JP6048744B2 - Oxygen-absorbing multilayer body and oxygen-absorbing container - Google Patents

Description

  The present invention relates to an oxygen-absorbing multilayer body and an oxygen-absorbing container using the same.

  For the purpose of preventing oxygen oxidation of various products, such as foods, beverages, pharmaceuticals, cosmetics, etc., which are easily altered or deteriorated by the influence of oxygen, and removing oxygen in the containers that contain them for long-term storage The oxygen absorber to be used is used.

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

  In addition, by configuring a container or the like with a multilayer material having an oxygen absorption layer made of an oxygen-absorbing resin composition in which an iron-based oxygen absorbent is blended with a thermoplastic resin, the gas barrier property of the container or the like is improved, and the container Development of packaging containers and the like imparting oxygen absorbability to itself has been carried out (see Patent Document 1). Specifically, in an oxygen-absorbing multilayer film, an oxygen absorbent is dispersed between a conventional gas-barrier multilayer film formed by laminating a heat seal layer and a gas barrier layer, optionally with an intermediate layer made of a thermoplastic resin. It has been used as an added oxygen absorbing layer, which is a thermoplastic resin layer, and has a function of absorbing oxygen in the container in addition to the function of preventing oxygen permeation from the outside, such as extrusion lamination, coextrusion lamination, and dry lamination. It is manufactured using a known manufacturing method. However, this also has the problem that it can not be heated by a microwave oven, and the object to be stored only has a high moisture content, as seen in metal detectors used for inspection of foreign substances such as food. doing. Furthermore, there is a problem that the internal visibility is insufficient due to the opaqueness. Those using oxygen absorbers such as iron powder are detected by metal detectors used to detect foreign substances such as food, and when iron is used as the content of alcohol beverages, the internal visibility is insufficient due to opacity. Aldehyde is generated by the oxidation reaction of alcohol using as a catalyst, and the flavor is lowered.

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

  On the other hand, an oxygen-absorbing resin composition comprising a resin and a transition metal catalyst is known. For example, a resin composition comprising a polyamide, particularly a xylylene group-containing polyamide and a transition metal catalyst as an oxidizable organic component is known (see Patent Documents 3 and 4). Further, Patent Documents 3 and 4 also exemplify packaging materials obtained by molding a resin composition.

  As an oxygen-absorbing resin composition that does not require moisture for oxygen absorption, an oxygen-absorbing resin composition comprising a resin having a carbon-carbon unsaturated bond and a transition metal catalyst is known (see Patent Document 5). .

  Furthermore, as a composition for collecting oxygen, a composition comprising a polymer containing a substituted cyclohexene functional group or a low molecular weight substance to which the cyclohexene functional group is bonded and a transition metal is known (see Patent Document 6). .

Japanese Patent Application Laid-Open No. 09-234832 JP-A-51-136845 JP 2001-252560 A JP 2009-108153 A Japanese Patent Laid-Open No. 05-115776 Special table 2003-521552 gazette

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

  Moreover, since the resin composition of patent document 3 expresses an oxygen absorption function by containing a transition metal catalyst and oxidizing a xylylene group-containing polyamide resin, the polymer chain due to oxidative degradation of the resin after oxygen absorption. There is a problem that cutting occurs and the strength of the packaging container itself is reduced. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture. Further, Patent Document 4 describes a method for improving delamination, but the effect is limited. Furthermore, this resin composition has a problem that oxygen absorption performance is still insufficient, and the object to be preserved exhibits only an effect of high moisture.

  Furthermore, the oxygen-absorbing resin composition of Patent Document 5 generates a low molecular weight organic compound that becomes an odor component by breaking the polymer chain accompanying the oxidation of the resin in the same manner as described above, and generates odor after oxygen absorption. There's a problem.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oxygen-absorbing multilayer body and an oxygen-absorbing container including the oxygen-absorbing multilayer body that have no oxygen generation after oxygen absorption and have excellent oxygen-absorbing performance. There is to do. Another object of the present invention is to provide an oxygen-absorbing multilayer body and an oxygen-absorbing container including the same, which have excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity.

  As a result of diligent investigations, the present inventors have determined that an oxygen-absorbing layer containing an oxygen-absorbing composition containing at least one compound having a predetermined tetralin ring, a transition metal catalyst, and a thermoplastic resin, The present inventors have found that an oxygen-absorbing multilayer body including a thermoplastic resin layer containing a plastic resin can solve the above-mentioned problems, and completed the present invention.

That is, the present invention is as follows.
[1]
An oxygen-absorbing multilayer body comprising an oxygen-absorbing layer containing an oxygen-absorbing composition and a thermoplastic resin layer containing a thermoplastic resin,
The oxygen-absorbing composition, at least one compound having a tetralin ring represented by the following general formula (1), seen containing a transition metal catalyst, and a thermoplastic resin,
(Wherein R _{1 to} R ₁₂ each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio group, imide And at least one selected from the group consisting of a substituent represented by the following general formula (1a) and a substituent represented by the following general formula (1b), and these further have a substituent. Alternatively, two substituents out of R _{1 to} R ₁₂ may be bonded to form a ring, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring.
(In the general formula (1a) and the general formula (1b), R each independently represents a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio These are at least one selected from the group consisting of a group and an imide group, which may further have a substituent, and two substituents of R may be bonded to form a ring. W is a bond or a divalent organic group, and the divalent organic group is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. Saturated fat Group hydrocarbon group and heterocyclic group, at least selected from the group consisting of —C (═O) —, —OC (═O) —, —N (H) C (═O) —, and any combination thereof. (M represents an integer of 0 to 4, n represents an integer of 0 to 7, p represents an integer of 0 to 8, and q represents an integer of 0 to 3.)
An oxygen-absorbing multilayer body , wherein the compound having a tetralin ring represented by the general formula (1) has two or more carbonyl groups .
[2 ]
In the general formula (1), at least two of R1 to R12 are monovalent substituents represented by the following general formula (2).

-C (= O) -X (2)

(Wherein X is one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a monoalkylamino group, and a dialkylamino group, and a plurality of Xs may be the same. And may be different.)
[ 1 ] The oxygen-absorbing multilayer body according to [ 1 ].
[ 3 ]
The oxygen-absorbing multilayer body according to [1] or [2] , wherein the compound having a tetralin ring represented by the general formula (1) has two or more tetralin rings.
[ 4 ]
The compound which has the tetralin ring represented by the said General formula (1) with respect to the total amount of the compound which has the tetralin ring represented by the said General formula (1) in the said oxygen absorptive composition, and the said thermoplastic resin. The oxygen-absorbing multilayer body according to any one of [1] to [ 3 ], wherein the ratio of is 1 to 30% by mass.
[ 5 ]
The thermoplastic resin according to any one of [1] to [ 4 ], wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and chlorine-based resin. Oxygen-absorbing multilayer body.
[ 6 ]
The oxygen-absorbing multilayer according to any one of [1] to [ 5 ], wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper. body.
[ 7 ]
In the oxygen-absorbing composition, the transition metal catalyst has a transition metal amount of 0 with respect to 100 parts by mass of the total amount of the compound having a tetralin ring represented by the general formula (1) and the thermoplastic resin. The oxygen-absorbing multilayer body according to any one of [1] to [ 6 ], which is contained in an amount of 0.001 to 10 parts by mass.
[ 8 ]
An oxygen-absorbing container having the oxygen-absorbing multilayer body according to any one of [1] to [ 7 ].
[ 9 ]
The oxygen-absorbing container according to [ 8 ], wherein the oxygen-absorbing container is one selected from the group consisting of a pouch, a cup, a tray, and a bottle.

  According to the present invention, it is possible to provide an oxygen-absorbing multilayer body and an oxygen-absorbing container including the same, which have no odor generation after oxygen absorption and have excellent oxygen absorption performance. The oxygen-absorbing multilayer body and the oxygen-absorbing container including the oxygen-absorbing multilayer body can absorb oxygen regardless of the presence or absence of moisture in the object to be stored, and there is no odor generation after oxygen absorption. It can be used in a wide range of applications regardless of the object, such as cooked foods, beverages, pharmaceuticals, and health foods. Moreover, according to the preferred embodiment of the present invention, an oxygen-absorbing multilayer body that is insensitive to a metal detector and an oxygen-absorbing container including the same are also realized.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

[Oxygen-absorbing multilayer]
The oxygen-absorbing multilayer body of this embodiment includes an oxygen-absorbing multilayer (layer A) containing an oxygen-absorbing composition and a thermoplastic resin layer (layer B) containing a thermoplastic resin. And the oxygen-absorbing composition includes at least one compound having a tetralin ring represented by the following general formula (1), a transition metal catalyst, and a thermoplastic resin.
(Wherein R _{1 to} R ₁₂ each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio group, imide And at least one selected from the group consisting of a substituent represented by the following general formula (1a) and a substituent represented by the following general formula (1b), and these further have a substituent. Alternatively, two substituents out of R _{1 to} R ₁₂ may be bonded to form a ring, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring.
(In the general formula (1a) and the general formula (1b), R each independently represents a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio These are at least one selected from the group consisting of a group and an imide group, which may further have a substituent, and two substituents of R may be bonded to form a ring. W is a bond or a divalent organic group, and the divalent organic group is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. Saturated fat Group hydrocarbon group and heterocyclic group, at least selected from the group consisting of —C (═O) —, —OC (═O) —, —N (H) C (═O) —, and any combination thereof. (M represents an integer of 0 to 4, n represents an integer of 0 to 7, p represents an integer of 0 to 8, and q represents an integer of 0 to 3.)
It is an oxygen-absorbing multilayer body.

  The layer structure in the oxygen-absorbing multilayer body of the present embodiment is not particularly limited, and the number and types of oxygen-absorbing layers (layer A) and thermoplastic resin layers (layer B) are not particularly limited. For example, it may be an A / B configuration consisting of one layer A and one layer B, or a three-layer configuration B / A / B consisting of one layer A and two layers B. Also good. Further, it may have a five-layer configuration of B1 / B2 / A / B2 / B1 composed of one layer A and two types and four layers B of layer B1 and layer B2, and one layer A and layer B1. And a three-layer configuration of B1 / A / B2 composed of two types and two layers of layer B2. Furthermore, the multilayer body of the present embodiment may include an arbitrary layer such as an adhesive layer (layer AD) as necessary. For example, the multilayer body has a seven-layer configuration of B1 / AD / B2 / A / B2 / AD / B1. There may be.

[Oxygen absorbing layer (layer A)]
The oxygen absorbing layer (layer A) of the oxygen-absorbing multilayer body of the present embodiment has at least one compound having a tetralin ring represented by the general formula (1) (hereinafter also simply referred to as “tetralin compound”). , A transition metal catalyst, and a layer containing an oxygen-absorbing composition containing a thermoplastic resin.

<Compound with tetralin ring>
In the general formula (1), examples of the monovalent substituent represented by R _{1 to} R ₁₂ include a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group (preferably having 1 to 15 carbon atoms, More preferably, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-octyl group, or 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 ), An alkynyl group (preferably an alkynyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, such as an ethynyl group or a propargyl group), an aryl group (preferably carbon Is an aryl group having 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). Monovalent groups obtained by removing one hydrogen atom from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound, for example, 1-pyrazolyl group, 1-imidazolyl group, 2-furyl Group), cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group (preferably linear or branched having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) A 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 such as a phenoxy 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 7 to 9 carbon atoms. An arylcarbonyl group such as an acetyl group, a pivaloyl group or a benzoyl group), an amino group (preferably an alkylamino group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, preferably 6 to 12 carbon atoms). , More preferably an anilino group having 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, a methylamino group, and an anilino group) , A thiol group, an alkylthio group (preferably an alkylthio group having 1 to 10 carbon atoms, more preferably an alkylthio group having 1 to 6 carbon atoms, such as a methylthio group or an ethylthio group), an arylthio group (Preferably an arylthio group having 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, such as a phenylthio group), a heterocyclic thio group (preferably having 2 to 10 carbon atoms, more preferably 1 carbon number) To 6 heterocyclic thio groups such as 2-benzothiazolylthio group), imide groups (preferably having 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, such as N-succinimide group). , N-phthalimido group) and the like, but not limited thereto.

In the compound represented by the general formula (1), at least one hydrogen atom is bonded to the benzyl position of the tetralin ring. As will be described later, an excellent oxygen absorption ability and the like can be expressed by the action of a hydrogen atom bonded to the benzyl position of the tetralin ring and a transition metal catalyst described later. Examples of the compound in which at least one hydrogen atom is bonded to the benzyl position of the tetralin ring include, for example, any one of R ₁ , R ₄ , R ₉ and R _{12 in} the general formula (1) is a hydrogen atom. The compound etc. which are are mentioned.

In addition, when the above monovalent substituents R _{1 to} R ₁₂ have a hydrogen atom, the hydrogen atom is a substituent T (wherein the substituent T is the same as that described for the monovalent substituent R above). It may be further substituted with the same meaning. 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.

Two of the monovalent substituents R _{1 to} R ₁₂ may be bonded to form a ring. Specific examples thereof include compounds in which two of R _{1 to} R ₁₂ are condensed to form a 5- to 8-membered ring. The ring herein may be any known ring structure and is not particularly limited, but is preferably an aromatic ring, aliphatic ring or heterocycle having 4 to 7 carbon atoms (more preferably , Cyclohexane ring, cycloheptane ring, acid anhydride ring (for example, succinic anhydride ring, glutaric anhydride ring, adipic anhydride ring, etc.), benzene ring, bicyclo ring, etc.). ).

From the viewpoint of suppressing loss due to volatilization during use and increasing the amount of oxygen absorbed per unit mass of the compound, the compound having a tetralin ring represented by the general formula (1) is at least _one of R _{1 to} R ₁₂ . One is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxy group, a carboxyl group, a substituted or unsubstituted ester group, an alkoxy group, an acyl group, a substituted or unsubstituted amide group, and a substituted or unsubstituted group. One selected from the group consisting of substituted imide groups (hereinafter also simply referred to as “substituent group S”); preferably one in which two or more Rs are condensed to form a 5- to 6-membered ring. . Among these substituent groups S, there are substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, hydroxy groups, carboxyl groups, alkoxy groups, substituted or unsubstituted ester groups, and substituted or unsubstituted amide groups. More preferred.

As a preferred first embodiment of the compound having a tetralin ring represented by the above general formula (1), there may be mentioned those having the structures shown below.
(In the general formula (1c), R _{1 to} R ₈ each independently represents a monovalent substituent, and the monovalent substituent has the same meaning as R _{1 to} R ₁₂ described above, provided that Two or more of R _{1 to} R ₈ are not bonded to form a ring.)

In the first aspect, at least two of R _{1 to} R ₈ are one selected from the substituent group S described above, and the other R _{1 to} R ₈ are hydrogen atoms. It is preferable that two of R _{1 to} R ₈ are one selected from the substituent group S, and 6 of R _{1 to} R ₈ is more preferably a hydrogen atom.

In the first aspect, various isomers are included. For example, when two substituents are introduced into tetralin represented by the following general formula (1-1), the structural isomers are represented by the following general formulas. Although tetralin derivatives represented by (1-2) to (1-15) may be generated, the introduction position (substitution position) of the substituent is not particularly limited.

Hereinafter, examples included in the first aspect are listed, but not limited thereto.
(In each formula, n is an integer of 0 to 3, each R independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is an aromatic hydrocarbon group, saturated or It is at least one selected from the group consisting of an unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and an acyl group.)

  Here, examples of the aromatic hydrocarbon group include, but are not particularly limited to, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a fluorenyl group. Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group, and a cycloalkenyl group, but are not particularly limited thereto. Examples of the aliphatic hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-hexyl group, and n-octyl group. Group, 2-ethylhexyl group, n-decyl group, lauryl group, stearyl group, palmityl group and other linear and branched alkyl groups, ethenyl group, propenyl group, butenyl group, octenyl group, nonadecenyl group, pentacosenyl group Examples include alkenyl groups such as groups, but are not limited thereto. Examples of the acyl group include, but are not limited to, an acetyl group, a pivaloyl group, and a benzoyl group. 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.

  Moreover, as a preferable 2nd aspect of the compound which has a tetralin ring represented by said general formula (1), the thing of the structure represented by the following general formula (2-1)-(2-5) is mentioned. It is done.

_(Wherein, R 1 to R ₈ each independently represent a hydrogen atom or a monovalent substituent, _{R 1} a monovalent substituent _R 1 to R ₈ are as described in the general formula (1) to R ₁₂ in the above formula, arc a is the number of carbon atoms of the substituted or unsubstituted is an aromatic ring, heterocyclic or acid anhydride ring of 4-7.)

  In said 2nd aspect, it is preferable that the circular arc A is a C4-C7 aromatic ring, an aliphatic ring, or a heterocyclic ring. Specific examples thereof include benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, acid anhydride ring (succinic acid anhydride ring, glutaric acid anhydride ring, adipic acid anhydride ring) and the like.

  Furthermore, a preferred third embodiment of the compound having a tetralin ring represented by the general formula (1) includes those having two or more carbonyl groups.

As an example of the third embodiment having two or more carbonyl groups, monovalent substitution in which two or more of R _{1 to} R ₁₂ of the general formula (1) are represented by the following general formula (2) It is preferably a group.
(In Formula (1), R < ₁ > -R < ₁₂ > shows a hydrogen atom or a monovalent substituent each independently, and monovalent substituent R < ₁ > -R < ₁₂ > is synonymous with what was demonstrated above. However, two or more of R _{1 to} R ₁₂ are not bonded to form a ring.)

-C (= O) X (2)

(In Formula (2), X is one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a monoalkylamino group, and a dialkylamino group, and the plurality of Xs are the same. May be different or different.)

Further, in the third embodiment of the _above, R 1 _{to R 12} are the following requirements (A) ~ (C);
(A) One or more monovalent substituents represented by the above general formula (2) are bonded to the aromatic ring of the tetralin ring, and the aliphatic ring of the tetralin ring is represented by the above general formula (2). One or more monovalent substituents are bonded.
(B) Two or more monovalent substituents represented by the general formula (2) are bonded to the aromatic ring of the tetralin ring.
(C) Two or more monovalent substituents represented by the general formula (2) are bonded to the aliphatic ring of the tetralin ring.
Those satisfying any of these are more preferable.

  In the monovalent substituent represented by the general formula (2), X is preferably an alkoxy group represented by an —O—Z group or a monoalkylamino group represented by an NH—Z group. -Z represents an aromatic hydrocarbon group having 1 to 10 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group, or a linear or branched saturated or unsaturated aliphatic hydrocarbon group. It is more preferable that In addition, since these specific examples overlap with what was demonstrated by the substituent R mentioned above, description here is abbreviate | omitted.

Hereinafter, although the example of the 3rd aspect which satisfy | fills said requirements (A)-(C) is enumerated, it does not specifically limit to these.
(In each formula, Z has the same meaning as described in the general formula (2).)

Among the above third embodiments, compounds represented by the following general formulas (3-10) to (3-20) are more preferable.

Specific examples of the compound having a tetralin ring represented by the general formula (1) are shown below, but are not particularly limited thereto.
(In the formula, n is an integer of 0 to 3.)

  Furthermore, as a preferable fourth aspect of the compound having a tetralin ring represented by the general formula (1), those having two or more tetralin rings can be mentioned. The upper limit of the tetralin ring is preferably 12 or less, and preferably 3 or less from the viewpoint of availability. In particular, the number of tetralin rings is more preferably 2 from the viewpoint of the balance between oxygen absorption performance and heat resistance and availability.

As an example of the fourth embodiment having two or more tetralin rings, at least one compound selected from the group consisting of the following general formulas (4-1) to (4-6) is preferable.
(In the formula, each R independently represents a monovalent substituent, and the monovalent substituent R has the same meaning as R _{1 to} R ₁₂ described above. M represents 0 to 7, and n represents 0. -3, p represents an integer of 0-4, q represents an integer of 0-6, and one or more hydrogen atoms are bonded to the benzylic position of the tetralin ring, and X represents an aromatic hydrocarbon group, saturated or Represents a divalent group containing at least one group selected from the group consisting of an unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group and a heterocyclic group. Y represents an ester group or an amide group, and t represents an integer of 0 to 6.)

Examples of the substituent represented by R in the general formulas (4-1) to (4-6) include those exemplified as R _{1 to} R ₁₂ above. Among these, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a hydroxy group, a carboxyl group, an ester group, an alkoxy group, an acyl group, an amide group, and an imide group are preferable, a hydrogen atom, a substituted group Or an unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, an ester group and an acyl group are more preferred, and a hydrogen atom, an unsubstituted alkyl group, an alkoxy group and an ester group are particularly preferred.

  The molecular weight of the compounds represented by the general formulas (4-1) to (4-6) is preferably 276 to 1000, more preferably 300 to 800, and particularly preferably 350 to 600. A molecular weight of 276 or more is preferable because loss due to volatilization during use can be suppressed as compared with a molecular weight of less than 276. Further, when the molecular weight is 1000 or less, the proportion of the tetralin ring moiety in the compound is higher than that when the molecular weight exceeds 1000, and this is preferable because the amount of oxygen absorbed per unit mass of the compound is increased.

  In addition, the compounds represented by the general formulas (4-1) to (4-6) preferably have a high boiling point and a low vapor pressure at the temperature at the time of use because loss due to volatilization at the time of use can be suppressed. Further, when the compound is an oxygen-absorbing composition to be described later, the vapor pressure at the kneading temperature with the thermoplastic resin is lower, and the higher the 3% weight loss temperature, the more loss due to volatilization during the production of the oxygen-absorbing composition. Since it can suppress, it is preferable. The 3% weight loss temperature is preferably 150 ° C. or higher, more preferably 200 ° C. or higher, and particularly preferably 250 ° C. or higher.

  Among the above functional groups, those having a hydrogen atom may be further substituted with the above group, for example, an alkyl group substituted with a hydroxy group (for example, a hydroxyethyl group), an alkyl substituted with an alkoxy group A group (eg, methoxyethyl group), an alkyl group substituted with an aryl group (eg, benzyl group), an aryl group substituted with alkyl (eg, p-tolyl group), an aryloxy group substituted with an alkyl group ( Examples thereof include, but are not limited to, 2-methylphenoxy group. In addition, when a functional group is further substituted, the carbon number mentioned above shall not include the carbon number of the further substituent. 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. The substituent of tetralin having a substituent may have a plurality of substituents. Moreover, it is not always necessary to use a single substance, and two or more kinds may be mixed and used.

  As the compounds represented by the general formulas (4-1) to (4-6), the compounds represented by the following general formulas (4-7) to (4-16) are more preferable. 7), (4-10), (4-13) or (4-16) is particularly preferred.

(In the formula, X represents an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group.)

Although the preferable specific example of the said General formula (4-7) is shown below, this embodiment is not limited to these.

Although the preferable specific example of the said General formula (4-10) is shown below, this embodiment is not limited to these.

Although the preferable specific example of the said General formula (4-13) is shown below, this embodiment is not limited to these.

Although the preferable specific example of the said General formula (4-16) is shown below, this embodiment is not limited to these.

  As a compound having two tetralin rings in one molecule, the above general formulas (4-1) to (4-16) and formulas (4-17) to (4-33) were shown. In the present embodiment, a compound having three or more tetralin rings is also preferably used.

  The manufacturing method of the compound represented by General Formula (4-1)-(4-6) is not limited at all, and can be manufactured by a known method. For example, a transesterification reaction between an ester of a polycarboxylic acid having two or more carboxyl groups and a compound having a hydroxy group and a tetralin ring, a polyol having two or more hydroxy groups, and a compound having a carboxyl group and a tetralin ring And the reaction of an aldehyde with a compound having a tetralin ring are preferably exemplified.

  In another preferred example of the fourth aspect having two or more tetralin rings, the tetralin ring has two or more tetralin rings, and at least one of the tetralin rings has a hydrogen atom bonded to its benzylic position. And compounds having two or more imide bonds.

By having two or more tetralin rings, many reaction points with oxygen can be included, and furthermore, by having two or more imide bonds, heat resistance can be further improved. As such a compound, for example, at least one selected from the group consisting of the following general formulas (4-34) to (4-37) is preferable.
(In the general formulas (4-34) to (4-37), R each independently represents a monovalent substituent, and the monovalent substituent R has the same meaning as R _{1 to} R ₁₂ described above. M is an integer from 0 to 6, n is an integer from 0 to 3, p is an integer from 0 to 7, q is an integer from 0 to 2, r is an integer from 0 to 4, and s is an integer from 0 to 5. In at least one tetralin ring, one or more hydrogen atoms are bonded to the benzyl position, X represents a divalent substituent, and the divalent substituent is aromatic. It is at least one selected from the group consisting of a hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated aliphatic hydrocarbon group, and a heterocyclic group. )

  The molecular weight of the compounds represented by the general formulas (4-34) to (4-37) is not particularly limited, but is preferably 414 to 1000, more preferably 430 to 800, and further preferably 450 to 600. When the molecular weight is 414 or more, loss due to volatilization during use can be further suppressed. When the molecular weight is 1000 or less, the oxygen absorption capacity is further improved.

  As the compounds represented by the general formulas (4-34) to (4-37), those having a high boiling point and a low vapor pressure at the temperature during use are preferable because loss due to volatilization during use can be further suppressed. Further, these compounds preferably have a low vapor pressure at the kneading temperature with the thermoplastic resin. Moreover, as these compounds, 3% weight loss temperature is so preferable that it is high. Although it does not specifically limit as 3% weight reduction | decrease temperature, 150 degreeC or more is preferable, 200 degreeC or more is more preferable, 250 degreeC or more is further more preferable, 270 degreeC or more is more preferable.

  It does not specifically limit as a manufacturing method of the compound represented by General formula (4-34)-(4-37), For example, it can manufacture by a well-known method. For example, it can be obtained by reacting a diamine compound and an acid anhydride compound.

  All of the compounds having a tetralin ring represented by the general formula (1) described above have hydrogen at the benzyl position of the tetralin ring, and when used in combination with a transition metal catalyst described later, the hydrogen at the benzyl position is pulled. By pulling out, it exhibits excellent oxygen absorption ability.

  Moreover, the oxygen-absorbing composition of the present embodiment is one in which an increase in odor intensity after oxygen absorption is suppressed. Although the reason is not clear, for example, the following oxidation reaction mechanism is assumed. That is, in the compound having a tetralin ring represented by the general formula (1), hydrogen at the benzyl position of the tetralin ring is first extracted to generate a radical, and then the benzyl position is obtained by the reaction between the radical and oxygen. It is considered that the carbon of this is oxidized to form a hydroxy group or a ketone group. Therefore, as an oxygen-absorbing composition, the molecular chain of the oxygen-absorbing main agent is not broken by an oxidation reaction as in the prior art, and the structure of the oxygen-absorbing main agent (compound) is maintained. It is presumed that the organic compound is hardly formed after oxygen absorption, and as a result, the increase in odor intensity after oxygen absorption is suppressed. Also from this viewpoint, in a compound having a tetralin ring, the larger the number of tetralin rings, the better. As a result, the number of reaction points with oxygen increases, and the oxygen absorbing ability is further improved. Further, the hydrogen at the benzyl position of the tetralin ring described above may be present on at least one tetralin ring. For example, when it has the general formula (1a) or the general formula (1b) as a substituent, From the above viewpoint, it is preferable that hydrogen bonded to the benzyl position described above also exists in the tetralin ring of the general formula (1a) or the general formula (1b).

The molecular weight of the compound having a tetralin ring represented by the general formula (1) described above can be appropriately adjusted according to desired properties and substituents R _{1 to} R ₈ to be introduced, and is not particularly limited. From the viewpoint of suppressing loss due to volatilization during use and increasing the amount of oxygen absorbed per unit mass of the compound, the molecular weight is preferably in the range of 190 to 1500, more preferably 210 to 1200, and even more preferably 250 to 1000. In addition, the compound which has a tetralin ring represented by General formula (1) mentioned above can be used individually by 1 type or in combination of 2 or more types.

  Among the compounds having a tetralin ring represented by the general formula (1), those having a high boiling point, that is, a low vapor pressure at the temperature during use, are preferably used from the viewpoint of suppressing loss due to volatilization during use. . For example, as the compound, a compound having a lower vapor pressure at a kneading temperature with a thermoplastic resin is preferable because loss due to volatilization during production of the oxygen-absorbing composition can be suppressed. As an index of loss due to volatilization, for example, a 3% weight loss temperature can be adopted. That is, the compound preferably has a 3% weight loss temperature of 100 ° C or higher, more preferably 150 ° C or higher, and further preferably 200 ° C or higher. The upper limit value of the 3% weight reduction temperature is not particularly limited.

  The ratio of the compound having the tetralin ring represented by the general formula (1) to the total amount of the compound having the tetralin ring represented by the general formula (1) and the thermoplastic resin described later in the oxygen-absorbing composition is: 1 to 30% by mass, more preferably 1.5 to 25% by mass, and still more preferably 2 to 20% by mass. By making the ratio of the compound having a tetralin ring represented by the general formula (1) equal to or higher than the above lower limit value, the oxygen absorption performance can be further increased, and by setting the ratio below the upper limit value, the moldability is further improved. Can be increased.

<Transition metal catalyst>
The transition metal catalyst used in the oxygen-absorbing 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 compound having a tetralin ring. 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 blending amount of the transition metal catalyst can be appropriately set according to the type of the compound having the tetralin ring used, the thermoplastic resin, the transition metal catalyst, and the desired performance, and is not particularly limited. From the viewpoint of the oxygen absorption amount of the oxygen-absorbing composition, the blending amount of the transition metal catalyst is 100 parts by mass with respect to the total amount of the compound having the tetralin ring represented by the general formula (1) and the thermoplastic resin. The amount of transition metal is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 2 parts by mass, and still more preferably 0.01 to 1 part by mass.

  Further, for example, the mixture of the compound and the transition metal catalyst is processed into a powder, granule, pellet or other small piece by applying a known granulation method or molding method, and this is described above. The layer A can also be blended with the thermoplastic resin.

  Here, the oxygen-absorbing composition used in the present embodiment may further contain a carrier substance as necessary. At this time, the oxygen-absorbing composition containing the carrier material can be used as an oxygen absorbent as it is as a mixture of the compound, the thermoplastic resin, the transition metal catalyst, and the carrier material. In addition, a carrier having the tetralin ring represented by the general formula (1) described above supported on or impregnated on a carrier material by supporting or impregnating the compound with a transition metal catalyst on a carrier material as necessary. (Hereinafter also referred to as “oxygen absorbent carrier”), and this carrier can also be used as an oxygen absorbent. Thus, by carrying or impregnating the above-mentioned compound on a carrier substance, the contact area with oxygen can be increased, the oxygen absorption rate or oxygen absorption amount can be increased, and handling can be simplified.

  The carrier material can be appropriately selected from those known in the art. Specific examples thereof include, for example, synthetic calcium silicate, slaked lime, activated carbon, zeolite, pearlite, diatomaceous earth, activated clay, silica, kaolin, talc, bentonite, activated alumina, gypsum, silica alumina, calcium silicate, magnesium oxide, graphite. , Powders of carbon black, aluminum hydroxide, iron oxide and the like are mentioned, but not limited thereto. Among these, synthetic calcium silicate, diatomaceous earth, silica, and activated carbon are preferably used. In addition, a carrier substance can be used individually by 1 type or in combination of 2 or more types.

  The amount of the carrier substance can be set as appropriate according to the type of the compound used, the thermoplastic resin or the transition metal catalyst and the desired performance, and is not particularly limited, but has a tetralin ring represented by the general formula (1). It is preferable that it is 10-1000 mass parts with respect to 100 mass parts of compounds, More preferably, it is 20-800 mass parts.

  The loading of the compound on the carrier material can be carried out according to a conventional method and is not particularly limited. For example, a mixed solution containing a compound having a tetralin ring represented by the above general formula (1) or a mixed solution containing this compound and a transition metal catalyst is prepared, and this mixed solution is applied to a support material. Alternatively, it is possible to obtain an oxygen absorbent carrier in which the above-mentioned compound (and a transition metal catalyst if necessary) is carried (impregnated) on the carrier material by immersing the carrier material in this mixed solution. In addition, a solvent can be further contained during the preparation of the mixed solution. When the compound or the transition metal catalyst is a solid, it can be efficiently supported on a support material by using a solvent. The solvent used here can be appropriately selected from known ones in consideration of the solubility of the compound and transition metal catalyst, and is not particularly limited. For example, methanol, 2-propanol, ethylene glycol , Toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, diisopropyl ether, tetrahydrofuran, methyl ethyl ketone, dichloromethane, chloroform, and other organic solvents are preferred, and methanol, 2-propanol, ethyl acetate, and methyl ethyl ketone are more preferred. In addition, a solvent can be used individually by 1 type or in combination of 2 or more types.

<Thermoplastic resin>
The oxygen-absorbing composition of the present embodiment contains a thermoplastic resin. At this time, the content of the compound having a tetralin ring and the transition metal catalyst in the oxygen-absorbing composition is not particularly limited. For example, even if the compound having the tetralin ring and the transition metal catalyst are contained as they are in the thermoplastic resin, the compound having the tetralin ring and the transition metal catalyst are supported on the above-described carrier material in the thermoplastic resin. It may be contained in.

  The method for preparing the oxygen-absorbing composition can be performed according to a conventional method and is not particularly limited. For example, an oxygen-absorbing composition can be obtained by mixing or kneading the compound having a tetralin ring, a transition metal catalyst, and a carrier material blended as necessary with a thermoplastic resin.

  As the above thermoplastic resin, known ones can be used as appropriate, and are not particularly limited. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra low density polyethylene, Polyolefin such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or a random or block copolymer of α-olefins such as ethylene, propylene, 1-butene, 4-methyl-1-pentene ; Acid-modified polyolefin such as maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene; ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene- (meth) acrylic acid copolymer Polymers and their ionic cross-linked products (ionomers) , Ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer; polymethyl acrylate, polymethacryl Polyvinyl compounds such as methyl acid; polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, polymetaxylylene adipamide (MXD6); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate ( PTT), polyethylene naphthalate (PEN), glycol-modified polyethylene terephthalate (PETG), polyethylene succinate (PES), polybutylene succinate (PBS), polylactic acid, polyglycolic acid, Polycarbonates; Li caprolactone, polyesters such as polyhydroxyalkanoates polyethers such as polyethylene oxide or mixtures thereof. In addition, a thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  Among these, the thermoplastic resin is preferably at least one selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, plant-derived resin, and chlorine-based resin. Furthermore, it is preferably at least one selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and chlorinated resin. Hereinafter, these preferable thermoplastic resins will be described in detail.

<Polyolefin>
Examples of the polyolefin used in the oxygen-absorbing composition of the present embodiment include, for example, polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, and linear ultra low density polyethylene, polypropylene, and polybutene- 1, olefin homopolymers such as poly-4-methylpentene-1; ethylene-propylene random copolymer, ethylene-propylene block copolymer, ethylene-propylene-polybutene-1 copolymer, ethylene-cycloolefin copolymer Copolymers of ethylene and α-olefins such as ethylene; ethylene-α, β-unsaturated carboxylic acid copolymers such as ethylene- (meth) acrylic acid copolymers, ethylene-ethyl (meth) acrylate copolymer Ethylene-α, β-unsaturated carboxylic acid ester copolymer, ethylene, etc. -Other ethylene copolymers such as ionic cross-linked products of α, β-unsaturated carboxylic acid copolymers, ethylene-vinyl acetate copolymers; ring-opening polymers of cyclic olefins and hydrogenated products thereof; cyclic olefins- And ethylene copolymers; and graft-modified polyolefins obtained by graft-modifying these polyolefins with acid anhydrides such as maleic anhydride.

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

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

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

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

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

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

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

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

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

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

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

  The polyester whose main acid component is terephthalic acid or an ester-forming derivative thereof is preferably a polyester containing terephthalic acid or an ester-forming derivative thereof in total of 70 mol% or more based on the total acid components, More preferred is a polyester containing 80 mol% or more, and even more preferred is a polyester containing 90 mol% or more. Similarly, the polyester in which the main acid component is naphthalenedicarboxylic acid or an ester-forming derivative thereof is preferably a polyester containing 70 mol% or more of naphthalenedicarboxylic acids or an ester-forming derivative thereof, more preferably It is a polyester containing 80 mol% or more, more preferably a polyester containing 90 mol% or more.

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

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

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

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

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

  Other preferable examples of the polyester used in the oxygen-absorbing composition of the present embodiment include a linear polyester containing 70 mol% or more of propylene terephthalate units, a linear polyester containing 70 mol% or more of propylene naphthalate units, A linear polyester containing 70 mol% or more of 1,4-cyclohexanedimethylene terephthalate units, a linear polyester containing 70 mol% or more of butylene naphthalate units, or a linear polyester containing 70 mol% or more of butylene terephthalate units.

  From the viewpoint of coexistence of transparency and moldability, particularly suitable polyesters include a combination of terephthalic acid / isophthalic acid / ethylene glycol, terephthalic acid / ethylene glycol / 1,4-cyclohexanedimethanol as a combination of the whole polyester. Combination, terephthalic acid / ethylene glycol / neopentyl glycol combination. Needless to say, the above polyester may contain a small amount (5 mol% or less) of diethylene glycol produced by dimerization of ethylene glycol during esterification (transesterification) reaction or polycondensation reaction. Nor.

  Other preferable examples of the polyester used in the oxygen-absorbing composition of the present embodiment include polyglycolic acid obtained by polycondensation of glycolic acid or methyl glycolate or ring-opening polycondensation of glycolide. The polyglycolic acid may be one in which other components such as lactide are copolymerized.

<Polyamide>
As the polyamide used in the oxygen-absorbing composition of the present embodiment, for example, a polyamide having a unit derived from lactam or aminocarboxylic acid as a main constituent unit, or derived from an aliphatic diamine and an aliphatic dicarboxylic acid. Units derived from aliphatic polyamides whose units are main constituent units, partially aromatic polyamides whose main constituent units are units derived from aliphatic diamines and aromatic dicarboxylic acids, and aromatic diamines and aliphatic dicarboxylic acids And partially aromatic polyamides having a main structural unit. In addition, the polyamide here may be copolymerized with monomer units other than the main structural unit, if necessary.

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

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

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

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

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

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

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

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

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

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

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

  Among the thermoplastic resins exemplified above, linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), nylon 6 (PA6), polyethylene terephthalate (PET), polyvinyl chloride (PVC), It is preferably used as a food packaging material.

  Note that the oxygen-absorbing 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 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.

  Moreover, said oxygen absorptive composition may contain various well-known additives in this industry in the range which does not impair the effect of this embodiment. Examples of such optional components include fillers such as calcium carbonate, clay, mica and silica, drying agents, pigments, dyes, antioxidants, slip agents, antistatic agents, stabilizers, plasticizers, deodorants and the like. Although it is mentioned, it is not specifically limited to these.

[Thermoplastic resin layer (layer B)]
The thermoplastic resin layer (layer B) of the oxygen-absorbing multilayer body of the present embodiment is a layer containing a thermoplastic resin. The content ratio of the thermoplastic resin in the layer B can be appropriately set and is not particularly limited, but is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably based on the total amount of the layer B. Is 90 to 100% by mass.

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

  As the thermoplastic resin of the layer B of the oxygen-absorbing multilayer body of the present embodiment, any thermoplastic resin can be used and is not particularly limited. For example, the thermoplastic resin used in the layer A described above may be the same or different. The layer B of this embodiment preferably contains at least one thermoplastic resin selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, plant-derived resin, and chlorine-based resin. In addition, the thermoplastic resin used in the layer B of the present embodiment preferably contains 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100% by mass with respect to the total amount of the layer B. is there.

  The polyolefins, polyesters, polyamides, ethylene-vinyl alcohol copolymers, plant-derived resins, and chlorine-based resins mentioned as the thermoplastic resins that can be used for the layer B are exemplified as the thermoplastic resins that can be used for the layer A. Each can be used.

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

[Other layers]
The oxygen-absorbing multilayer body of the present embodiment may further include an arbitrary layer in addition to the above-described oxygen-absorbing layer (layer A) and resin layer (layer B) depending on the desired performance and the like. Examples of such an arbitrary layer include an adhesive layer, a metal foil, a metal vapor deposition layer, and an organic-inorganic film.

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

  Further, from the viewpoint of further improving gas barrier properties and light shielding properties, it is preferable to provide a metal foil, a metal vapor deposition layer, an organic-inorganic film, or the like on one surface of the layer A or the layer B described above. Here, the metal foil is not particularly limited, but an aluminum foil is preferable. In addition, the thickness of the metal foil is preferably 3 to 50 μm, more preferably 3 to 30 μm, and further preferably 5 to 15 μm from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like. On the other hand, although it does not specifically limit as a metal vapor deposition layer, The resin film etc. in which the metal or metal oxide films, such as aluminum and an alumina, were vapor-deposited are preferable. Examples of the method for forming a vapor deposition film include physical vapor deposition methods such as vacuum vapor deposition, sputtering, and ion plating, and chemical vapor deposition methods such as PECVD, but are not particularly limited and are publicly known. This method is applicable. The thickness of the deposited film is preferably from 5 to 500 nm, more preferably from 5 to 200 nm, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like. On the other hand, the organic-inorganic film layer is not particularly limited, but a resin film coated with a silica-polyvinyl alcohol hybrid film or the like prepared from a sol-gel method or the like is preferable. The thickness of the coating film is preferably 100 nm to 50 μm, more preferably 1 to 15 μm, from the viewpoints of gas barrier properties, light shielding properties, bending resistance, and the like.

  Further, when the oxygen-absorbing multilayer body of the present embodiment is used as a container or the like to be described later, an easily peelable layer or an easily tearable layer may be included in order to facilitate the opening of the oxygen-absorbing container. As an easily peelable layer, for example, a film in which two or more different polyolefins are blended to control the seal strength and peel strength is generally known. As an easy tear layer, for example, an easy tear film in which nylon MXD6 is blended with nylon 6 is generally known.

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

[Oxygen absorbing container]
The oxygen-absorbing container of this embodiment includes the above-described oxygen-absorbing multilayer body in the whole or a part of the packaging container. The oxygen-absorbing container of the present embodiment absorbs oxygen in the container, and when there is a small amount of oxygen that permeates or penetrates from the outside of the container, also absorbs this permeating or penetrating oxygen, It is possible to prevent alteration or the like due to oxygen of the content item to be stored (stored material).

  The shape of the oxygen-absorbing container of the present embodiment is not particularly limited, and can be set as appropriate according to the article to be stored and stored. Such containers can be suitably used as pouches, cups, trays, bottles and the like.

  Furthermore, for example, by making a bag of the above-mentioned film-like or sheet-like oxygen-absorbing multilayer body, a three-side sealed flat bag, a standing pouch, a gusset packaging bag, a pillow packaging bag, a main chamber and a sub-chamber, A multi-chamber pouch provided with an easily peelable wall between the sub chamber and the sub chamber, shrink film packaging, and the like. Moreover, it can also be set as the container of arbitrary shapes by performing thermoforming.

  More specifically, the film- or sheet-like oxygen-absorbing multilayer body is formed by a method such as vacuum forming, pressure forming, plug assist forming, etc., so that a tray, cup, bottle, tube, PTP (press -An oxygen-absorbing container having a predetermined shape such as a through pack can be produced. Moreover, it is also possible to mold the molten resin into a multilayer container having a predetermined shape by co-injecting or sequentially injecting the molten resin into an injection mold through a multilayer multiple die using an injection machine.

  In addition, when producing the thermoformed container which has a flange part, you may give the special process which provides an easy peeling function to the flange part. Further, by using the oxygen-absorbing multilayer body as a member such as a container lid or a top seal, an oxygen absorbing function can be imparted to these containers.

  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.

  The oxygen-absorbing multilayer body of the present embodiment does not require moisture for oxygen absorption, in other words, it can absorb oxygen regardless of the presence or absence of moisture in the object to be preserved. Can be used in applications. In particular, since there is no generation of odor after oxygen absorption, it can be particularly suitably used in, for example, foods, cooked foods, beverages, health foods, pharmaceuticals and the like. That is, the oxygen-absorbing composition of this embodiment and various molded articles such as laminates using the same absorb oxygen under a wide range of humidity conditions (relative humidity 0% to 100%) from low humidity to high humidity. Since it is excellent in performance and excellent in flavor retention of contents, it is suitable for packaging of various articles.

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 an article is P, the water vapor pressure in the space after the article is sealed and reaches equilibrium, the water vapor pressure in pure water is P0, the relative humidity in the space is RH (%), If
Aw = P / P0 = RH / 100
Is defined.

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

  The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. Unless otherwise specified, NMR measurements were performed at room temperature.

Synthesis Example 1 Diester Compound A Having a Tetralin Ring
In a reactor equipped with a thermometer, a partial condenser, a total condenser, and a stirrer, 248 g (1.0 mol) of dimethyl 1,2,3,4-tetrahydronaphthalene-2,6-dicarboxylate, 409 g of n-hexyl alcohol (4.0 mol) and 0.34 g of tetrabutyl titanate were charged, the temperature was raised to 150 ° C. under a nitrogen atmosphere, and the reaction was carried out while removing the produced methanol out of the system. After the formation of methanol stopped, the mixture was cooled to room temperature, and unreacted n-hexyl alcohol was removed under reduced pressure to obtain diester compound A. Using a differential heat / thermogravimetric simultaneous measurement device (manufactured by Shimadzu Corporation, trade name “DTG-60”), the 3% weight reduction temperature of the obtained compound was measured. Table 1 shows the structural formula, molecular weight, and 3% weight loss temperature of the obtained compound. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.73-7.79 (2H m), 7.16 (1H d), 4.29 (2H t), 4.10 (2H t), 3.01-3 .08 (2H m), 2.82-2.97 (2H m), 2.70-2.78 (1H m), 2.18-2.24 (1H m), 1.84-1.94 (1H m), 1.71-1.79 (2H m), 1.58-1.68 (2H m), 1.25-1.48 (12H m), 0.90 (6H t).

(Synthesis example 2) Diester compound B having a tetralin ring
The same procedure as in Synthesis Example 1 was performed except that n-octyl alcohol was used instead of n-hexyl alcohol, the blending amount was 521 g (4.0 mol), and the reaction temperature was 190 ° C. Diester compound B Got. The structural formula of the obtained compound is shown in Table 1. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.68-7.74 (2H m), 7.10 (1H d), 4.23 (2H t), 4.04 (2H t), 2.92-3 0.00 (2H m), 2.72-2.89 (2H m), 2.63-2.70 (1H m), 2.10-2.18 (1H m), 1.76-1.85 (1H m), 1.63-1.72 (2H m), 1.50-1.59 (2H m), 1.9-1.40 (20H m), 0.90 (6H t).

Synthesis Example 3 Diester Compound C Having a Tetralin Ring
The same as Synthesis 2 except that dimethyl 1,2,3,4-tetrahydronaphthalene-1,8-dicarboxylate was used instead of dimethyl 1,2,3,4-tetrahydronaphthalene-2,6-dicarboxylate. Operation was performed to obtain a diester compound C. The structural formula of the obtained compound is shown in Table 1. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.78 (1H d), 7.17-7.29 (2H m), 4.50 (1H t), 4.22 (2H t), 3.98-4 .12 (2H m), 2.76-2.93 (2H m), 2.21-2.30 (1H m), 1.89-1.99 (1H m), 1.67-1.83 (4H m), 1.50-1.63 (3H m), 1.18-1.44 (19H m), 0.89 (6H t).

Synthesis Example 4 Diester Compound D Having a Tetralin Ring
In a reactor equipped with a thermometer, a partial condenser, a total condenser, and a stirrer, dimethyl adipate 108 g (0.62 mmol), 6-hydroxymethyl-1,2,3,4-tetrahydronaphthalene 300 g (1.85 mmol) ) And the temperature was raised to 130 ° C. After adding 0.58 g of titanium tetrabutoxide, the temperature was raised to 200 ° C., and the reaction was carried out while removing the produced methanol out of the system. After the production of methanol ceased, the reaction mixture was cooled to room temperature, unreacted 6-hydroxymethyl-1,2,3,4-tetrahydronaphthalene was removed under reduced pressure, and then diester compound D was obtained by recrystallization. The structural formula of the obtained compound is shown in Table 1. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.00 (6H m), 5.02 (4H s), 2.70-2.79 (8H m), 2.34 (4H t), 1.74-1 .83 (8H m), 1.64-1.70 (4H m).

Synthesis Example 5 Diamide Compound E Having a Tetralin Ring
A 2000 mL autoclave equipped with a thermometer and a stirrer was charged with 248 g (1.0 mol) of dimethyl 1,2,3,4-tetrahydronaphthalene-2,6-dicarboxylate and 607 g (6.0 mol) of n-hexylamine, and then nitrogen. After the replacement, the temperature was raised to 220 ° C. and stirred for 5 hours. After cooling to room temperature, filtration was performed, and diamide compound E was obtained by recrystallization. The structural formula of the obtained compound is shown in Table 1. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.42 (1H s), 7.37 (1H d), 7.04 (1H d), 5.99 (1H m), 5.53 (1H m), 3 .32-3.41 (2H m), 3.15-3.24 (2H m), 2.68-3.03 (4H m), 2.35-2.43 (1H m), 1.97 -2.05 (1Hm), 1.76-1.87 (1Hm), 1.17-1.58 (12Hm), 0.83 (6Ht).

Synthesis Example 6 Acid anhydride F having a tetralin ring
Into an 18 L autoclave, 1.8 g of 1,8-naphthalic anhydride and 300 g of a catalyst (dry product) in which 5 wt% palladium was supported on activated carbon and 7.5 kg of ethyl acetate were charged. At room temperature, the inside of the autoclave was replaced twice with 1 MPa of nitrogen, and then replaced twice with 1 MPa of hydrogen. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 80 ° C., the pressure was increased to 5 MPa with hydrogen, and the mixture was stirred at 500 rpm at the same temperature and the same pressure for 2 hours. After the reaction, the reaction mixture was cooled to room temperature, released hydrogen, and replaced with 1 MPa of nitrogen twice. Then, the catalyst was filtered off, and the catalyst was washed with 1.0 kg of acetone three times. The solvent was removed from the obtained mother liquor under reduced pressure by an evaporator to obtain a crude product. The acid anhydride F was obtained by recrystallizing the obtained composition organism. The NMR analysis results are as follows. ¹ H-NMR (400 MHz CDCl ₃ ) δ 7.98 (1H d), 7.47 (1H d), 7.38 (1H dd), 3.93 (1H t), 2.80-3.00 (2H m), 2.55-2.64 (1H m), 2.14-2.24 (1H m), 1.77-1.94 (2H m).

Example 1
Using a twin screw extruder having two screws with a diameter of 37 mm, 95 parts by mass of an ethylene-vinyl alcohol copolymer (product name; “Eval L171B” manufactured by Kuraray Co., Ltd., hereinafter also abbreviated as “EVOH”) is used. On the other hand, 5 parts by mass of the diester compound A and cobalt (II) stearate are melt-kneaded at 220 ° C. so that the amount of cobalt is 0.05 parts by mass, the strand is extruded from the extruder head, cooled, and pelletized. An oxygen-absorbing composition was obtained.

  Next, polypropylene (product name: Nippon Polypro Co., Ltd.) was used from the first extruder using a three-kind five-layer multilayer sheet forming apparatus equipped with first to third extruders, a feed block, a T die, a cooling roll, and a sheet take-up machine. “NOVATEC PP FY6C” manufactured by the company, hereinafter also abbreviated as “PP”), the oxygen-absorbing composition from the second extruder, and the adhesive polypropylene from the third extruder (product name; “Modic” manufactured by Mitsubishi Chemical Corporation) P604V ", hereinafter also abbreviated as" adhesive PP ") were extruded to obtain an oxygen-absorbing multilayer sheet via a feed block. The layer structure of the multilayer sheet was PP (250 μm) / adhesive PP (15 μm) / oxygen absorbing layer (100 μm) / adhesive PP (15 μm) / PP (250 μm) from the inner layer. The obtained oxygen-absorbing multilayer sheet was evaluated as shown below. The evaluation results are shown in Table 2.

(1) Oxygen absorption amount of oxygen-absorbing multilayer sheet Two gas barrier bags made of an aluminum foil laminated film were prepared. Then, two test pieces (length 10 cm × width 10 cm) of the obtained oxygen-absorbing multilayer sheet were filled in two gas barrier bags together with 500 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 in an atmosphere at a temperature of 40 ° C. for 30 days, and the total amount of oxygen absorbed during that period was measured.

(2) Odor after Oxygen Absorption of Oxygen Absorbing Multilayer Sheet Similar to the above oxygen absorption measurement, the sealed bag after opening it for 30 days at a temperature of 40 ° C. and a relative humidity of 100% is opened, and the odor in the sealed bag It was confirmed.
About the odor, the presence or absence of the odor of the sheet itself and the presence or absence of the odor change before and after oxygen absorption were evaluated. The case where the sheet itself had no odor and there was no change in odor before and after oxygen absorption was judged as “no odor after oxygen absorption”.

(3) Oxygen permeability of oxygen-absorbing multilayer sheet Measurement using an oxygen permeability measuring device (“OX-TRAN 2-61” manufactured by MOCON) under an atmosphere of temperature: 23 ° C. and relative humidity of 60%. The oxygen transmission rate on the 30th day from the start was measured. It shows that oxygen barrier property is so favorable that a measured value is low. The oxygen permeability was measured according to ASTM D3985.

(Example 2)
An oxygen-absorbing multilayer sheet was produced in the same manner as in Example 1 except that the diester compound A was replaced with the diester compound B, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

Example 3
An oxygen-absorbing multilayer sheet was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the diester compound C, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

Example 4
An oxygen-absorbing multilayer sheet was produced in the same manner as in Example 1 except that the diester compound A was replaced with the diester compound D, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Example 5)
An oxygen-absorbing multilayer sheet was produced in the same manner as in Example 1 except that the diester compound A was replaced with the diamide compound E, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Example 6)
An oxygen-absorbing multilayer sheet was prepared in the same manner as in Example 1 except that the diester compound A was replaced with the acid anhydride F, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 1)
A multilayer sheet was prepared in the same manner as in Example 1 except that the diester compound A and cobalt (II) stearate were not used, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 2)
A multilayer sheet was prepared in the same manner as in Example 1 except that the diester compound A was not used, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

(Comparative Example 3)
A multilayer sheet was prepared in the same manner as in Example 1 except that cobalt stearate (II) was not used, and the same evaluation as in Example 1 was performed. These results are shown in Table 2.

  As is clear from Table 2, in the oxygen-absorbing multilayer sheet using the compounds having a tetralin ring of Examples 1 to 6, oxygen is absorbed by the oxygen-absorbing layer, so that the oxygen permeability is higher than that of Comparative Examples 1 to 3. Was able to be reduced. Further, it was confirmed that the sheet not only has no odor but also has no odor after oxygen absorption.

(Example 7)
Using a twin screw extruder having two screws having a diameter of 37 mm, 95 parts by mass of polyethylene terephthalate (product name: “1101E” manufactured by Invista, hereinafter also abbreviated as “PET”) is 5 parts by mass of diester compound A. In addition, cobalt (II) stearate is melt-kneaded at 260 ° C. so that the amount of cobalt is 0.05 parts by mass, the strand is extruded from the extruder head, cooled, and pelletized to obtain an oxygen-absorbing composition. It was.

  Next, using a two-type three-layer multilayer sheet forming apparatus equipped with a first to third extruder, a feed block, a T die, a cooling roll and a sheet take-up machine, polyethylene terephthalate from the first extruder and the third extruder, The oxygen-absorbing composition obtained above was extruded from the second extruder, and an oxygen-absorbing multilayer sheet was obtained via a feed block. The layer structure of the multilayer sheet was PET (100 μm) / oxygen absorbing layer (300 μm) / PET (100 μm).

  Next, the oxygen transmission rate of the obtained oxygen-absorbing multilayer sheet was measured in an atmosphere at a temperature of 23 ° C., a relative humidity of 60%, and a relative humidity of 90%. Table 3 shows the oxygen permeability 30 days after the start of measurement. Note that the oxygen permeability was measured using the same oxygen permeability measuring apparatus as in Example 1. Further, as in Example 1, the odor of the multilayer sheet after the oxygen transmission rate measurement was confirmed. The results are shown in Table 3.

(Example 8)
Except that the diester compound A was replaced with the diester compound B, an oxygen-absorbing multilayer sheet was prepared in the same manner as in Example 7, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

Example 9
An oxygen-absorbing multilayer sheet was prepared in the same manner as in Example 7 except that the diester compound A was replaced with the diester compound C, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

(Example 10)
An oxygen-absorbing multilayer sheet was produced in the same manner as in Example 7 except that the diester compound A was replaced with the diester compound D, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

(Example 11)
An oxygen-absorbing multilayer sheet was produced in the same manner as in Example 7 except that the diester compound A was replaced with the diester compound E, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

(Comparative Example 4)
A multilayer sheet was prepared in the same manner as in Example 7 except that the diester compound A and cobalt (II) stearate were not used, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

(Comparative Example 5)
A multilayer sheet was produced in the same manner as in Example 7 except that the diester compound A was not used, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

(Comparative Example 6)
A multilayer sheet was prepared in the same manner as in Example 7 except that cobalt stearate (II) was not used, and the same evaluation as in Example 7 was performed. These results are shown in Table 3.

  As is clear from Table 3, in the oxygen-absorbing multilayer sheets of Examples 7 to 11, oxygen was absorbed by the oxygen absorbing layer, so that the oxygen permeability was reduced compared to Comparative Examples 4 to 6. . Further, it was confirmed that the sheet not only has no odor but also has no odor after oxygen absorption.

(Example 12)
Diester with respect to 95 parts by mass of polyamide 6 (product name: “UBE nylon 1024B” manufactured by Ube Industries, Ltd., hereinafter also abbreviated as “PA6”) using a twin screw extruder having two screws with a diameter of 37 mm. Compound A 5 parts by mass and cobalt (II) stearate are melt-kneaded at 250 ° C. so that the amount of cobalt is 0.05 parts by mass, the strand is extruded from the extruder head, cooled, and pelletized after cooling. A composition was obtained.

  Next, using a two-type three-layer multilayer film forming apparatus equipped with two extruders, a feed block, a T die, a cooling roll, and a sheet take-up machine, PA6 is obtained from the first extruder and the above from the second extruder. Each of the obtained oxygen-absorbing compositions was extruded to obtain an oxygen-absorbing multilayer film through a feed block. The layer structure of the multilayer sheet was PA6 (90 μm) / oxygen absorption layer (180 μm) / PA6 (90 μm). Next, the obtained multilayer film was stretched 3 times to MD and 3 times to TD at a stretching temperature of 80 ° C. using a batch type biaxial stretching machine (manufactured by Toyo Seiki Co., Ltd., center stretching type biaxial stretching machine). And a biaxially stretched film heat-fixed at 210 ° C. for 30 seconds was obtained. In addition, the thickness of each layer after extending | stretching became 10/20/10 (micrometer).

  The oxygen permeability of the obtained oxygen-absorbing multilayer film was measured in an atmosphere at a temperature of 23 ° C. and a relative humidity of 60%. Table 4 shows the oxygen transmission rate 30 days after the start of measurement. Note that the oxygen permeability was measured using the same oxygen permeability measuring apparatus as in Example 1. Further, as in Example 1, the odor of the multilayer film after measuring the oxygen transmission rate was confirmed. The results are shown in Table 4.

(Example 13)
An oxygen-absorbing multilayer film was produced in the same manner as in Example 12 except that the diester compound A was replaced with the diester compound B, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

(Example 14)
An oxygen-absorbing multilayer film was produced in the same manner as in Example 12 except that the diester compound A was replaced with the diester compound C, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

(Example 15)
An oxygen-absorbing multilayer film was produced in the same manner as in Example 12 except that the diester compound A was replaced with the diester compound D, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

(Example 16)
An oxygen-absorbing multilayer film was produced in the same manner as in Example 12 except that the diester compound A was replaced with the diamide compound E, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

(Example 17)
An oxygen-absorbing multilayer film was produced in the same manner as in Example 12 except that the amount of polyamide compound was 90 parts by mass and the amount of diamide compound E was 10 parts by mass, and the same evaluation as in Example 12 was performed. It was. These results are shown in Table 4.

(Comparative Example 7)
A multilayer film was produced in the same manner as in Example 12 except that the diester compound A and cobalt (II) stearate were not used, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

(Comparative Example 8)
A multilayer film was produced in the same manner as in Example 12 except that the diester compound A was not used, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

(Comparative Example 9)
A multilayer film was produced in the same manner as in Example 12 except that cobalt (II) stearate was not used, and the same evaluation as in Example 12 was performed. These results are shown in Table 4.

  As apparent from Table 4, in the oxygen-absorbing multilayer films of Examples 12 to 17, oxygen was absorbed by the oxygen-absorbing layer, so that the oxygen permeability could be reduced as compared with Comparative Examples 7 to 9. . In addition, it was confirmed that the film had no odor and no odor after oxygen absorption.

(Example 18)
Using a twin screw extruder having two screws with a diameter of 37 mm, 95 parts by mass of linear low density polyethylene (product name: “Umerit 140HK” manufactured by Ube Maruzen Polyethylene Co., Ltd., hereinafter also abbreviated as “LLDPE1”). On the other hand, 5 parts by mass of the diester compound A and cobalt (II) stearate are melt-kneaded at 200 ° C. so that the amount of cobalt is 0.05 parts by mass, the strand is extruded from the extruder head, cooled, and pelletized. Thus, an oxygen-absorbing composition was obtained.

  Next, using a two-type three-layer multilayer film production apparatus equipped with two extruders, a feed block, a T-die, a cooling roll, a corona discharge treatment apparatus, a winder, etc., the linear low density from the first extruder Polyethylene (product name; “ELITE 5220G” manufactured by Dow Chemical Co., Ltd., hereinafter also abbreviated as “LLDPE2”) was extruded from the second extruder to the oxygen-absorbing composition obtained above, through a feed block, After producing the 2 types 3 layer film, the surface of one LLDPE2 layer was corona discharge-treated at 60 m / min, and the film roll was produced. The layer structure of the multilayer film was LLDPE2 (20 μm) / oxygen absorption layer (40 μm) / LLDPE2 (20 μm).

  Next, a nylon 6 film (product name: “N1202” manufactured by Toyobo Co., Ltd.) was used on the corona-treated surface side using an urethane dry laminate adhesive (product name: “TM251 / CAT-RT88” manufactured by Toyo Morton Co., Ltd.). )) And an alumina-deposited PET film (product name: “GL-ARH-F” manufactured by Toppan Printing Co., Ltd.) are laminated by dry lamination, and an alumina-deposited PET film (12 μm) / urethane-based dry laminate adhesive ( 3 [mu] m) / nylon 6 film (15 [mu] m) / urethane-based adhesive for dry laminate (3 [mu] m) / LLDPE2 (20 [mu] m) / oxygen absorbing layer (40 [mu] m) / transparent oxygen absorbing layer composed of LLDPE2 (20 [mu] m) A multilayer film was obtained. The obtained oxygen-absorbing multilayer film was evaluated as described below. The evaluation results are shown in Table 5.

(1) Oxygen absorption amount of oxygen-absorbing multilayer film Two gas barrier bags made of an aluminum foil laminated film were prepared. Then, two test pieces (length 10 cm × width 10 cm) of the obtained oxygen-absorbing multilayer film were filled in two gas barrier bags together with 500 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 in an atmosphere at a temperature of 40 ° C. for 30 days, and the total amount of oxygen absorbed during that period was measured.

(2) Odor after Oxygen Absorption of Oxygen Absorbing Multilayer Film The sealed bag after measuring the oxygen absorption amount was opened, and the odor in the sealed bag was confirmed.

(3) Seal strength From the obtained oxygen-absorbing multilayer film, a 10 cm x 18 cm three-side sealed bag was produced with the LLDPE2 layer side as the inner surface. Then, after storing for 100 days at a temperature of 40 ° C. and a relative humidity of 90%, the sealing strength of the bag was measured. In the measurement of the seal strength, the seal strength of the short side portion of the three-side seal bag was measured according to JIS Z0238.

(Example 19)
An oxygen-absorbing multilayer film was obtained in the same manner as in Example 18 except that the diester compound A was replaced with the diester compound B. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Example 20)
An oxygen-absorbing multilayer film was obtained in the same manner as in Example 18 except that the diester compound A was replaced with the diester compound C. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Example 21)
An oxygen-absorbing multilayer film was obtained in the same manner as in Example 18 except that the diester compound A was replaced with the diester compound D. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Example 22)
An oxygen-absorbing multilayer film was obtained in the same manner as in Example 18 except that the diester compound A was replaced with the diamide compound E. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Example 23)
An oxygen-absorbing multilayer film was obtained in the same manner as in Example 18 except that the diester compound A was replaced with the acid anhydride F. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Comparative Example 10)
A multilayer film was obtained in the same manner as in Example 18 except that the diester compound A and cobalt (II) stearate were not used. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Comparative Example 11)
A multilayer film was obtained in the same manner as in Example 18 except that the diester compound A was not used. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Comparative Example 12)
A multilayer film was obtained in the same manner as in Example 18 except that cobalt (II) stearate was not used. Thereafter, in the same manner as in Example 18, the oxygen absorption amount was measured, the odor after oxygen absorption was confirmed, and the bag seal strength was measured. These results are shown in Table 5.

(Comparative Example 13)
Iron powder having an average particle size of 30 μm and calcium chloride were mixed at a mass ratio of 100: 1, and this mixture and LLDPE1 were kneaded at a mass ratio of 30:70 to obtain an iron-based oxygen-absorbing composition. An attempt was made to produce a two-layer three-layer film in the same manner as in Example 18 except that this iron-based oxygen-absorbing composition was used in place of the oxygen-absorbing composition described in Example 18. The unevenness | corrugation originating in powder generate | occur | produced and the film with the smooth surface which can endure subsequent examination was not obtained. Therefore, a linear low-density polyethylene film having a thickness of 50 μm (product name: “Tosero TUX HC” manufactured by Tosero Co., Ltd., hereinafter referred to as “LLDPE3”) is used as the oxygen absorbing layer as the iron. The system oxygen-absorbing composition was laminated by extrusion lamination with a thickness of 40 μm, and then the layer-side surface of the iron-based oxygen absorbing composition was subjected to corona discharge treatment at 60 m / min to obtain a laminate film.

  Next, on the corona-treated surface side of the laminate film, the following layers were laminated by dry lamination in the same manner as in Example 18 to obtain an alumina-deposited PET film (12 μm) / urethane dry laminate adhesive (3 μm) / nylon 6 An iron-based oxygen-absorbing multilayer film of film (15 μm) / urethane-based dry laminate adhesive (3 μm) / oxygen absorbing layer (40 μm) / LLDPE3 (50 μm) was produced. The obtained iron-based oxygen-absorbing multilayer film was opaque due to iron.

  Next, using the obtained iron-based oxygen-absorbing multilayer film, the oxygen absorption amount, the odor after oxygen absorption, and the bag seal strength were measured in the same manner as in Example 18. These results are shown in Table 5.

(Comparative Example 14)
Using a twin screw extruder having two screws having a diameter of 37 mm, 100 parts by mass of nylon MXD6 (product name; “MX nylon S6011” manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter also abbreviated as “N-MXD6”). On the other hand, cobalt stearate (II) was melt kneaded at 260 ° C. so that the amount of cobalt was 0.05 parts by mass, the strand was extruded from the extruder head, cooled, and pelletized after cooling to obtain an oxygen-absorbing composition. .

  Next, using a three-kind five-layer multilayer film production apparatus equipped with three extruders, a feed block, a T-die, a cooling roll, a corona discharge treatment apparatus, a winder, etc., the LLDPE 2 From the third extruder, the oxygen-absorbing composition obtained above from the extruder was adhered to polyethylene ((Product name: “Modic M545” manufactured by Mitsubishi Chemical Corporation, hereinafter also referred to as “adhesive PE”). And a three-layer five-layer film was produced through a feed block, and then the surface of one LLDPE2 layer was subjected to corona discharge treatment at 60 m / min to produce a film roll. LLDPE2 (10 μm) / adhesive PE (10 μm) / oxygen absorbing layer (40 μm) / adhesive PE (10 μm) / LLDPE2 (10 μm).

  Next, on the corona-treated surface side of the laminate film, the following layers were laminated by dry lamination in the same manner as in Example 18 to obtain an alumina-deposited PET film (12 μm) / urethane dry laminate adhesive (3 μm) / nylon 6 Nylon MXD6 series of film (15 μm) / urethane-based dry laminate adhesive (3 μm) / LLDPE2 (10 μm) / adhesive PE (10 μm) / oxygen absorbing layer (40 μm) / adhesive PE (10 μm) / LLDPE2 (10 μm) An oxygen-absorbing multilayer film was produced.

  Next, using the obtained nylon MXD6 oxygen-absorbing multilayer film, the oxygen absorption amount, the odor after oxygen absorption, and the bag seal strength were measured in the same manner as in Example 18. These results are shown in Table 5.

  As is apparent from Table 5, the oxygen-absorbing multilayer films of Examples 18 to 23 show oxygen absorption under high and low humidity, no odor is generated after oxygen absorption, and after oxygen absorption Also maintained the seal strength.

  Since the oxygen-absorbing multilayer body and the oxygen-absorbing container of the present invention have an excellent oxygen-absorbing property, they can be used widely and effectively in general technical fields that require oxygen absorption. In addition, it is possible to absorb oxygen regardless of the presence or absence of moisture in the object to be stored, and further, since the increase in odor intensity after oxygen absorption is suppressed, for example, foods, cooked foods, beverages, pharmaceuticals, health foods In particular, it can be used effectively. Moreover, since it is not sensitive to metal detectors, it can be used widely and effectively in applications in which metals, metal pieces, etc. are inspected from the outside by metal detectors, such as packaging and containers.

Claims (9)

An oxygen-absorbing multilayer body comprising an oxygen-absorbing layer containing an oxygen-absorbing composition and a thermoplastic resin layer containing a thermoplastic resin,
The oxygen-absorbing composition, at least one compound having a tetralin ring represented by the following general formula (1), seen containing a transition metal catalyst, and a thermoplastic resin,
(Wherein R _{1 to} R ₁₂ each independently represents a hydrogen atom or a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio group, imide And at least one selected from the group consisting of a substituent represented by the following general formula (1a) and a substituent represented by the following general formula (1b), and these further have a substituent. Alternatively, two substituents out of R _{1 to} R ₁₂ may be bonded to form a ring, and at least one hydrogen atom is bonded to the benzyl position of the tetralin ring.
(In the general formula (1a) and the general formula (1b), R each independently represents a monovalent substituent, and the monovalent substituent includes a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxy group, carboxyl group, ester group, amide group, nitro group, alkoxy group, aryloxy group, acyl group, amino group, thiol group, alkylthio group, arylthio group, heterocyclic thio These are at least one selected from the group consisting of a group and an imide group, which may further have a substituent, and two substituents of R may be bonded to form a ring. W is a bond or a divalent organic group, and the divalent organic group is an aromatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, a linear or branched saturated or unsaturated group. Saturated fat Group hydrocarbon group and heterocyclic group, at least selected from the group consisting of —C (═O) —, —OC (═O) —, —N (H) C (═O) —, and any combination thereof. (M represents an integer of 0 to 4, n represents an integer of 0 to 7, p represents an integer of 0 to 8, and q represents an integer of 0 to 3.)
An oxygen-absorbing multilayer body , wherein the compound having a tetralin ring represented by the general formula (1) has two or more carbonyl groups . In the general formula (1), at least two of R _{1 to} R ₁₂ are monovalent substituents represented by the following general formula (2).

-C (= O) -X (2)

(Wherein X is one selected from the group consisting of a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a monoalkylamino group, and a dialkylamino group, and a plurality of Xs may be the same. And may be different.)
The oxygen-absorbing multilayer body according to claim 1 . The oxygen-absorbing multilayer body according to claim 1 or 2 , wherein the compound having a tetralin ring represented by the general formula (1) has two or more tetralin rings. Of the compound having the tetralin ring represented by the general formula (1) with respect to the total amount of the compound having the tetralin ring represented by the general formula (1) and the thermoplastic resin in the oxygen-absorbing composition. The oxygen-absorbing multilayer body according to any one of claims 1 to 3 , wherein the ratio is 1 to 30% by mass. The oxygen according to any one of claims 1 to 4 , wherein the thermoplastic resin is at least one selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and chlorine resin. Absorbent multilayer body. The oxygen-absorbing multilayer body according to any one of claims 1 to 5 , wherein the transition metal catalyst includes at least one transition metal selected from the group consisting of manganese, iron, cobalt, nickel, and copper. In the oxygen-absorbing composition, the transition metal catalyst has a transition metal amount of 0 with respect to 100 parts by mass of the total amount of the compound having a tetralin ring represented by the general formula (1) and the thermoplastic resin. The oxygen-absorbing multilayer body according to any one of claims 1 to 6 , which is contained in an amount of 0.001 to 10 parts by mass. An oxygen-absorbing multilayered body according to any one of claims 1 to 7 oxygen-absorbing container. The oxygen-absorbing container according to claim 8 , wherein the oxygen-absorbing container is one selected from the group consisting of a pouch, a cup, a tray, and a bottle.