JP2014087970A - Oxygen-absorbable multilayer body and oxygen-absorbable multilayer container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel oxygen-absorbable multilayer body having excellent oxygen absorbing performance in which generation of odor after absorbing oxygen is suppressed without responding to a metal detector and an oxygen-absorbable multilayer container using the multilayer body, and to provide an oxygen-absorbable multilayer body having excellent oxygen absorbing performance under a wide range of humidity conditions from low humidity to high humidity and an oxygen-absorbable multilayer container using the multilayer body.SOLUTION: There is provided an oxygen-absorbable multilayer body composed of at least three layers which is obtained by laminating a sealant layer (layer C) containing a thermoplastic resin, an oxygen-absorbing layer (layer A) composed of an oxygen-absorbable resin composition containing a polyester compound and a transition metal catalyst and a gas barrier layer (layer D) containing a gas barrier substance in this order, wherein the polyester compound contains a constitutional unit having at least one tetralin ring.

Description

  The present invention is obtained by thermoforming an oxygen-absorbing multilayer body excellent in oxygen absorption performance, resin strength, resin processability and no odor generation under a wide range of humidity conditions from low humidity to high humidity. The present invention relates to an oxygen-absorbing multilayer container.

  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 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 a multilayer body and an oxygen-absorbing multilayer container including the multilayer body. Another object of the present invention is to provide an oxygen-absorbing multilayer body and an oxygen-absorbing multilayer container including the multilayer body, which have excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity. There is.

  As a result of studying the oxygen-absorbing multilayer body, the present inventors have found that the above problems can be solved by using a polyester compound having a tetralin ring and a transition metal catalyst, and have completed the present invention.

（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、酸素吸収性多層体。
＜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＞記載の酸素吸収性多層体。
＜３＞ 前記遷移金属触媒が、前記ポリエステル化合物１００質量部に対し、遷移金属量として０．００１〜１０質量部含まれる、上記＜１＞または＜２＞に記載の酸素吸収性多層体。
＜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多層体。

＜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ポリオレフィン樹脂の合計量１００質量部に対し、１０〜８０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多層体。
＜６＞ 上記＜１＞〜＜５＞のいずれかに記載の酸素吸収性多層体を含む酸素吸収性多層容器。 That is, the present invention provides the following <1> to <6>.
<1> A sealant layer (layer C) containing a thermoplastic resin, an oxygen absorbing layer (layer A) made of an oxygen absorbing resin composition containing a polyester compound, a transition metal catalyst and a polyolefin resin, and a gas barrier material. An oxygen-absorbing multilayer body containing at least three layers, in which gas barrier layers (layer D) are laminated in this order,
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 multilayer body comprising a structural unit having at least one tetralin ring selected from the group consisting of:
<2> The oxygen-absorbing multilayer body according to <1>, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.
<3> The oxygen-absorbing multilayer body 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 polyester compound.
<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. The oxygen-absorbing multilayer body described in 1.

<5> The oxygen-absorbing multilayer according to any one of <1> to <4>, wherein the polyester compound is contained in an amount of 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the polyester compound and the polyolefin resin. body.
<6> An oxygen-absorbing multilayer container comprising the oxygen-absorbing multilayer body according to any one of <1> to <5>.

  According to the present invention, an oxygen-absorbing multilayer body having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity and an oxygen-absorbing multilayer container including the multilayer body can be realized. The oxygen-absorbing multilayer body and the oxygen-absorbing multilayer container including the multilayer body can absorb oxygen regardless of the presence or absence of moisture in the storage object, and the generation of odor after oxygen absorption is suppressed. Therefore, for example, it can be used in a wide range of applications such as foods, cooked foods, beverages, pharmaceuticals, health foods and the like. It is also possible to realize an oxygen-absorbing multilayer body that is not sensitive to a metal detector and an oxygen-absorbing multilayer container including the multilayer body. Furthermore, since the strength reduction of the polyester compound due to oxidation is extremely small even after oxygen absorption, and the strength of the oxygen-absorbing resin layer is maintained even in long-term use, the oxygen-absorbing multilayer body that hardly causes delamination and the multilayer body An oxygen-absorbing multilayer container 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.

[Sealant layer (layer C)]
The layer C of this embodiment is a sealant layer containing a thermoplastic resin. In addition to the role as a sealant, the layer C has a role of isolating the oxygen absorbing layer (layer A) from the contents. Further, the oxygen permeability of the layer C is preferably 300 mL / (m ² · day · atm) or more when measured under the conditions of 23 ° C. and 60% relative humidity for a film having a thickness of 20 μm. 400 mL / (m ² · day · atm) or more is more preferable, and 500 mL / (m ² · day · atm) or more is particularly preferable. When the oxygen permeability is in the above range, the oxygen absorption rate in the layer A can be further increased as compared with a case where the oxygen permeability is less than 300 mL / (m ² · day · atm). The thermoplastic resin used for layer C includes high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, various polyethylenes such as polyethylene using a metallocene catalyst, polystyrene, poly Polypropylenes such as methylpentene, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, polyesters such as PET, A-PET, PETG, and PBT having heat seal properties, amorphous nylon, etc. They can be used alone or in combination. These thermoplastic resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid, if necessary. A copolymer, ethylene-methyl methacrylate copolymer, or thermoplastic elastomer may be added. The melt flow rate (hereinafter referred to as MFR) of the thermoplastic resin is 1 to 35 g / 10 min at 200 ° C. and 2 to 45 g / 10 min at 240 ° C., considering the processability of the multilayer body. Preferably used. In addition, MFR as used in this specification is MFR of the said resin measured on the conditions of the load of 2160g in specific temperature using the apparatus based on JISK7210, unless there is particular notice, "g / 10. Expressed with the measured temperature in units of minutes.

  Further, the thermoplastic resin used for the layer C of the present embodiment includes coloring pigments such as titanium oxide, antioxidants, slip agents, antistatic agents, stabilizers, additives such as lubricants, calcium carbonate, clay, mica, A filler such as silica or a deodorant may be added. In particular, it is preferable to add an antioxidant in order to recycle and reprocess offcuts generated during production.

  The content of the thermoplastic resin in the layer C is not particularly limited, but the content of the thermoplastic resin relative to the total amount of the layer C is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 90%. 100% by mass is particularly preferred. Moreover, in the said thermoplastic resin, it is preferable that content of thermoplastic resins other than the said polyester compound of this invention is 50-100 mass%, 70-100 mass% is more preferable, 90-100 mass% Is particularly preferred.

[Oxygen absorbing layer (layer A)]
The oxygen absorption layer (layer A) of the present embodiment includes a polyester compound containing a structural unit having at least one tetralin ring selected from the group consisting of the general formulas (1) to (4), a transition metal catalyst, And an oxygen-absorbing resin composition containing a polyolefin resin.

  The content of the polyester compound in the layer A is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, and more preferably 30 to 70 parts by weight with respect to 100 parts by weight of the total amount of the polyester compound and the polyolefin resin. Is particularly preferred. In the case of the said range, oxygen absorption performance can be improved more compared with the case of less than 10 mass parts. Moreover, a moldability can be improved compared with the case where it exceeds 90 mass parts.

[Polyester compound]
The polyester compound of this embodiment contains the structural unit which has at least 1 type of tetralin ring selected from the group which consists of 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-absorbing resin composition 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 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 polyester compound is maintained, which causes odor. It is presumed that low molecular weight organic compounds are not easily formed after oxygen absorption, and as a result, 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.

[Transition metal catalyst]
The transition metal catalyst used in the oxygen-absorbing resin composition of the present embodiment can be appropriately selected from known ones as long as it can function as a catalyst for the oxidation reaction of the polyester compound, There is no particular limitation.

  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-absorbing resin composition, 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.

[Polyolefin resin]
Polyolefin resins used in the oxygen absorbing layer of the present embodiment include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, various polyethylenes such as polyethylene by metallocene catalyst, Polypropylenes such as polystyrene, polymethylpentene, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, and cyclic polyolefins such as cycloolefin polymer and cycloolefin copolymer using cyclic olefin Or can be used in combination. These polyolefin resins include ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, if necessary. A polymer, an ethylene-methyl methacrylate copolymer, or a thermoplastic elastomer may be added. The polyolefin resin of the oxygen absorbing layer is preferably the same type as that of the polyolefin resin of the sealant layer, considering the processability of the resin and the adhesion to the sealant layer. The MFR of the polyolefin resin is preferably 1 to 35 g / 10 minutes at 200 ° C. and 2 to 45 g / 10 minutes at 240 ° C. in consideration of film processability. From the viewpoint of oxygen absorption performance, the oxygen permeability coefficient is preferably 50 to 200 cc · mm / (m ² · day · atm) (23 ° C. · 60% RH), and when a polyolefin resin having an oxygen permeability coefficient in this range is used, Good oxygen absorption performance can be obtained.

  In consideration of miscibility with the polyester compound, a maleic anhydride-modified polyolefin resin can be added. The addition amount of the maleic anhydride-modified polyolefin resin is preferably 1 to 30 parts by mass, particularly preferably 3 to 15 parts by mass with respect to 100 parts by mass of the polyolefin resin.

  Further, the polyolefin resin of the present embodiment includes coloring pigments such as titanium oxide, additives such as antioxidants, slip agents, antistatic agents, stabilizers, fillers such as calcium carbonate, clay, mica and silica, An odorant or the like may be added. In particular, it is preferable to add an antioxidant in order to recycle and reprocess offcuts generated during production.

  The polyester compound, the transition metal catalyst and the polyolefin resin can be mixed by a known method, but can be preferably used as an oxygen-absorbing resin composition having good dispersibility by kneading with an extruder. Further, in the oxygen-absorbing resin composition, additives such as a desiccant, a pigment, a dye, an antioxidant, a slip agent, an antistatic agent, a stabilizer, etc., calcium carbonate, A filler such as clay, mica, and silica, a deodorant, and the like may be added, but various materials can be mixed without being limited to the above-described ones.

  Note that the oxygen-absorbing resin composition of the present embodiment may further contain a radical generator or a photoinitiator as necessary in order to promote the oxygen absorption reaction. 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.

  In addition, the oxygen-absorbing resin composition of the present embodiment can be kneaded with another thermoplastic resin and an extruder as long as the purpose of the present embodiment is not impaired. Examples of the thermoplastic resin used for kneading include an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-vinyl chloride copolymer, an ethylene- (meth) acrylic acid copolymer, and ionic crosslinking thereof. (Ionomer), ethylene-vinyl compound copolymer such as ethylene-methyl methacrylate copolymer, styrene resin such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer, polyacrylic acid Polyvinyl compounds such as methyl and polymethyl methacrylate, nylon 6, nylon 66, nylon 610, nylon 12, polymetaxylylene adipamide (MXD6) and other polyamides, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), poly Trimethylene tele Talate (PTT), polyethylene naphthalate (PEN), glycol modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, etc. Polyethers such as polyester, polycarbonate, polyethylene oxide, etc., or a mixture thereof.

[Gas barrier layer (layer D)]
The layer D of this embodiment is a gas barrier layer containing a gas barrier substance. The oxygen permeability of the layer D is preferably 100 mL / (m ² · day · atm) or less when measured for a 20 μm thick film at 23 ° C. and a relative humidity of 60%, and 80 mL / (m ² · day · atm) or less, more preferably 50 mL / (m ² · day · atm) or less. As the gas barrier material used for the layer D, 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.

[Oxygen-absorbing multilayer]
The oxygen-absorbing multilayer body of this embodiment comprises an oxygen-absorbing layer (layer A) comprising a sealant layer (layer C) containing a thermoplastic resin, an oxygen-absorbing resin composition containing a polyester compound, a transition metal catalyst and a polyolefin resin. ), And a gas barrier layer (layer D) containing a gas barrier substance is stacked in this order. In addition, the multilayer body can be provided with a layer other than the three layers at an arbitrary position as required.

  For example, in order to prevent damage to the layer D and pinholes, a protective layer made of a thermoplastic resin can be provided inside or outside the layer D. Examples of the resin used for the protective layer include polyethylenes such as high density polyethylene, polypropylenes such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, nylon 6, nylon 6,6 and the like. Polyamides, polyesters such as PET, and combinations thereof.

  In consideration of processability, it is preferable to interpose an intermediate layer made of polyolefin resin between the layer D and the layer A. The thickness of the intermediate layer is preferably substantially the same as the thickness of the layer C from the viewpoint of workability. In this case, considering variations due to processing, the thickness is the same if the thickness ratio is within ± 10%.

  Although there is no restriction | limiting in particular in the thickness of the oxygen absorption layer (layer A) of the oxygen absorptive multilayer body of this embodiment, 5-200 micrometers is preferable and 10-100 micrometers is especially preferable. In this case, compared with the case where the thickness is out of the above range, the ability of the layer A to absorb oxygen can be further enhanced, and the workability and economy can be prevented from being impaired. The thickness of the sealant layer (layer C) made of a thermoplastic resin is preferably 5 to 200 μm, particularly preferably 10 to 80 μm. In this case, the oxygen absorption rate of the layer A can be further increased and the workability can be prevented from being impaired as compared with the case where the thickness is out of the above range. Further, in consideration of the workability of the oxygen-absorbing multilayer body, the thickness ratio of the layer C and the layer A is preferably 1: 0.5 to 1: 3, and 1: 1.5 to 1: 2.5. Is particularly preferred.

  When a thermoplastic resin is used as the gas barrier substance, the thickness of the gas barrier layer (layer D) is preferably 5 to 200 μm, particularly preferably 10 to 100 μm. When a thermosetting resin such as an amine-epoxy curing agent is used for the gas barrier adhesive layer as the gas barrier substance, the thickness of the layer D is preferably 0.1 to 100 μm, and preferably 0.5 to 20 μm. Particularly preferred. When the thickness is within the above range, the gas barrier property can be further improved and the workability and economy can be prevented from being impaired as compared with the case where the thickness is not within the above range.

  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 used depending on the properties of various materials, processing purposes, processing steps, and the like. For example, for film and sheet molding, a resin composition melted through a T die, a circular die, or the like is extruded from an attached extruder, or an adhesive is applied to an oxygen-absorbing film or sheet. There is a method of manufacturing by laminating the film and sheet. In addition, by using an injection machine, molten resin can be molded into a multilayer container having a predetermined shape by co-injection or sequential injection into an injection mold through a multilayer multiple die.

  The oxygen-absorbing multilayer body of the present embodiment can be produced as a film, processed into a bag shape and a lid material, and used. Moreover, a paper base material can be laminated | stacked on the outer layer of the layer D, and it can also be used as an oxygen absorptive paper container. In consideration of workability when laminated with a paper base material to form a paper container, the inner portion of the layer D is preferably 100 μm or less, and particularly preferably 80 μm or less. When the internal thickness is larger than that of the layer D, a problem arises in workability to the container when the paper base material is laminated and formed into a container shape.

  In addition, the oxygen-absorbing multilayer body of the present embodiment is produced as a sheet and formed into a tray, a cup, a bottle, a tube, a PTP (press-through pack), or the like by a molding method such as vacuum forming, pressure forming, or plug assist molding. It can be thermoformed into an oxygen-absorbing multilayer container of a predetermined shape. Moreover, it is preferably used for a microwave cooking-compatible pouch that fills a bag-like container with contents such as food, provides an opening, and releases steam from the opening when cooking with a microwave oven. it can.

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

  By using the oxygen-absorbing multilayer body of this embodiment as a part or all of the sealing packaging container with the layer C as the inside, oxygen in the container is absorbed in addition to oxygen that slightly enters from the outside of the container. Further, it is possible to prevent deterioration of the contents stored in the container due to oxygen.

Since the oxygen-absorbing multilayer body of this embodiment and the container including the multilayer body do not require moisture for oxygen absorption, it can be used under a wide range of humidity conditions (relative humidity 0% to 100%) from low humidity to high humidity. It is suitable for packaging various articles because of its excellent oxygen absorption performance and 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 (Food with low water activity); Chemicals such as agricultural chemicals and insecticides; pharmaceuticals; pet foods; detergents and other various articles can be mentioned, but not limited thereto. 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. The water activity is a scale indicating the free water content in an article, and is represented 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
It is defined as

  In addition, before and after filling these objects to be preserved, the oxygen-absorbing multilayer body of the present embodiment, the container containing the multilayer body, and the objects to be preserved can be sterilized in a form suitable for the object to be preserved. Sterilization methods include hot water treatment at 100 ° C. or lower, pressurized hot water treatment at 100 ° C. or higher, heat sterilization such as ultrahigh temperature heat treatment at 130 ° C. or higher, 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 250 ° 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)
In the same manner as in Production Example 1, 554 g of dimethyl tetralin-2,6-dicarboxylate, 52 g of ethylene glycol, 227 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. An exchange 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 4-butanediol molar ratio of 10:90 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
30 parts by mass of polyester compound (1), 0.02 parts by mass of cobalt stearate (II) as a cobalt amount, polyolefin resin (product name: “Umerit 4040F” manufactured by Ube Maruzen Polyethylene Co., Ltd., MFR 4.0 g / 10 min (JIS 70 parts by weight of MFR 7.9 g / 10 min at 240 ° C., MFR 8.7 g / 10 min at 250 ° C., hereinafter referred to as LLDPE1) and dry blended to obtain an oxygen-absorbing resin composition . Next, the obtained oxygen-absorbing resin composition was used as an oxygen-absorbing layer, and linear low-density polyethylene (product name: “Novatech LL UF641” manufactured by Nippon Polyethylene Co., Ltd., MFR 2.1 g / 10 min (according to JIS K7210) ), A two-type two-layer film having a width of 800 mm (thickness; oxygen absorption) using MFR 4.4 g / 10 min at 240 ° C., MFR 5.2 g / 10 min at 250 ° C., hereinafter referred to as LLDPE2) as a sealant layer A film roll was produced while subjecting the oxygen absorbing layer surface to corona discharge treatment at a rate of 100 m / min for a layer 20 μm / sealant layer 20 μm).
The film roll had no uneven thickness such as bumps, the appearance of the obtained film was good, and the HAZE was 20%. Nylon film A (product name: “N1202” manufactured by Toyobo Co., Ltd.) using a urethane dry laminate adhesive (product name: “TM-320 / CAT-13B” manufactured by Toyo Morton Co., Ltd.) on the corona-treated surface side ), Aluminum foil and PET film (product name: “E5102” manufactured by Toyobo Co., Ltd.), PET film (12) / adhesive (3) / aluminum foil (9) / adhesive (3) / nylon film An oxygen-absorbing multilayer film comprising an oxygen-absorbing multilayer body of A (15) / adhesive (3) / oxygen-absorbing resin composition (20) / LLDPE2 (20) was obtained. The numbers in parentheses mean the thickness of each layer (unit: μm). In the following examples, the same notation is used unless otherwise specified.
Next, a 15 cm × 20 cm three-side sealed bag with the LLDPE2 layer side as the inner surface was prepared, and 200 g of a powder seasoning “Dashi no Moto” having a water activity of 0.35 was filled and sealed. The sealed bag was stored at 23 ° C., and the oxygen concentration in the bag was measured after 7 days and 1 month. Moreover, the said sealing bag was opened 1 month afterward and the flavor of the powder seasoning was investigated. These results are shown in Table 1.

(Example 2)
After obtaining an oxygen-absorbing multilayer film in the same manner as in Example 1 except that 20 parts by mass of the polyester compound (1) and 80 parts by mass of the polyolefin resin were obtained, a three-side sealed bag was prepared, and the same as in Example 1 A storage test was performed. These results are shown in Table 1.

(Example 3)
After obtaining an oxygen-absorbing multilayer film in the same manner as in Example 1 except that the polyester compound (1) was 50 parts by mass and the polyolefin resin was 50 parts by mass, a three-side sealed bag was prepared, and the same as in Example 1 A storage test was performed. These results are shown in Table 1.

(Example 4)
After obtaining an oxygen-absorbing multilayer film in the same manner as in Example 1 except that the polyester compound (1) was changed to the polyester compound (2), a three-side sealed bag was prepared and the same storage test as in Example 1 was performed. did. These results are shown in Table 1.

(Example 5)
After obtaining an oxygen-absorbing multilayer film in the same manner as in Example 1 except that the polyester compound (1) was changed to the polyester compound (3), a three-side sealed bag was prepared and the same storage test as in Example 1 was performed. did. These results are shown in Table 1.

(Example 6)
After obtaining the oxygen-absorbing multilayer film in the same manner as in Example 1 except that the polyester compound (1) was changed to the polyester compound (4), a three-sided seal bag was prepared and the same storage test as in Example 1 was performed. did. These results are shown in Table 1.

(Example 7)
After obtaining an oxygen-absorbing multilayer film in the same manner as in Example 1 except that 80 parts by mass of the polyester compound (1) and 20 parts by mass of the polyolefin resin were prepared, a three-sided seal bag was prepared, and the same as in Example 1 A storage test was performed. These results are shown in Table 1.

  As is clear from Examples 1 to 7, the oxygen-absorbing multilayer body of the present invention showed good oxygen absorption performance under low humidity.

(Example 8)
An oxygen absorption layer used in Example 1 is a core layer and a skin layer is LLDPE2, and a two-type three-layer film (thickness: 10 μm / 20 μm / 10 μm) having a width of 120 mm is subjected to corona discharge treatment on one side at 120 m / min. While making.
The appearance of the obtained film was good, and HAZE was 25%. Urethane-based dry laminating adhesive (product name: “AD817 / CAT-RT86L-60” manufactured by Toyo Morton Co., Ltd.) on the corona-treated surface side, PET (product name: “E5100” manufactured by Toyobo Co., Ltd., 12 ) / Adhesive (3) / Aluminum foil (9) / Adhesive (3) / Nylon (Product name: “N1202”, 15 manufactured by Toyobo Co., Ltd.) / Adhesive (3) / LLDPE2 (10) / Oxygen absorption An oxygen-absorbing multilayer film of resin (20) / LLDPE2 (10) was obtained.
When this film was processed into a self-supporting bag (130 mm × 175 mm × 35 mm) of two side films and one bottom film with the LLDPE 2 layer side as the inner surface, the bag processability was good. The self-supporting bag was filled with 150 g of cucumber and 150 g of an acetic acid aqueous solution (acetic acid concentration: 10% by mass) at a rate of 40 bags / min, and heat sealed. The opening of the self-supporting bag was good, and heat sealing could be performed without any problem. The 100 sealed bags were boiled at 90 ° C. for 30 minutes and stored at 23 ° C. One month after storage, the color of the cucumber and the appearance of the self-supporting bag were observed, and the sealed bag was opened to examine the flavor of the cucumber. The sealed bag was transparent, and the cucumber was visible from outside the bag without opening. The color of the cucumber was well maintained, and there was no abnormality in the appearance of the bag. The cucumber flavor was also good.

(Comparative Example 1)
Iron powder having an average particle diameter of 20 μm and calcium chloride were mixed at a mass ratio of 100: 1, and the mixture and LLDPE1 were kneaded at a mass ratio of 30:70 to obtain an iron-based oxygen-absorbing resin composition A. An iron-based oxygen-absorbing resin composition A was used as a core layer, and an attempt was made to produce a two-layer / three-layer film in the same manner as in Example 8. However, iron powder irregularities occurred on the film surface, and no film was obtained.
(Comparative Example 2)
An iron-based oxygen-absorbing resin composition A is used as an oxygen-absorbing layer on a linear low-density polyethylene film (product name; “Tosero TUX HC”, hereinafter referred to as LLDPE3) manufactured by Tosero Co., Ltd., having a thickness of 40 μm. Was laminated by extrusion at a thickness of 20 μm to obtain a laminate film in which the oxygen absorbing layer surface was subjected to corona discharge treatment.
The laminate film was laminated in the same manner as in Example 8, and the alumina-deposited PET film (12) / laminating adhesive (3) / nylon film A (15) / urethane anchor coating agent (0.5) / LLDPE3 (15 ) / Iron-based oxygen-absorbing resin (20) / LLDPE3 (40), an iron-based oxygen-absorbing multilayer film was produced and processed into a self-supporting bag in the same manner as in Example 8.
As in Example 8, when trying to fill 150 g of cucumber and 150 g of acetic acid aqueous solution (acetic acid concentration 10% by mass), 30% of the defective products could not be filled due to poor bag opening. Climbed up. The storage test and evaluation were performed after the boil treatment in the same manner as in Example 8 using the self-supporting bag that could be filled. Since the self-supporting bag in the previous period was opaque, the cucumber was not visible from the outside of the bag. When the bag was opened and evaluated, the cucumber flavor and color tone were well maintained, but the bag had irregularities and some delamination occurred.

Example 9
A two-type three-layer film was prepared in the same manner as in Example 8, and this was used for extrusion laminating with low-density polyethylene (product name: “Mirason 18SP” manufactured by Mitsui Chemicals, Inc.), and bleached kraft paper (basis weight 340 g). / M ² ) / urethane-based adhesive for dry lamination (product name: “AD817 / CAT-RT86L-60” manufactured by Toyo Morton Co., Ltd., 3) / alumina-deposited PET film (product name: “GL-” manufactured by Toppan Printing Co., Ltd.) AEH ", 12) / urethane anchor coating agent (" EL-557A / B ", 0.5 manufactured by Toyo Morton Co., Ltd.) / Low density polyethylene (20) / LLDPE (10) / oxygen absorbing resin composition (20 ) / LLDPE (10) was obtained. This base material was formed into a 1-liter paperbell-top type paper container. The moldability of the container was good. This paper container was filled with sake, sealed and stored at 23 ° C. When the evaluation was performed one month later, the oxygen concentration in the paper container was 0.1 vol% or less, and the flavor of sake was well maintained.

(Example 10)
Instead of LLDPE1, an ethylene-propylene random copolymer (product name: “NOVATEC PP FW4BT” manufactured by Nippon Polypro Co., Ltd., MFR 6.5 g / 10 min at 230 ° C., MFR 8.3 g / 10 min at 240 ° C., hereinafter referred to as PP1) The oxygen-absorbing layer was obtained in the same manner as in Example 1 except that was used. A two-layer two-layer film is prepared by laminating an oxygen absorbing layer 30 μm and an olefin polymer alloy (product name: “VMX X270F” manufactured by Mitsubishi Chemical Corporation, MFR 6.5 g / 10 min at 190 ° C.) 30 μm. did. Subsequently, using a laminating adhesive, an ethylene-vinyl alcohol copolymer film (product name: “Eval F104B” manufactured by Kuraray Co., Ltd.) 15 μm and a nylon film B (product name: “N1202” manufactured by Toyobo Co., Ltd.) 15 μm laminated, nylon film B (15) / laminate adhesive (3) / ethylene-vinyl alcohol copolymer film (15) / laminate adhesive (3) / oxygen absorbing resin (30) / olefin polymer An oxygen-absorbing multilayer film of alloy (30) was obtained. The appearance of the film was good.

  Next, an ethylene-propylene random copolymer (product name: “NOVATEC PP EG7F” manufactured by Nippon Polypro Co., Ltd., MFR 1.3 g / 10 min (measured in accordance with JIS K7210), MFR 8.2 g / 10 min at 240 ° C. , 250 ° C. MFR 9.8 g / 10 min, hereinafter referred to as PP2), PP2 (400) / maleic anhydride modified polypropylene (product name; “Admer QF500”, 15) manufactured by Mitsui Chemicals, Inc./ethylene A sheet of vinyl alcohol copolymer A (product name: “EVAL L104B”, 40, manufactured by Kuraray Co., Ltd.) / Maleic anhydride modified polypropylene (product name: same as above, 15) / PP2 (400) was prepared, and the drawing ratio was obtained. Molded into a 70 cc cup at 2.5. The cup was filled with orange jelly, and the produced oxygen-absorbing multilayer film was sealed as a cover material with the nylon film B layer side as the outer surface. The color tone of the contents was visible from the lid. The sealed container was heat-treated at 85 ° C. for 30 minutes and stored at 23 ° C. for 1 month. One month later, the container was opened, and it did not become a double lid. The opening was good, and the flavor and color of the contents were well maintained.

(Example 11)
Using an oxygen-absorbing multilayer film obtained in the same manner as in Example 10 and a 70 cc cup, hydrogen peroxide sterilization was performed by immersion. There was no abnormality in the oxygen-absorbing multilayer film during sterilization. The cup was hot-filled with orange jam kept at 80 ° C., and the oxygen-absorbing multilayer film was sealed as a lid with the nylon film B layer side outside. The sealed container was stored at 23 ° C. for 1 month. One month later, when the contents were visually confirmed from the lid material, the color tone was kept good. When the lid was opened, the opening was good and the flavor of the contents was well maintained without becoming a double lid.

(Comparative Example 3)
When an iron-based oxygen-absorbing multilayer film having an iron-based oxygen absorption layer obtained in the same manner as in Comparative Example 1 was sterilized with hydrogen peroxide by the same method as in Example 11, bubbles were generated in the hydrogen peroxide, and sterilization was performed. Could not continue.

  As is clear from Examples 8 to 11, the oxygen-absorbing multilayer body of the present invention is excellent in oxygen absorption performance, workability and strength, and can be heat-treated, and oxygen absorption using an iron-based oxygen absorber. It can be applied to foods and the like that cannot be stored with a functional multilayer body, and becomes a storage container that can be sterilized with hydrogen peroxide. Moreover, it also has internal visibility, can confirm the color tone of the contents, etc., and can also be used for a container lid.

(Example 12)
Using each of the four types of 6-layer multi-layer sheet forming apparatus comprising a first to a fourth extruder, a feed block, a T die, a cooling roll, and a sheet take-up machine, from each extruder, a first extruder; PP2, a second extruder; Oxygen absorbing layer used in Example 1, third extruder; ethylene-vinyl alcohol copolymer B (product name; “EVAL L171B” manufactured by Kuraray), and fourth extruder; polypropylene-based adhesive resin (product name; “Modic AP P604V” manufactured by Mitsubishi Chemical Corporation) was extruded to obtain an oxygen-absorbing multilayer sheet. The multilayer sheet is composed of PP2 (80) / oxygen absorbing resin (100) / adhesive layer (15) / ethylene-vinyl alcohol copolymer B (30) / adhesive layer (15) / PP2 (250) from the inner layer. Met. Further, the multilayer sheet obtained by coextrusion was a multilayer sheet having a good appearance without thickness unevenness.

Next, the obtained multilayer sheet was thermoformed into a tray-like container (inner volume 350 cc, surface area 200 cm ² ) with the inner layer inside using a vacuum forming machine. The obtained oxygen-absorbing multilayer container had good appearance with no thickness unevenness. This container was sterilized by ultraviolet sterilization, and 200 g of aseptic cooked rice immediately after cooking was placed in the container, and oxygen in the container was replaced with nitrogen gas to adjust the oxygen concentration to 0.5 vol%. Next, PET film, MXD6 multilayer coextruded nylon film (product name: “Super Neal SP-R” manufactured by Mitsubishi Plastics Co., Ltd.), unstretched polypropylene film (product name: “Allomer UT21” manufactured by Okamoto Co., Ltd.) for lamination Gas barrier film dry-laminated with adhesive (PET film (12) / laminate adhesive (3) / MXD6 multilayer coextruded nylon film (15) / laminate adhesive (3) / unstretched polypropylene film (60) ) Was used as a top film and sterilized with ultraviolet rays in the same manner as the container, and then the container was sealed and stored under conditions of 23 ° C. and 50% RH. The container was opened after measuring the oxygen concentration in the container 3 months after the start of storage, and the flavor of the cooked rice and the strength of the oxygen absorbing container were confirmed. The results are shown in Table 2.
(Example 13)
A tray-like container was produced in the same manner as in Example 12 except that 20 parts by mass of the polyester compound (1) and 80 parts by mass of the polyolefin resin were used, and a storage test was performed. These results are shown in Table 1.

(Example 14)
A tray-like container was prepared in the same manner as in Example 12 except that the polyester compound (1) was 50 parts by mass and the polyolefin resin was 50 parts by mass, and a storage test was performed. These results are shown in Table 1.

(Example 15)
A tray-like container was prepared in the same manner as in Example 12 except that the polyester compound (1) was changed to the polyester compound (2), and a storage test was performed. These results are shown in Table 1.

(Example 16)
A tray-like container was produced in the same manner as in Example 12 except that the polyester compound (1) was changed to the polyester compound (3), and a storage test was performed. These results are shown in Table 1.

(Example 17)
A tray-like container was prepared in the same manner as in Example 12 except that the polyester compound (1) was changed to the polyester compound (4), and a storage test was performed. These results are shown in Table 1.

(Comparative Example 4)
Iron powder having an average particle diameter of 20 μm and calcium chloride were mixed at a mass ratio of 100: 1, and the mixture and LLDPE1 were kneaded at a mass ratio of 30:70 to obtain an iron-based oxygen-absorbing resin composition B. Subsequently, an iron-based oxygen-absorbing multilayer sheet was produced in the same manner as in Example 12 except that the iron-based oxygen-absorbing resin composition B was used for the oxygen-absorbing layer. The multilayer sheet is composed of PP2 (80) / iron-based oxygen-absorbing resin composition B (100) / adhesive layer (15) / ethylene-vinyl alcohol copolymer B (30) / adhesive layer (15) from the inner layer. / PP2 (250). The obtained iron-based oxygen-absorbing multilayer sheet was thermoformed to produce a tray-like container, but it was difficult to process because a drawdown occurred. Moreover, since the produced container used iron powder, it was opaque and the external appearance was bad because of unevenness caused by the iron powder. However, since a container having an appearance was obtained, the same storage test as in Example 12 was performed. The results are shown in Table 2.

  As is clear from Examples 12 to 17, the oxygen-absorbing multilayer container of the present invention exhibits good moldability and oxygen-absorbing performance, is transparent, and can maintain the strength of the container even after oxygen absorption. It is.

Claims (6)

A sealant layer (layer C) containing a thermoplastic resin, an oxygen absorbing layer (layer A) made of an oxygen absorbing resin composition containing a polyester compound, a transition metal catalyst and a polyolefin resin, and a gas barrier layer made of a gas barrier material (layer A) An oxygen-absorbing multilayer comprising at least three layers, wherein layers D) are laminated in this order,
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 multilayer body comprising a structural unit having at least one tetralin ring selected from the group consisting of:   The oxygen-absorbing multilayer body according to claim 1, wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper.   The oxygen-absorbing multilayer body 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). Multilayer body.

  The oxygen-absorbing multilayer body according to any one of claims 1 to 4, wherein the polyester compound is contained in an amount of 10 to 80 parts by mass with respect to 100 parts by mass of the total amount of the polyester compound and the polyolefin resin.   The oxygen absorptive multilayer container containing the oxygen absorptive multilayer body in any one of Claims 1-5.