composition containing a polyamide compound and a transition metal catalyst, wherein 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 resin composition comprising a structural unit having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing resin composition 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 resin composition 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 resin composition according to any one of <1> to <3>, which is at least one selected from the group consisting of:

  According to the present invention, an oxygen-absorbing resin composition having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity can be realized. And this oxygen-absorbing resin composition can absorb oxygen regardless of the presence or absence of moisture in the object to be preserved, and since there is no odor generation after oxygen absorption, for example, foods, cooked foods, beverages, pharmaceuticals It can be used in a wide range of applications, including health foods, regardless of the object. It is also possible to realize an oxygen-absorbing resin composition that is not sensitive to a metal detector.

  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 resin composition]
The oxygen-absorbing resin composition of this embodiment is a polyamide compound containing a structural unit having at least one tetralin ring selected from the group consisting of structural units represented by the general formulas (1) to (2). (Hereinafter also simply referred to as “tetralin ring-containing polyamide compound”) and at least 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, m-xylylenediamine, p-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 acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acids 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 for a predetermined time.

  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.

<Usage pattern>
For the oxygen-absorbing resin composition of the present embodiment, a known granulation method or a known molding method such as extrusion molding can be applied. For example, powder, granule, pellet, film or sheet Alternatively, it can be formed into other small pieces. Therefore, the oxygen-absorbing resin molded body obtained in this way can be used as an oxygen absorbent as it is, or by filling the obtained oxygen-absorbing resin molded body into a breathable packaging material, It can also be used as an oxygen absorbent package. Moreover, the oxygen-absorbing resin composition of the present embodiment formed into a film shape or a sheet shape can also be used in the form of a label, a card, a packing or the like. Here, a film having a thickness of 0.1 to 500 μm is classified as a film and a sheet having a thickness exceeding 500 μm.

  Here, the pellet-shaped oxygen-absorbing resin molded body is preferably further pulverized into a powder form from the viewpoint of increasing the contact area with oxygen and expressing the oxygen absorption performance more effectively. .

  In addition, as said breathable packaging material, the well-known packaging material which has air permeability can be applied, and it is not specifically limited. From the viewpoint of sufficiently exhibiting the oxygen absorbing effect, the breathable packaging material is preferably highly breathable. Specific examples of breathable packaging materials include highly breathable packaging materials used in various applications, for example, paper such as Japanese paper, western paper, rayon paper, various fibers obtained from pulp, cellulose, and synthetic resin. Nonwoven fabric, plastic film or perforated material thereof used, microporous film stretched after adding calcium carbonate or the like, and those obtained by laminating two or more selected from these, etc. are particularly limited to these. Not. In addition, as a plastic film, for example, a film of polyethylene terephthalate, polyamide, polypropylene, polycarbonate or the like and a film of polyethylene, ionomer, polybutadiene, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer or ethylene vinyl acetate copolymer as a sealing layer are laminated. Adhered laminated films can also be used.

  In addition, when shape | molding and using the oxygen absorptive resin composition of this embodiment in a film form or a sheet form, it is preferable to extend | stretch etc. and to provide a micro space | gap in a film or a sheet | seat. In this way, the oxygen permeability of the film or sheet to be molded is enhanced, and the oxygen absorption performance of the tetralin ring-containing polyamide compound described above tends to be particularly effectively expressed. In addition, when a polyolefin resin is contained in the oxygen-absorbing resin composition, the polyolefin resin and the tetralin ring-containing polyamide compound can form a sea-island structure in the film or sheet, but there are voids at these interfaces due to stretching or the like. Is preferably provided. Thus, as a polyolefin resin used when extending | stretching a film or a sheet | seat, a high density polyethylene is preferable.

  Furthermore, the oxygen-absorbing resin composition of the present embodiment molded into a film or sheet can be used as a packaging material or a packaging container in a single layer form, and this is laminated with another substrate. It can be used in the form of a combined laminate. As a typical example of such a laminate, at least one layer composed of the oxygen-absorbing resin composition of the present embodiment and at least one layer selected from other resin layers, paper base material layers, metal foil layers, and the like are overlapped. Which can be used as oxygen-absorbing multilayer packaging materials or oxygen-absorbing multilayer packaging containers. In general, the oxygen-absorbing resin composition of the present embodiment formed into a film or a sheet and the oxygen-absorbing layer made of the composition are exposed from the outer surface of the container or the like so as not to be exposed on the outer surface of the container or the like. Is also preferably provided inside. In addition, from the viewpoint of avoiding direct contact with the contents, the oxygen-absorbing resin composition of the present embodiment formed into a film or sheet and the oxygen-absorbing layer made of the composition are used on the inner surface of a container or the like. It is preferable to provide the outer side. Thus, when used in a multilayer laminate, as the at least one intermediate layer, the oxygen-absorbing resin composition of the present embodiment formed into a film or sheet and the oxygen-absorbing layer comprising the composition are used. It is preferable to arrange.

  As a preferable aspect of the above laminate, at least three of a sealant layer containing a thermoplastic resin, an oxygen absorbing layer containing the oxygen absorbing resin composition of the present embodiment, and a gas barrier layer containing a gas barrier substance are used. An oxygen-absorbing multilayer body having layers in this order may be mentioned. Here, having at least three layers in this order means that the sealant layer, the oxygen absorption layer, and the gas barrier layer are arranged in this order, and the sealant layer, the oxygen absorption layer, and the gas barrier layer are directly overlaid. Not only the mode (hereinafter referred to as “sealant layer / oxygen absorption layer / gas barrier layer”), but also a resin layer between the sealant layer and the oxygen absorption layer, or between the oxygen absorption layer and the gas barrier layer. , At least one or more other layers (hereinafter also referred to as “intermediate layer”) such as a metal foil layer or an adhesive layer (for example, “sealant layer / resin layer / oxygen absorbing layer / adhesive layer / Gas barrier layer ”,“ sealant layer / resin layer / adhesive layer / oxygen absorption layer / adhesive layer / resin layer / adhesive layer / gas barrier layer / adhesive layer / support ”, etc. Even in The way is.).

  In addition, as another preferable aspect of the laminate, a sealant layer containing a polyolefin resin, an oxygen absorbing layer containing the oxygen absorbing resin composition of the present embodiment, and a gas barrier layer containing a gas barrier substance And an oxygen-absorbing multilayer body having at least three layers in this order.

  As the thermoplastic resin and polyolefin resin used in the sealant layer, the same thermoplastic resin and polyolefin resin as described in the oxygen-absorbing resin composition of the present embodiment can be used. The thermoplastic resin and polyolefin resin used in the sealant layer are appropriately selected in consideration of compatibility with other adjacent layers (oxygen absorption layer, gas barrier layer, resin layer, adhesive layer, support, etc.). It is preferable.

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

  As a method for producing the oxygen-absorbing multilayer body, known methods such as a co-extrusion method, various laminating methods, and various coating methods can be applied depending on the properties of various materials, processing purposes, processing steps, and the like. There is no particular limitation. For example, a film or sheet is produced by extruding a resin composition melted through a T die, a circular die, or the like from an attached extruder, or an oxygen absorbing film or sheet is coated with an adhesive and another film or sheet is produced. It can shape | mold by the method of bonding together. In addition, a multilayer container having a predetermined shape or a preform for manufacturing a container can be formed by co-injecting or sequentially injecting a molten resin into an injection mold through a multilayer multiple die using an injection machine. The preform is heated to a stretching temperature, stretched in the axial direction, and blow stretched in the circumferential direction by fluid pressure to obtain a stretch blow bottle.

  Furthermore, for example, a film-like oxygen-absorbing multilayer body can be processed into a bag shape or a lid material. For example, a sheet-like oxygen-absorbing multilayer body is thermoformed into an oxygen-absorbing multilayer container having a predetermined shape such as a tray, a cup, a bottle, or a tube by a molding method such as vacuum forming, pressure forming, or plug assist molding. Can do. In addition, the bag-like container is a pouch with an easy-to-open mouth that is compatible with microwave cooking, by filling the contents such as food, and then providing an opening to release steam from the opening during microwave cooking. It can be preferably used.

  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 resin composition of the present embodiment and various molded articles such as laminates using the same do not require moisture for oxygen absorption, in other words, absorb oxygen 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, sake, shochu, fruit juice drinks, fruit juices, vegetable juices, soft carbonated drinks, teas in beverages, fruits, nuts, vegetables in foods , Meat products, infant food, coffee, jam, mayonnaise, ketchup, cooking oil, dressing, sauces, boiled foods, dairy products, etc. The water activity is a scale indicating the free water content in an article, and is indicated by a number from 0 to 1, with 0 for an article without moisture and 1 for pure water. That is, the water activity Aw of a certain article is expressed as follows: the water vapor pressure in the space after the article is sealed and reached an equilibrium state is P, the water vapor pressure of pure water is P ₀ , and the relative humidity in the space is RH (%). , And
Aw = P / P ₀ = RH / 100
Is defined.

  In addition, before and after filling (packaging) of these objects to be preserved, the container or the object to be preserved can be sterilized in a form suitable for the object to be preserved. As the sterilization method, for example, heat sterilization at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultra-high temperature heat treatment at 130 ° C. or higher, sterilization by electromagnetic waves such as ultraviolet rays, microwaves, and gamma rays, Examples thereof include gas treatment such as ethylene oxide, 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 twin-screw extrusion having two screws having a diameter of 15 mm for a mixture obtained by dry blending cobalt stearate (II) with a cobalt content of 0.1 part by mass with respect to 100 parts by mass of the polyamide compound (1) An oxygen-absorbing film having a width of 80 mm and a thickness of 95 to 105 μm is produced by film formation under the conditions of an extrusion temperature of 290 ° C., a screw rotation speed of 20 rpm, a feed screw rotation speed of 16 rpm, and a take-off speed of 0.3 m / min. did.
Next, two gas barrier bags made of an aluminum foil laminated film were prepared. Then, one test piece (length 50 mm × width 200 mm) of the obtained oxygen-absorbing film was filled in two gas barrier bags together with 300 cc of air, and the relative humidity in one bag was adjusted to 100%. After the relative humidity in the other bag was adjusted to 30%, each was sealed. The sealed body thus obtained was stored at 40 ° C. for 14 days, and the total amount of oxygen absorbed during that period was measured. In addition, a sealed body in which the relative humidity in the bag is adjusted to 100% is prepared in the same manner, and stored for one month at 40 ° C. and 100% relative humidity, and the appearance of the film after one month storage is confirmed visually. The odor after opening was confirmed. These results are shown in Table 2.

(Example 2)
An oxygen-absorbing film was produced in the same manner as in Example 1 except that the polyamide compound (2) was used instead of the polyamide compound (1) and the extrusion temperature was 270 ° C. Measurement of the oxygen absorption amount of the film, visual confirmation of appearance, and odor confirmation were performed. These results are shown in Table 2.

(Example 3)
An oxygen-absorbing film was produced in the same manner as in Example 1 except that the polyamide compound (3) was used instead of the polyamide compound (1) and the extrusion temperature was 270 ° C. Measurement of the oxygen absorption amount of the film, visual confirmation of appearance, and odor confirmation were performed. These results are shown in Table 2.

Example 4
An oxygen-absorbing film was produced in the same manner as in Example 1 except that the polyamide compound (4) was used instead of the polyamide compound (1) and the extrusion temperature was 240 ° C. Measurement of the oxygen absorption amount of the film, visual confirmation of appearance, and odor confirmation were performed. These results are shown in Table 2.

(Comparative Example 1)
Oxygen absorption was carried out in the same manner as in Example 1 except that N-MXD6 (Mitsubishi Gas Chemical Co., Ltd., trade name: MX nylon S6011) was used instead of the polyamide compound (1), and the extrusion temperature was 240 ° C. A conductive film was prepared. Measurement of the oxygen absorption amount of the film, visual confirmation of appearance, and odor confirmation were performed. These results are shown in Table 2.

  As is clear from Examples 1 to 4, the oxygen-absorbing resin composition of the present invention exhibits good oxygen absorption performance under both high humidity and low humidity, and the shape of the film collapses even after oxygen absorption. It was kept without any odor and had no odor.

Claims (4)

An oxygen-absorbing resin composition containing a polyamide compound and a transition metal catalyst, wherein 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 resin composition comprising a structural unit having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing resin composition 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 resin composition 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. The structural unit represented by the general formula (1) is represented by the following formulas (3) to (6);

At least one selected from the group consisting of:
The oxygen-absorbing resin composition according to any one of claims 1 to 3.