JP6048745B2 - Oxygen-absorbing multilayer injection molding - Google Patents

Description

  The present invention relates to an oxygen-absorbing multilayer injection molded article.

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

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

  In addition, the container is made of a multilayer material in which an oxygen absorbing layer made of an oxygen absorbing resin composition in which an iron-based oxygen absorber is blended with a thermoplastic resin, thereby improving the gas barrier property of the container and improving the container itself. Development of packaging containers having an oxygen absorbing function has been carried out (see Patent Document 1). Specifically, in an oxygen-absorbing multilayer film, an oxygen absorbent is dispersed between a conventional gas-barrier multilayer film formed by laminating a heat seal layer and a gas barrier layer, optionally with an intermediate layer made of a thermoplastic resin. It has been used as an oxygen absorbing layer that is a thermoplastic resin layer that has been added to provide a function to absorb oxygen in the container in addition to the function of preventing oxygen permeation from the outside, such as extrusion lamination, co-extrusion lamination, and dry lamination. It is manufactured using a known manufacturing method. However, this is also a problem that it can not be detected by metal detectors used for detecting foreign substances such as food, it can not be heated with a microwave oven, and the object to be stored only exhibits high moisture content have. Furthermore, there is a problem that the internal visibility is insufficient due to the problem of opacity. Those using oxygen absorbers such as iron powder are detected by metal detectors used to detect foreign objects such as food, when internal visibility is insufficient due to opacity problems, and the contents are alcoholic drinks There has been a problem that an aldehyde is generated by an oxidation reaction of alcohol using iron 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 an oxygen absorbent, a packaging material, and a multilayer laminated film for packaging obtained by molding this resin composition.

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

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

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

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

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

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

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

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

  On the other hand, the composition of Patent Document 6 needs to use a special material containing a cyclohexene functional group, and this material still has a problem that it is relatively easy to generate an odor.

  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 injection molded article that has no odor generation after oxygen absorption and has excellent oxygen absorption performance. Another object of the present invention is to provide an oxygen-absorbing multilayer injection molded article having excellent oxygen absorption performance under a wide range of humidity conditions from low humidity to high humidity.

  As a result of diligent investigations, the present inventors have found 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 (a). And an oxygen-absorbing multilayer injection-molded article containing the thermoplastic resin layer containing the thermoplastic resin (b) has found that the above problems can be solved, and the present invention has been completed.

That is, the present invention is as follows.
[1]
An oxygen-absorbing multilayer injection molded article having an oxygen-absorbing layer containing an oxygen-absorbing composition and a thermoplastic resin layer containing a thermoplastic resin (b),
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 (a),
(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 injection molded article , 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 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.)
[ 1 ] The oxygen-absorbing multilayer injection molded article according to [ 1 ].
[3]
The oxygen-absorbing multilayer injection molded article 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 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 (a) in the oxygen-absorbing composition. The oxygen-absorbing multilayer injection molded article according to any one of [1] to [ 3 ], wherein the ratio of the compound having 1 to 30% by mass.
[ 5 ]
[1] The thermoplastic resin (a) in the oxygen-absorbing composition is at least one selected from the group consisting of polyolefins, polyesters, polyamides, ethylene-vinyl alcohol copolymers, and chlorine-based resins. The oxygen-absorbing multilayer injection molded article according to any one of to [ 4 ].
[ 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. Injection molded body.
[ 7 ]
In the oxygen-absorbing composition, the amount of the transition metal catalyst is 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 (a). As an oxygen-absorbing multilayer injection molded article according to any one of [1] to [ 6 ], which is contained as 0.001 to 10 parts by mass.
[ 8 ]
An oxygen-absorbing multilayer container obtained by further processing the oxygen-absorbing multilayer injection molded article according to any one of [1] to [ 7 ].
[ 9 ]
The oxygen-absorbing multilayer container according to [ 8 ], obtained by stretch blow molding.

  According to the present invention, it is possible to provide an oxygen-absorbing multilayer injection molded article that has no odor generation after oxygen absorption and has excellent oxygen absorption performance. And this oxygen-absorbing injection-molded body can absorb oxygen regardless of the presence or absence of moisture in the object to be preserved, and since there is no odor generation after oxygen absorption, for example, foods, cooked foods, beverages, pharmaceuticals It can be used in a wide range of applications, including health foods, regardless of the object. Moreover, according to a preferred embodiment of the present invention, an oxygen-absorbing multilayer injection molded body that is insensitive to a metal detector is 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 injection molded product]
An oxygen-absorbing multilayer injection molded article having an oxygen-absorbing layer containing an oxygen-absorbing composition and a thermoplastic resin layer containing a thermoplastic resin (b),
The oxygen-absorbing composition contains at least one compound having a tetralin ring represented by the following general formula (1), a transition metal catalyst, and a thermoplastic resin (a).
(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.)
Oxygen-absorbing multilayer injection molding.

  The oxygen-absorbing multilayer injection molded article of the present embodiment can be used as, for example, a container for storing a content article (a storage object). In this case, the oxygen in the container is absorbed, and if there is a small amount of oxygen that permeates or penetrates from the outside of the container, the permeated or invading oxygen is also absorbed and stored. Can be prevented from being deteriorated by oxygen.

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

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

<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.

  The oxygen-absorbing composition 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.

The molecular weight of the compound having a tetralin ring represented by the general formula (1) described above can be appropriately adjusted according to the desired properties and the substituents R _{1 to} R ₁₂ 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.

  Compound having tetralin ring represented by general formula (1) with respect to total amount of compound having tetralin ring represented by general formula (1) and thermoplastic resin (a) described later in oxygen-absorbing composition Is preferably 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 can be 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. It is not limited.

  Specific examples of the transition metal catalyst include, for example, organic acid salts, halides, phosphates, phosphites, hypophosphites, nitrates, sulfates, oxides and hydroxides of transition metals. Here, examples of the transition metal contained in the transition metal catalyst include, but are not limited to, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, ruthenium, and rhodium. Among these, manganese, iron, cobalt, nickel, and copper are preferable. Examples of organic acids include acetic acid, propionic acid, octanoic acid, lauric acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, Although capric acid and naphthenic acid are mentioned, it is not limited to these. The transition metal catalyst is preferably a combination of these transition metals and an organic acid, the transition metal is manganese, iron, cobalt, nickel or copper, and the organic acid is acetic acid, stearic acid, 2-ethylhexanoic acid, olein. A combination that is an acid or naphthenic acid is more preferred. In addition, a transition metal catalyst can be used individually by 1 type or in combination of 2 or more types.

  The compounding amount of the transition metal catalyst can be appropriately set according to the compound having the tetralin ring used, the thermoplastic resin (a), the type of 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 in total of the compound having a tetralin ring represented by the general formula (1) and the thermoplastic resin (a). On the other hand, it is preferable that it is 0.001-10 mass parts as transition metal amount, More preferably, it is 0.005-2 mass part, More preferably, it is 0.01-1 mass part.

  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 a thermoplastic resin. It can also mix | blend with and can also be set as the layer A.

  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 (a), 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, 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 appropriately set according to the compound used, the thermoplastic resin (a), the type of the transition metal catalyst, and the desired performance, and is not particularly limited, but tetralin represented by the general formula (1) It is preferable that it is 10-1000 mass parts with respect to 100 mass parts of compounds which have a ring, 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 (a)>
The oxygen-absorbing composition contains a thermoplastic resin (a). At this time, the content of the compound and the transition metal catalyst in the oxygen-absorbing composition is not particularly limited. For example, even if the compound and the transition metal catalyst are contained as they are in the thermoplastic resin (a), the compound and the transition metal catalyst are contained in the thermoplastic resin (a) in a state where they are supported on the carrier material described above. May be.

  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, the transition metal catalyst, and a support material blended as necessary with the thermoplastic resin (a).

  As said thermoplastic resin (a), a well-known thing can be used suitably, Although it does not specifically limit, For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, linear ultra-low Random or block copolymer of α-olefins such as density polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, or ethylene, propylene, 1-butene, 4-methyl-1-pentene Polyolefins such as maleic anhydride-grafted polyethylene and maleic anhydride-grafted polypropylene, etc .; ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer, ethylene- (meth) Acrylic acid copolymer and its ionic cross-linked product (Io ), Ethylene-vinyl compound copolymers such as ethylene-methyl methacrylate copolymer; styrene resins such as polystyrene, acrylonitrile-styrene copolymer, α-methylstyrene-styrene copolymer; methyl polyacrylate, Polyvinyl compounds such as polymethyl methacrylate; 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, polyglycol Polycarbonates; acid, polycaprolactone, polyesters such as polyhydroxyalkanoates polyethers such as polyethylene oxide or mixtures thereof. In addition, a thermoplastic resin (a) can be used individually by 1 type or in combination of 2 or more types.

  Among these, the thermoplastic resin (a) 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 (a) will be described in detail.

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

<Polyester>
Examples of the polyester used in the oxygen-absorbing composition include, for example, one kind selected from a polyhydric carboxylic acid containing dicarboxylic acid and one or more kinds selected from these ester-forming derivatives and a polyhydric alcohol containing glycol. Or what consists of 2 or more types, 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 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 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 include linear polyesters containing 70 mol% or more of propylene terephthalate units, linear polyesters containing 70 mol% or more of propylene naphthalate units, 1,4- They are linear polyesters containing 70 mol% or more of cyclohexanedimethylene terephthalate units, linear polyesters containing 70 mol% or more of butylene naphthalate units, or linear polyesters 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 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, for example, a polyamide mainly composed of a unit derived from lactam or aminocarboxylic acid, or a unit derived from an aliphatic diamine and an aliphatic dicarboxylic acid is mainly composed. Aliphatic polyamide as a unit, partially aromatic polyamide having a unit derived from an aliphatic diamine and an aromatic dicarboxylic acid as a main constituent unit, and a unit derived from an aromatic diamine and an aliphatic dicarboxylic acid as a main constituent unit And partially aromatic polyamides. The polyamide here may be a copolymer of monomer units other than the main structural unit, if necessary.

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

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

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

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

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

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

  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, 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 preferable. 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 may be a resin containing a plant-derived substance as a raw material, and the plant as the raw material is not particularly limited. Specific examples of plant-derived resins include aliphatic polyester-based biodegradable resins. Examples of the aliphatic polyester biodegradable resin include poly (α-hydroxy acids) such as polyglycolic acid (PGA) and polylactic acid (PLA); polybutylene succinate (PBS), polyethylene succinate (PES). And polyalkylene alkanoates.

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

  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.

  In addition, in order to accelerate | stimulate oxygen absorption reaction, the oxygen absorptive composition may contain the radical generator and the photoinitiator further as needed. Specific examples of the radical generator include various N-hydroxyimide compounds such as N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxyhexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl-N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3 -Hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxyphthalimide, 4-dimethylamino -N-hydroxyphthalimide, 4-carboxy-N-hydroxyhexahydrophthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic acid imide, N-hydroxyhymic acid imide, N-hydroxytrimellitic acid imide , N, N-dihydroxypyromellitic acid diimide and the like, but are not particularly limited thereto. Specific examples of the photoinitiator include, but are not limited to, benzophenone and its derivatives, thiazine dyes, metal porphyrin derivatives, anthraquinone derivatives, and the like. In addition, these radical generators and photoinitiators can be used individually by 1 type or in combination of 2 or more types.

  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 injection molded article of this embodiment is a layer containing a thermoplastic resin (b). The content ratio of the thermoplastic resin (b) 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 with respect to the total amount of the layer B. More preferably, it is 90-100 mass%.

  The oxygen-absorbing multilayer injection molded article of this embodiment may have a plurality of layers B, and the configurations of the plurality of layers B may be the same as or different from each other. Further, in the oxygen-absorbing multilayer injection molded article 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 the drop resistance required for the multilayer body, etc. From the viewpoint of securing various physical properties such as strength and flexibility, the thickness is preferably 5 to 1000 μm, more preferably 10 to 800 μm, and still more preferably 20 to 500 μm.

  Any thermoplastic resin can be used as the thermoplastic resin (b) of the layer B of the oxygen-absorbing multilayer injection molded article of the present embodiment, and is not particularly limited. For example, it may be the same as or different from the thermoplastic resin (a) used in the layer A described above. 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. Further, the thermoplastic resin (b) used for the layer B of the present embodiment is preferably contained in an amount of 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 90 to 100%, based on the total amount of the layer B. % By mass.

  For the polyolefins, polyesters, polyamides, ethylene-vinyl alcohol copolymers, plant-derived resins, and chlorine-based resins mentioned as the thermoplastic resin (b) that can be used for the layer B, the thermoplastic resins that can be used for the layer A Each of those exemplified as (a) can be used.

  Further, the layer B of the oxygen-absorbing multilayer injection molded article 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 injection molded article of the present embodiment may further include an optional 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. Good. Examples of such an arbitrary layer include an adhesive layer.

  For example, from the viewpoint of further increasing the interlayer adhesive strength between two adjacent layers, it is preferable to provide an adhesive layer (layer AD) between the two layers. The adhesive layer preferably contains a thermoplastic resin having adhesiveness. As the thermoplastic resin having adhesiveness, for example, an acid modification 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.

[Manufacturing method]
The method for producing the oxygen-absorbing multilayer injection molded article of the present embodiment is not particularly limited, and a known method can be applied depending on the properties of various materials, the target shape, and the like. Various injection molding methods can be applied to produce a multilayer injection molded article.

  For example, using a molding machine equipped with two or more injection machines and an injection mold, the material constituting the layer A and the material constituting the layer B are passed from the respective injection cylinders through the mold hot runner into the cavity. The two-layer structure A / B multilayer injection molded product having a shape corresponding to the cavity shape of the injection mold can be manufactured. First, the material constituting the layer B is injected from the injection cylinder, then the material constituting the layer A is injected from another injection cylinder simultaneously with the material constituting the layer B, and then the material constituting the layer B By injecting a necessary amount of the solution to fill the cavity, a multilayer injection molded body having a three-layer structure B / A / B can be manufactured. Further, first, the material constituting the layer B is injected, then the material constituting the layer A is injected alone, and finally the necessary amount of the material constituting the layer B is injected to fill the cavity. A multilayer injection molded article having the structure B / A / B / A / B can be produced. Furthermore, first, the material constituting the layer B1 is injected from the injection cylinder, then the material constituting the layer B2 is injected from another injection cylinder at the same time as the material constituting the layer B1, and then the layer A is constituted. By injecting the material simultaneously with the materials constituting the layer B1 and the layer B2, and then injecting a necessary amount of the material constituting the layer B1 to fill the cavity, the five-layer structure B1 / B2 / A / B2 / B1 A multilayer injection molded article can be produced.

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

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

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

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

  Suitable methods for secondary processing of the oxygen-absorbing multilayer injection molded article of the present embodiment include, for example, blow molding, but are not particularly limited thereto, and known molding methods can be applied. As blow molding, stretch blow molding etc. may be sufficient, for example.

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

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

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

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

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

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

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

  As an inorganic substance or inorganic oxide of a vapor deposition film, although aluminum, an alumina, a silicon oxide etc. are mentioned, for example, it does not specifically limit. By coating the vapor deposition film of an inorganic substance or an inorganic oxide, the elution of a low molecular weight organic compound can be shielded from the oxygen-absorbing multilayer injection molded article of this embodiment and a container obtained by secondary processing thereof. Examples of the method for forming the vapor deposition film include physical vapor deposition methods such as vacuum vapor deposition method, sputtering method, ion plating method, chemical vapor deposition methods such as PECVD, etc. The method can be applied. In addition, although the thickness of a vapor deposition film is not specifically limited, From viewpoints, such as gas-barrier property, light-shielding property, and bending resistance, 5-500 nm is preferable, More preferably, it is 5-200 nm.

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

  In using the oxygen-absorbing multilayer injection molded article of the present embodiment, energy rays can be irradiated to promote the start of the oxygen absorption reaction or increase the oxygen absorption rate. Examples of energy rays include visible light, ultraviolet rays, X-rays, electron beams, and γ rays. The amount of irradiation energy can be appropriately selected according to the type of energy beam used.

  The oxygen-absorbing multilayer injection molded article of the present embodiment does not require moisture for oxygen absorption, in other words, oxygen can be absorbed regardless of the presence or absence of moisture in the preserved object. It can be used for a wide range of 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 multilayer injection molded article of this embodiment and various molded articles such as a laminate using the same are used under a wide range of humidity conditions (relative humidity 0% to 100%) from low humidity to high humidity. Since it has excellent oxygen absorption performance and excellent flavor retention of contents, it is suitable for packaging 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. 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 7.68-7.74 (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. 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 7.78 (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. 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 7.00 (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. 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 7.42 (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).

Example 1
Using a twin screw extruder having two screws having a diameter of 37 mm, 95 parts by mass of polyethylene terephthalate (product name: “BK-2180” manufactured by Nihon Unipet Co., Ltd., hereinafter referred to as “PET”) is used. 5 parts by mass of diester compound A and cobalt (II) stearate are 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 after cooling. Sex composition (1) was obtained.

  Next, under the following conditions, the thermoplastic resin (b) constituting the layer B is injected from the injection cylinder, and then the resin composition constituting the oxygen absorbing layer (layer A) is constituted from another injection cylinder to constitute the layer B. The layer B / oxygen absorbing layer (layer A) / layer is injected simultaneously with the thermoplastic resin (b) to be injected, and then the required amount of the thermoplastic resin (b) constituting the layer B is injected to fill the cavity. A three-layer injection molded body (Parison) consisting of B was molded. The total mass of the parison was 28 g, and the mass of the layer A was 30% by mass of the total mass of the parison. The oxygen-absorbing composition (1) was used as the resin composition constituting the oxygen-absorbing layer (layer A), and PET was used as the thermoplastic resin (b).

(Parison shape)
The total length was 95 mm, the outer diameter was 22 mm, and the wall thickness was 2.7 mm. For the manufacture of the parison, an injection molding machine (manufactured by Meiki Seisakusho Co., Ltd., model: M200, 4 pieces) was used.
(Parison molding conditions)
Injection cylinder temperature for layer A: 270 ° C
Injection cylinder temperature for layer B: 270 ° C
Resin channel temperature in mold: 270 ° C
Mold cooling water temperature: 15 ° C

  After cooling the obtained parison, as a secondary process, the parison was heated and biaxial stretch blow molding was performed to produce a bottle.

(Bottle shape obtained by secondary processing)
The total length was 160 mm, the outer diameter was 60 mm, the inner volume was 350 mL, and the wall thickness was 0.40 mm. The draw ratio was 1.9 times in length and 2.7 times in width. The bottom shape is a champagne type. The body has dimples. For secondary processing, a blow molding machine (manufactured by Frontier Corporation, model: EFB1000ET) was used.
(Secondary processing conditions)
Parison heating temperature: 102 ° C
Stretching rod pressure: 0.5 MPa
Primary blow pressure: 0.7 MPa
Secondary blow pressure: 2.5 MPa
Primary blow delay time: 0.30 sec
Primary blow time: 0.30 sec
Secondary blow time: 2.0 sec
Blow exhaust time: 0.6 sec
Mold temperature: 30 ° C.

[Performance evaluation of bottles]
The measurement of the oxygen permeability of the obtained bottle, the visibility of the contents, and the odor test were measured and evaluated according to the following methods and standards. The evaluation results are shown in Table 2.

(1) Measurement of oxygen permeability of bottle The oxygen permeability after 30 days from the start of measurement was measured in an atmosphere of 23 ° C, 50% relative humidity outside the bottle, and 100% relative humidity inside the bottle. For the measurement, an oxygen permeability measuring device (product name: “OX-TRAN 2-21 ML” manufactured by MOCON) was used. The lower the measured value, the better the oxygen barrier property, and the lower limit of detection of the measurement is 5 × 10 ⁻⁵ cc / (package · day · 0.21 atm). The oxygen permeability was measured according to ASTM D3985.

(2) Bottle content visibility The resulting bottle content visibility was visually observed.

(3) Odor test (odor)
The obtained bottle was filled with 350 mL of distilled water and sealed with a polyethylene lid. Thereafter, the odor of distilled water after storage in an atmosphere of 40 ° C. and 90% relative humidity was confirmed.

(Example 2)
Except that diester compound B was used in place of diester compound A, an oxygen-absorbing multilayer bottle was prepared in the same manner as in Example 1, the oxygen permeability was measured, and the contents visibility and odor properties were confirmed. The evaluation results are shown in Table 2.

Example 3
Except that the diester compound C was used in place of the diester compound A, an oxygen-absorbing multilayer bottle was prepared in the same manner as in Example 1, the oxygen permeability was measured, and the contents visibility and odor property were confirmed. The evaluation results are shown in Table 2.

Example 4
Except that diester compound D was used in place of diester compound A, an oxygen-absorbing multilayer bottle was prepared in the same manner as in Example 1, the oxygen permeability was measured, and the contents visibility and odor properties were confirmed. The evaluation results are shown in Table 2.

(Example 5)
Except that the diamide compound E was used in place of the diester compound A, an oxygen-absorbing multilayer bottle was prepared in the same manner as in Example 1, the oxygen permeability was measured, and the contents visibility and odor property were confirmed. The evaluation results are shown in Table 2.

(Comparative Example 1)
A single-layer bottle having the same shape as in Example 1 was prepared using PET, the oxygen permeability was measured, and the contents visibility and odor property were confirmed. The evaluation results are shown in Table 2.

(Comparative Example 2)
Except that the diester compound A was not used, an oxygen-absorbing multilayer bottle was prepared in the same manner as in Example 1, the oxygen permeability was measured, and the contents visibility and odor were confirmed. The evaluation results are shown in Table 2.

(Comparative Example 3)
Except that cobalt stearate (II) was not used, an oxygen-absorbing multilayer bottle was prepared in the same manner as in Example 1, the oxygen permeability was measured, and the contents visibility and odor were confirmed. The evaluation results are shown in Table 2.

(Example 6)
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 (2) was obtained.

  Next, under the following conditions, the thermoplastic resin (b) constituting the layer B is injected from the injection cylinder, and then the resin composition constituting the oxygen absorbing layer (layer A) is constituted from another injection cylinder to constitute the layer B. The layer B / oxygen absorbing layer (layer A) / layer is injected simultaneously with the thermoplastic resin (b) to be injected, and then the required amount of the thermoplastic resin (b) constituting the layer B is injected to fill the cavity. A three-layer injection cup consisting of B was molded. The total mass of the injection cup was 31 g, and the mass of layer A was 20% by mass of the total mass of the injection cup. In addition, as the resin composition constituting the oxygen absorbing layer (layer A), the oxygen absorbing composition (2) is used, and as the thermoplastic resin (b), polypropylene (product name; “NOVATEC PP” manufactured by Nippon Polypro Co., Ltd.) is used. MG03B ", hereinafter also abbreviated as" PP ").

(Cup shape)
The total length was 125 mm, the bottom diameter was 52 mm, the flange outer diameter was 70 mm, the flange inner diameter was 62 mm, the wall thickness was 1.1 mm, and the internal volume was 320 ml. For the production of the cup, an injection molding machine (manufactured by Meiki Seisakusho Co., Ltd., model: M200, 4 pieces) was used.
(Cup molding conditions)
Injection cylinder temperature for layer A: 220 ° C
Injection cylinder temperature for layer B: 220 ° C
Resin channel temperature in mold: 220 ° C
Mold cooling water temperature: 15 ° C

[Evaluation of cup performance]
The measurement of the oxygen permeability of the obtained cup, the measurement of the oxygen concentration in the sealed container after sealed storage, and the odor test were measured and evaluated according to the following methods and standards. The evaluation results are shown in Table 3.

(1) Oxygen permeability of cup The oxygen permeability of the obtained cup was measured in the same manner as in Example 1.

(2) Measurement of oxygen concentration in sealed container 200g of humidity control agent was filled in the obtained cup, the relative humidity in the container was adjusted to 100% or 30%, and an aluminum foil laminated film was used as the top film, The initial oxygen concentration was set to 2 vol% by nitrogen substitution, and sealed to prepare a sealed container. Then, it preserve | saved at 23 degreeC and 50% of relative humidity, and measured the oxygen concentration in the container after one month.

(3) Odor test The aluminum foil laminated film of the sealed container after measuring the oxygen concentration in the sealed container was opened, and the odor in the container was confirmed. In addition, about the odor, the presence or absence of the odor of the container itself and the presence or absence of the odor change before and after oxygen absorption were evaluated, respectively. When there was no odor in the container itself and there was no change in odor before and after oxygen absorption, it was judged as “no odor in the container”.

(Example 7)
An oxygen-absorbing multilayer cup was prepared in the same manner as in Example 6 except that the diester compound B was used in place of the diester compound A, and the odor was confirmed by measuring the oxygen permeability and the oxygen concentration in the sealed container. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

(Example 8)
An oxygen-absorbing multilayer cup was prepared in the same manner as in Example 6 except that the diester compound C was used in place of the diester compound A, and the odor was confirmed by measuring the oxygen transmission rate and the oxygen concentration in the sealed container. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

Example 9
An oxygen-absorbing multilayer cup was prepared in the same manner as in Example 6 except that the diester compound D was used in place of the diester compound A, and the oxygen permeability and the oxygen concentration in the sealed container were measured to confirm the odor. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

(Example 10)
An oxygen-absorbing multilayer cup was prepared in the same manner as in Example 6 except that the diamide compound E was used in place of the diester compound A, and the odor was confirmed by measuring the oxygen permeability and the oxygen concentration in the sealed container. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

(Comparative Example 4)
A multilayer cup was prepared in the same manner as in Example 6 except that the diester compound A and cobalt stearate were not used, and the oxygen transmission rate and the oxygen concentration in the sealed container were measured to confirm the odor. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

(Comparative Example 5)
A multilayer cup was produced in the same manner as in Example 6 except that cobalt stearate was not used, and the odor was confirmed by measuring the oxygen transmission rate and the oxygen concentration in the sealed container. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

(Comparative Example 6)
A multilayer cup was prepared in the same manner as in Example 6 except that the diester compound A was not used, and the oxygen transmission rate and the oxygen concentration in the sealed container were measured to confirm the odor. The evaluation results are shown in Table 3. In addition, the delamination of the cup was not recognized when the aluminum foil laminated film of the sealed container was opened.

(Comparative Example 7)
Nylon MXD6 (product name; “MX nylon S6011” manufactured by Mitsubishi Gas Chemical Co., Inc., hereinafter also abbreviated as “N-MXD6”) was used in place of EVOH, and Example 6 was used except that diester compound A was not used. Similarly, an oxygen-absorbing multilayer cup was prepared, and the oxygen transmission rate and the oxygen concentration in the sealed container were measured to confirm odor. The evaluation results are shown in Table 3. In addition, since the sealed container with a relative humidity of 100% in the container absorbed oxygen, the strength was reduced by oxidative decomposition of the oxygen absorbing layer (N-MXD6 layer), and delamination of the cup occurred when the aluminum foil laminated film was opened.

  In the containers of Examples 1 to 10, oxygen was absorbed by the oxygen absorption layer, so that the oxygen permeability was reduced as compared with Comparative Examples 1 to 6. Moreover, the intensity | strength was maintained after oxygen absorption and generation | occurrence | production of the odor was suppressed.

  Since the oxygen-absorbing multilayer injection molded article of the present invention has an excellent oxygen-absorbing property, it can be widely and effectively used 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 injection molded article having an oxygen-absorbing layer containing an oxygen-absorbing composition and a thermoplastic resin layer containing a thermoplastic resin (b),
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 (a),
(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 injection molded article , 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 injection molded article according to claim 1 . The oxygen-absorbing multilayer injection molded article 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. 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 (a) in the oxygen-absorbing composition. The oxygen-absorbing multilayer injection molded article according to any one of claims 1 to 3 , wherein a ratio of the compound having 1 to 30% by mass. The thermoplastic resin (a) in the oxygen-absorbing composition is at least one selected from the group consisting of polyolefin, polyester, polyamide, ethylene-vinyl alcohol copolymer, and chlorine-based resin. The oxygen-absorbing multilayer injection molded article according to any one of to 4 . The oxygen-absorbing multilayer injection molding 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. body. In the oxygen-absorbing composition, the amount of the transition metal catalyst is 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 (a). The oxygen-absorbing multilayer injection molded article according to any one of claims 1 to 6 , which is contained in an amount of 0.001 to 10 parts by mass. The oxygen-absorbing multi-layer injection molded article according to any one of claims 1 to 7 further processed oxygen-absorbing multilayered container obtained. The oxygen-absorbing multilayer container according to claim 8 , obtained by stretch blow molding.