JP2002069263A - Oxygen absorbing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition or a resin that has an excellent oxygen of scavenging or absorbing property for articles highly sensitive to the presence of oxygen and susceptible to deterioration due to oxygen, especially such as foods, beverages, pharmaceuticals, cosmetics or the like and a slight or odor provide a resin composition or a resin that has excellent gas barrier properties, moisture resistance, fragrance and flavor retaining properties and slight odor keeping the excellent oxygen scavenging or absorbing properties, and provide a molded article excellent in oxygen absorption capability, gas barrier properties, having slight odor or the like by using the resin composition or the resin. SOLUTION: The oxygen absorbing resin composition comprises (a) a thermoplastic resin which has a number average molecular weight in a range of 1,000-500,000, contains a carbon-to-carbon double bond in a ratio of 0.0001 eq/g or more and has a predetermined structural unit, (b) a deodorizer and (c) a transition metal salt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-absorbing resin and a resin composition which are used for products which are sensitive to oxygen and are easily deteriorated, especially for packaging materials and containers for foods, beverages, pharmaceuticals, cosmetics and the like. . The present invention also relates to an oxygen-absorbing resin composition having excellent gas barrier properties, moisture-proof properties, fragrance retention properties, flavor barrier properties, and low odor properties in addition to the oxygen absorbing properties described above. Furthermore, the present invention relates to molded articles using such a composition or resin, for example, packaging materials, containers, and the like for foods, beverages, pharmaceuticals, cosmetics, etc.

[0002]

2. Description of the Related Art Products that are sensitive to oxygen and are susceptible to deterioration are prevented from being exposed to oxygen, thereby maintaining the quality of the products and having a shelf life, so-called "Shelf Life".
It is well known that this can be extended. For example, by using a packaging material to suppress the exposure of food to oxygen that is easily degraded in an oxygen atmosphere, the quality of the food is maintained, and the food is prevented from spoiling. This type of packaging also
Maintain the product's commercial value longer and reduce the costs associated with the need for disposal and restocking. In the food packaging field, some means of limiting oxygen exposure have already been developed. Currently, commonly used means include modified atmospheric packaging (MAP), vacuum packaging and oxygen barrier film packaging. In the first two cases, an atmosphere with a low oxygen concentration is used for packaging, and in the latter case, oxygen is physically prevented from entering the packaging environment.

[0003] The oxygen barrier film packaging is the most classically used means, and various gas barrier resins are used as film materials.

As such a gas barrier resin, ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as EVOH), polyamide, polyvinyl chloride, polyacrylonitrile and the like are widely used. These resins are materials having excellent oxygen or carbon dioxide gas barrier properties, can be melt-molded, and can be widely used for packaging films, sheets, bottles, containers, and the like. Such a resin is laminated with a layer of a thermoplastic resin having excellent moisture resistance, mechanical properties and the like, especially a layer of a polyolefin resin, and is suitably used as a multilayer plastic packaging material. For example, as containers having excellent oxygen barrier properties in the form of bags, bottles, cups, pouches and the like, they are widely used in various fields such as foods, cosmetics, medicinal chemicals, and toiletries.

[0005] A packaging material using such a gas barrier resin is excellent in barrier properties against oxygen and carbon dioxide gas, but is not suitable for a metal material used for canning or a glass used for bottling. As described above, the permeability to gas such as oxygen is not always close to zero, and the gas permeates a non-negligible amount of gas. In particular, in packaging materials for food applications, there is a concern that the quality may deteriorate due to oxidation of the contents when stored for a long period of time. Further, when packaging contents that are easily oxidized, it is also desired to prevent deterioration of the contents by scavenging oxygen mixed into the packaging container together with the contents when the contents are packed or filled. For this reason, it has been proposed to enclose an oxygen scavenger in a packaging environment or to mix the oxygen scavenger into a gas barrier resin to give the gas barrier resin an oxygen scavenging function. In particular, when an oxygen absorbing function is imparted to the gas barrier resin, a uniform scavenging effect can be obtained throughout the inside of the package, and in addition, oxygen passing through the packaging material wall is scavenged by the scavenger. This allows the level of oxygen to be kept to a minimum throughout the interior of the package.

Various compounds are known as the above-mentioned oxygen scavenger. As the improved oxygen scavenger, a transition metal catalyst and an ethylenically unsaturated compound (for example, polybutadiene, polyisoprene, etc.) are contained. A composition has been proposed (see JP-A-5-115776). This publication discloses trans-1,4- as an ethylenically unsaturated compound.
Polyisoprene, and 1,2-polybutadiene, and cobalt compounds as transition metal catalysts are exemplified. However, there is a problem that the oxygen scavenging effect of the oxygen scavenger is not always sufficient, and in some cases, a delay until the start of useful oxygen scavenging (hereinafter referred to as induction period) becomes long. ing.

[0007] As a method for imparting an oxygen absorbing function (scavenging function) to a gas barrier resin, the following method has been proposed: EVOH is oxidized by adding an oxidation catalyst such as a transition metal to EVOH. A method of causing oxygen to be permeated to react with the EVOH, thereby imparting an oxygen absorbing function to the EVOH (Japanese Patent Laid-Open Publication No.
No. 211444); By adding an oxidation catalyst such as a transition metal to polyvinyl chloride, the polyvinyl chloride is easily oxidized, and the oxygen to be permeated is reacted with the polyvinyl chloride. A method of imparting an oxygen-absorbing function to a product (JP-A-4-45144);
EVO using a resin composition comprising a polyolefin and an oxidation catalyst
A method of obtaining a resin composition having an oxygen absorbing function by dispersing in oxygen H and reacting oxygen to be permeated with polyolefin in EVOH (Japanese Patent Laid-Open No. 05-15)
No. 6095); and a method of obtaining a resin composition having an oxygen absorbing function by blending EVOH, a polyolefin and an oxidation catalyst, and reacting oxygen to be permeated with the polyolefin and EVOH (Japanese Patent Application Laid-Open No. 05-2005).
170980).

However, the above methods (1) and (2) have a problem that the effect of improving the oxygen barrier property is not sufficient, and the transparency is not sufficient because a large amount of an oxidation catalyst is added. Also in the methods of (1) and (2), there is a problem that the transparency is significantly impaired by adding a polyolefin to the gas barrier resin.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide products which are sensitive to oxygen and which are susceptible to deterioration, in particular foods and beverages,
An object of the present invention is to provide a composition excellent in the effect of scavenging or absorbing oxygen and excellent in low odor when packaging pharmaceuticals, cosmetics, and the like. Another object of the present invention is, in addition to the effect of scavenging or absorbing oxygen, excellent gas barrier properties, transparency, moisture resistance, fragrance retention, and flavor barrier properties, and excellent low odor properties. An object of the present invention is to provide an oxygen-absorbing resin composition. Still another object of the present invention is to provide a resin having the above properties. Still another object of the present invention is to provide a molded article using the above-described composition or resin, which is excellent in low odor in addition to the above-described oxygen absorbing property and gas barrier property.

[0010]

The first oxygen-absorbing resin composition of the present invention has a number average molecular weight in the range of 1,000 to 500,000, and has a structural formula (I):

[0011]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group or an alkoxy group, and R ₂ and R ₃ are each a hydrogen atom and 1 to 10 carbon atoms. alkyl group, a substituted aryl group, an unsubstituted aryl group, -COOR _4, -OCOR _5, a cyano group or a halogen atom,, R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, aryl Group, an alkylaryl group or an alkoxy group], a thermoplastic resin (a) having at least one structural unit represented by the formula:
It consists of a deodorant (b) and a transition metal salt (c). This thermoplastic resin (a) contains the carbon-carbon double bond in the above structural unit at a rate of 0.0001 eq / g or more.

[0013] In a preferred embodiment, the first aspect of the present invention.
The oxygen absorption rate of the resin composition is 0.01 ml / m ² · d
ay or more.

The second resin composition of the present invention has a number average molecular weight in the range of 1,000 to 500,000, and has a structural formula (I):

[0015]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group or an alkoxy group, and R ₂ and R ₃ are each a hydrogen atom and 1 to 10 carbon atoms. alkyl group, a substituted aryl group, an unsubstituted aryl group, -COOR _4, -OCOR _5, a cyano group or a halogen atom,, R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, aryl Group, an alkylaryl group, or an alkoxy group].
It consists of a thermoplastic resin (a) and a deodorant (b) containing a carbon double bond at a rate of 0.0001 eq / g or more, and has an oxygen absorption rate of 0.01 ml / m ² · day.
The above is the oxygen-absorbing resin composition.

In a preferred embodiment, the resin composition comprises:
It comprises 50 to 99.9 parts by weight of a thermoplastic resin (a) and 0.1 to 50% by weight of the deodorant (b). In a preferred embodiment, the content of the transition metal salt (c) in the resin composition is 1 to 10000 ppm in terms of a metal element.

In a preferred embodiment, the thermoplastic resin (a) used in the present invention has a structural unit represented by the structural formula (I), wherein R ₁ is a methyl group. , R ₂ and R ₃ are each a hydrogen atom.

In a preferred embodiment, the thermoplastic resin (a) has a structural unit derived from an aromatic vinyl compound.

In a preferred embodiment, the thermoplastic resin (a) mainly comprises a polyisoprene block containing the structural formula (I) and a polystyrene block, and more preferably, the thermoplastic resin (a) comprises a polystyrene block. -Polyisoprene block containing structural formula (I)-
It is a ternary block copolymer composed of polystyrene blocks.

In a preferred embodiment, the carbon-carbon double bond of the thermoplastic resin (a) contains 0.002
eq / g or more.

In a preferred embodiment, the transition metal salt (c) is any one of an iron salt, a nickel salt, a copper salt, a manganese salt, and a cobalt salt.

In one embodiment, the resin composition of the present invention further contains a thermoplastic resin other than the above-mentioned thermoplastic resin (a). This resin has, for example, an oxygen transmission rate of 500 ml · 20 μm / m ² · day · atm (20
C., 65% RH) or less.

In a preferred embodiment, the resin composition of the present invention comprises the thermoplastic resin (a) and the gas-barrier resin (d), and the particles comprising the thermoplastic resin (a) are It is dispersed in the resin (d) matrix.

The present invention includes a molded article comprising the above-mentioned oxygen-absorbing resin composition.

The present invention includes a multilayer structure having a layer comprising the above-mentioned oxygen-absorbing resin composition.

The present invention includes a multilayer container having a layer made of the above-mentioned oxygen-absorbing resin composition.

The present invention includes a multilayer container comprising a multilayer film having a layer comprising the above-mentioned oxygen-absorbing resin composition and having a total thickness of 300 μm or less.

The present invention includes a multilayer container having a layer composed of the oxygen-absorbing resin composition and a layer composed of a thermoplastic polyester layer.

The present invention includes a cap provided with a gasket comprising the above-mentioned oxygen-absorbing resin composition.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, "scavenging" oxygen means absorbing and consuming oxygen from a given environment,
Or to reduce that amount.

The thermoplastic resin (a) contained in the oxygen-absorbing resin composition of the present invention has a number average molecular weight of 1,000 to 500,000.
And the structural formula (I):

[0033]

Embedded image

Wherein R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group or an alkoxy group, and R ₂ and R ₃ are each a hydrogen atom and 1 to 10 carbon atoms. alkyl group, a substituted aryl group, an unsubstituted aryl group, -COOR _4, -OCOR _5, a cyano group or a halogen atom,, R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, aryl Group, an alkylaryl group, or an alkoxy group]. The carbon-carbon double bond derived from this structural unit is contained in the resin at a rate of 0.0001 eq / g or more.

The carbon number of the aryl group in the definition of the structural formula (I) is preferably 6 to 10, the carbon number of the alkylaryl group is preferably 7 to 11, and the carbon number of the alkoxy group is Preferably, it is 1 to 10.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group, examples of the aryl group include a phenyl group, examples of the alkylaryl group include a benzyl group, examples of the alkoxy group include a methoxy group and ethoxy group. Examples of the group in which the group is a halogen atom include a chlorine atom.

Since the thermoplastic resin (a) has a carbon-carbon double bond in the molecule as described above, it can react efficiently with oxygen and has an oxygen scavenging function (oxygen absorbing function). ) Is obtained. The carbon-carbon double bond includes a conjugated double bond but does not include a multiple bond contained in an aromatic ring.

As described above, the carbon-carbon double bond is contained in the thermoplastic resin (a) at a rate of 0.0001 eq / g or more. This double bond is preferably
0.0005 eq / g or more, more preferably 0.001 eq / g
eq / g or more, more preferably 0.002 eq / g or more. When the content of the carbon-carbon double bond is less than 0.0001 eq / g, the oxygen absorption rate is not sufficient, and the oxygen scavenging effect of the composition of the present invention is not sufficiently improved. The lower limit of the oxygen absorption rate of the thermoplastic resin (a) is preferably 0.01 ml / m ² · day or more, more preferably 0.1 ml / m ² · day or more, and still more preferably 1 ml / m 2. It is at least ² · day, particularly preferably at least 10 ml / m ² · day.

The molecular weight of the thermoplastic resin (a) is preferably from 1,000 to 500,000, as described above. Further, in consideration of the moldability and processability of the resin composition, the mechanical properties of the molded article obtained therefrom and the dispersibility of the thermoplastic resin other than the thermoplastic resin (a), more preferably,
10,000 to 250,000, most preferably 40,000
２００200,000.

If the molecular weight of the thermoplastic resin (a) is less than 1,000, the moldability and workability of the resin composition or the easiness of handling may be significantly reduced. There is also a possibility that the mechanical properties such as the degree may decrease. Further, a thermoplastic resin other than the thermoplastic resin (a) (for example,
When used in admixture with a gas barrier resin), the dispersibility is reduced, and as a result, the gas barrier properties and oxygen scavenging performance may be reduced. Number average molecular weight of 50,000
Even when it exceeds 0, the moldability and processability of the resin composition may be reduced. Furthermore, when used in combination with a thermoplastic resin other than the thermoplastic resin (a), the dispersibility decreases, and the gas barrier properties and oxygen scavenging performance may decrease.

The carbon-carbon double bond of the thermoplastic resin (a) is generally derived from a diene compound, but is not limited thereto. Examples of the diene compound used in the synthesis of the thermoplastic resin (a) used in the present invention include isoprene, butadiene, 2-ethyl-butadiene, 2-butyl-butadiene and the like. As a diene compound, 1
Only the components may be used, or two components may be used simultaneously, and there is no particular limitation.

The carbon-carbon double bond of the thermoplastic resin (a) used in the present invention may be contained in a main chain or a side chain, but may be contained in a side chain. Is more preferred (i.e., the group having a carbon-carbon double bond in the side chain is larger) since the oxygen absorption rate is increased. For example, when isoprene or butadiene is used as a raw material for synthesizing the thermoplastic resin (a), a vinyl bond content in the obtained thermoplastic resin (a) is 10%.
It is preferably at least 20%, more preferably at least 20%, even more preferably at least 30%. The vinyl bond content refers to the ratio of units forming a vinyl bond (CH ₂ = CH-) (1,2 addition polymerized) among all diene-derived units in the polymer. The double bond existing after the polymerization may be partially reduced by hydrogen as long as the performance of the composition of the present invention is not hindered.

In order to increase the content of vinyl bonds to 10% or more, a Lewis base is used as a cocatalyst when a diene compound such as isoprene is polymerized. Examples of Lewis bases are dimethyl ether, diethyl ether, methyl ethyl ether, ethers such as tetrahydrofuran, ethylene glycol diethyl ether, glycol ethers such as ethylene glycol dimethyl ether,
Examples include tertiary amines such as N, N, N ', N'-tetramethylethylenediamine (TMEDA) and triethylenediamine, and ether-containing amines such as N-methylmorpholine and N-ethylmorpholine. The Lewis base is used in an amount of 0.1 to 400 parts by weight per 100 parts by weight of the initiator described below.

As the solvent, an inert organic solvent is used.
Particularly suitable are hydrocarbons having 6 to 12 carbon atoms, such as hexane, heptane, octane, decane and their cyclic analogues. Aromatic solvents such as toluene,
Benzene, xylene and the like are also suitable. The polymerization is usually -20
The reaction is performed in a temperature range of 〜80 ° C. for 1 to 50 hours.

The thermoplastic resin (a) thus obtained contains a large number of double bonds in the side chain, and thus is easily oxidized and has excellent oxygen absorbing performance.

When the above structural formula (I) of the thermoplastic resin (a) has an alkyl group having 1 to 3 carbon atoms as R ₁ (particularly, isoprene, 2-ethylbutadiene,
(In the case of having a structural unit obtained by polymerizing -butylbutadiene), the thermoplastic resin (a) is easily oxidized and is preferable as an oxygen-absorbing resin. Above all, thermoplastic resin (a)
Contains a structural unit obtained by polymerizing isoprene as the structural unit represented by the structural formula (I) (that is, when R ₁ in the structural formula (I) is a methyl group, and R ₂ and R ₃ are hydrogen atoms) Is the double bond (vinyl bond) of the structural unit
Reacts effectively with oxygen, so that the thermoplastic resin (a) is particularly easily oxidized and has excellent oxygen absorbability. Further, isoprene is easily available and is easily polymerized with other monomers, so that isoprene is preferable from the viewpoint of the synthesis cost of the thermoplastic resin (a).

The thermoplastic resin (a) used in the present invention
Is preferably a copolymer of an aromatic vinyl compound and a diene compound. When the thermoplastic resin (a) is a copolymer of an aromatic vinyl compound and a diene compound, a double bond derived from the diene compound easily reacts with oxygen, thereby improving oxygen barrier properties and oxygen scavenging effects. be able to. Further, by adjusting the copolymerization ratio of the aromatic vinyl compound and the diene compound, the moldability and workability of the thermoplastic resin (a) can be improved, and the hardness can be changed. By adjusting the copolymerization ratio of the aromatic vinyl compound and the diene compound, the refractive index of the obtained thermoplastic resin (a) can be adjusted. Therefore,
As described later, when the composition of the present invention contains the gas barrier resin (d), the difference between the refractive index of the gas barrier resin (d) and the refractive index of the thermoplastic resin (a) is set to be small. As a result, a product having excellent transparency can be obtained. Thus, the composition of the present invention can be adjusted to physical properties suitable for various packaging materials.

The aromatic vinyl compound used in the synthesis of the thermoplastic resin (a) used in the present invention includes styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 3-vinylnaphthalene, 3-methylstyrene,
4-propylstyrene, 4-cyclohexylstyrene,
4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like. Among them, styrene is most preferred from the viewpoint of cost and ease of polymerization.

When the thermoplastic resin (a) is a copolymer of an aromatic vinyl compound and a diene compound, the copolymer may be a random copolymer, a block copolymer, a graft copolymer, or a copolymer thereof. May be used without any particular limitation. From the viewpoints of manufacturability, mechanical properties of the thermoplastic resin (a), ease of handling, and oxygen absorption rate, a block copolymer is preferable.

When the thermoplastic resin (a) is a block copolymer, its production method is not particularly limited, but it is preferable to use an anionic polymerization method. At this time, the number average molecular weight of the aromatic vinyl compound block is preferably 3
In the range of 100 to 100,000, more preferably 10
In the range of 00 to 50,000, more preferably 300
The range is from 0 to 50,000. When the molecular weight of the aromatic vinyl compound block is less than 300, the melt viscosity of the thermoplastic resin (a) is low, and the resin composition may have poor moldability, processability, or handleability. In addition, mechanical properties such as strength and elongation when formed into a molded article tend to decrease. Further, as described later, in a mode in which the thermoplastic resin (a) is dispersed in another resin such as the gas barrier resin (d), the dispersibility of the thermoplastic resin (a) decreases,
As a result, oxygen scavenging performance may decrease. If the molecular weight of the aromatic vinyl compound block exceeds 100,000, the melt viscosity is high and the thermoplasticity is impaired, so that the moldability and processability of the resin composition is reduced. Further, since the dispersibility is also reduced as described above, the oxygen scavenging performance tends to be reduced as a result.

The block form of the block copolymer is A
(BA) _n and (AB) _n . Here, A represents a block composed of an aromatic vinyl compound, B represents a block composed of a diene compound, and n is an integer of 1 or more.

The thermoplastic resin (a) used in the present invention is preferably a binary block copolymer or a ternary block copolymer, and more preferably a ternary block copolymer. Among them, it is preferable that the block composed of the aromatic vinyl compound is a polystyrene block and the block composed of the diene compound is polyisoprene from the viewpoint of cost and ease of polymerization. In particular, when the thermoplastic resin (a) is a diblock copolymer composed of a polyisoprene block and a polystyrene block containing the structural formula (I), the polymerization is easy, the handling is easy, the oxygen absorption rate and the cost are low. It is preferred in that respect.
When the thermoplastic resin (a) is a ternary block copolymer composed of a polystyrene block-a polyisoprene block-a polystyrene block containing the structural formula (I), ease of polymerization, ease of handling, oxygen absorption rate and cost In addition to the above points, it is more preferable because the mechanical properties are improved.

Further, the thermoplastic resin (a) of the present invention
Is the ta in the block derived from the diene compound
The main dispersion peak temperature of nδ is preferably in the range of −40 ° C. to 60 ° C. The main dispersion peak temperature of tan δ is -4
If the temperature is lower than 0 ° C., the oxygen absorption rate tends to be low, and the oxygen scavenging performance tends to decrease. When the main dispersion peak temperature of tan δ exceeds 60 ° C., the oxygen absorption rate at a low temperature becomes slow, and the oxygen scavenging performance tends to decrease. In consideration of the oxygen scavenging performance, the main dispersion peak temperature of tan δ in the block derived from the diene compound is from −20 ° C. to 4 ° C.
The temperature is more preferably in the range of 0 ° C, and even more preferably in the range of -10 ° C to 30 ° C.

The block copolymer of an aromatic vinyl compound and a diene compound can be obtained by the following various methods. A method of polymerizing an aromatic vinyl compound and a diene compound with an alkyllithium compound as an initiator and coupling with a coupling agent, or a method of sequentially polymerizing a diene compound and an aromatic vinyl compound with a dilithium compound as an initiator Is a typical example,
It is not limited to these. Examples of the alkyl lithium compound include an alkyl compound having 1 to 10 carbon atoms in the alkyl residue. Particularly, methyl lithium, ethyl lithium, benzyl lithium and butyl lithium are preferred.

As coupling agents, dichloromethane,
Dibromomethane, dichloroethane, dibromoethane and the like are used. Examples of the dilithium compound include naphthalenedilithium, oligostilidilithium, dilithiohexylbenzene, and the like. The amount used is 0.01 to 0.01 parts by weight based on 100 parts by weight of all monomers used in the polymerization.
0.2 parts by weight and 0.04 to 0.8 parts by weight of the coupling agent are suitable.

The block copolymer is prepared by adding the polymerization reaction solution to a poor solvent such as methanol and coagulating the mixture, followed by heating or drying under reduced pressure, or by dropping the polymerization reaction solution into boiling water to form an azeotropic solvent. -It is obtained by heating or drying under reduced pressure after removal.

The thermoplastic resin (a) may be a single resin or a mixture of a plurality of resins. When it is desired to obtain a molded article having good transparency when it is a mixture, the internal haze value of the film having a thickness of 20 μm is preferably 10% or less.

Since the thermoplastic resin (a) is susceptible to oxidation due to its structure, it is recommended to add an antioxidant in advance, for example, to prevent oxidation during storage.

Examples of the antioxidant include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, and 4,4'-thiobis- (6-t-butylphenol. ), 2,2'-methylene-bis- (4-
Methyl-6-t-butylphenol), octadecyl-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6
-Tert-butylphenol), 2-tert-butyl-6
-(3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, pentaerythritol tetrakis (3-laurylthiopropionate), 2,6-di- (t-butyl) -4 -Methylphenol (BHT), 2,2'-methylenebis- (6
-T-butyl-p-cresol), triphenyl phosphite, tris- (nonylphenyl) phosphite, dilauryl thiodipropionate, and the like.

The optimal amount of the antioxidant to be added is determined in consideration of the type and content of the components in the composition, the purpose of use, storage conditions and the like. In general, when a large amount of an antioxidant is contained, a reaction between oxygen which tends to pass through the resin composition containing the thermoplastic resin (a) and the thermoplastic resin (a) is hindered. Therefore, the oxygen barrier properties and the oxygen scavenging function of the composition of the present invention may not be sufficiently exhibited. On the other hand, if the antioxidant is not contained or its content is too small, the reaction with oxygen proceeds during the storage or melt processing of the thermoplastic resin (a), and the oxygen absorption performance is reduced during actual use. It may have dropped.

When the thermoplastic resin (a) is stored in an inert gas atmosphere, or when the resin composition is produced by melting and blending at a relatively low temperature or with a nitrogen seal, the amount of the antioxidant is May be less.

When the transition metal salt (c), which is an oxidation catalyst, is added at the time of melt blending to promote oxidation, the thermoplastic resin (a) contains a certain amount of an antioxidant. However, a resin composition having good oxygen absorbing ability can be obtained. In such a case, the content of the antioxidant is preferably 0.01 to 1% by weight, and
0.5% by weight is more preferred. This antioxidant may be added to the thermoplastic resin (a) in advance as described above, or the respective components of the oxygen-absorbing resin composition are mixed in the same manner as other general additives described below. May be added sometimes.

The deodorant (b) used in the present invention refers to a porous active substance which deodorizes odor components by physical adsorption or physical adsorption and chemical adsorption, and a catalytic substance which decomposes odor components by redox reaction. .

The deodorant (b) is used to reduce the odor due to the low-molecular reaction products generated when the resin composition of the present invention is scavenged with oxygen.

Examples of suitable deodorants include, but are not particularly limited to, zinc compounds, aluminum compounds, silicon compounds, iron (II) compounds, organic acids, iron (II) compound-organic acid compositions, and the like. Is raised. These may be used alone, or may be a mixture of multiple types or a double salt.

Examples of the zinc compound include zinc silicate, zinc oxide, zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate,
Zinc carbonate, zinc acetate, zinc oxalate, zinc citrate, zinc fumarate, zinc formate and the like.

Examples of the aluminum compound include aluminum sulfate, aluminum phosphate, aluminum silicate and potassium aluminum sulfate.

Examples of the silicon compound include silicon dioxide, silicon orthophosphate, silicon phosphate compounds such as silicon pyrophosphate-I type and silicon pyrophosphate-II type, activated silica gel and the like.

As the iron (II) compound, any iron compound can be used as long as it forms a divalent iron ion.
Examples are ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous bromide, ferrous iodide and other inorganic iron (II) salts, ferrous gallate, ferrous malate, Iron (I) such as ferrous fumarate
I) Organic salts, of which ferrous sulfate and ferrous chloride are preferred.

A composition (mixture or double salt) containing a zinc compound and a silicon compound is also preferably used. Specific examples of this composition include zinc silicate having a weight ratio of zinc oxide to silicon dioxide in the range of 1: 5 to 5: 1 and having a mostly amorphous structure. Preferred are substantially amorphous particles. The ratio of zinc oxide to silicon dioxide is preferably in the range from 1: 4 to 4: 1, more preferably in the range from 1: 3 to 3: 1.

A composition of a zinc compound and an aluminum compound is also suitably used. As a specific example of this, a mixture of zinc oxide and / or zinc carbonate, and aluminum sulfate and / or potassium aluminum sulfate is preferable. Preferably 30 to
It is mixed at a ratio of 300 parts by weight.

The organic acids are preferably organic acids having 8 or more carbon atoms, such as aliphatic monocarboxylic acids, aliphatic polycarboxylic acids, aromatic monocarboxylic acids, and aromatic polycarboxylic acids, and particularly preferably aromatic carboxylic acids. . Examples of aromatic polycarboxylic acids include phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, 1,2,3-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzenehexacarboxylic acid, naphthalene Dicarboxylic acid, naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, diphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, azobenzene tetracarboxylic acid or anhydrides thereof, among which benzene tricarboxylic acid, especially trimellitic acid Is preferred.

Iron (II) Compound--As the iron (II) compound used in the organic acid composition, any compound can be used as long as it is a compound which dissolves in water to form a divalent iron ion as described above. Can be used. For example, ferrous (II) inorganic salts such as ferrous sulfate, ferrous chloride, ferrous nitrate, ferrous bromide, and ferrous iodide, ferrous gallate, ferrous malate, and fumaric acid Organic salts of iron (II) such as ferrous acid may be mentioned, among which ferrous sulfate and ferrous chloride are preferred.

The organic acid used in the iron (II) compound-organic acid composition may be any water-soluble organic acid. Examples thereof include ascorbic acids such as ascorbic acid, isoascorbic acid and metal salts thereof, and citric acid. Acid, isocitric acid,
Examples thereof include carboxylic acids such as lactic acid, tartaric acid, and malic acid, and among them, L-ascorbic acid is preferable.

The iron (II) compound-organic acid composition used is preferably bonded to each other, for example, by spray-drying an aqueous solution in which both components have been mixed and dissolved once.
It can be prepared by drying and powdering by freeze-drying or the like. Iron (I
I) The component ratio of the compound to the organic acid is 1: 0.01 by weight.
１ ： 1: 1.0, more preferably 1: 1.
It is in the range of 0.02-1: 0.80. When the organic acid component is an ascorbic acid, the weight ratio of the iron (II) compound to the organic acid is preferably in the range of 1: 0.02 to 1: 0.30, more preferably 1: 0.02 to 1 : 0.13,
Particularly preferably, it is in the range of 1: 0.05 to 1: 0.13. In the present invention, two or more iron (II) compounds or two or more organic acids may be used in combination. Further, it is preferable to add 2 to 20% by weight of alum as a stabilizer for the deodorizing function to the total amount of the iron (II) compound and the organic acid to the iron (II) compound-organic acid composition. The alum is not particularly limited, but potash alum, ammonia alum, and sodium alum are preferred.

Further, as other deodorants, a composition in which a metal compound such as a composition comprising a zinc compound and a polycarboxylic acid is stabilized, a biological enzyme model compound such as an iron (II) -phthalocyanine derivative, a drill, Magnesium silicate clay minerals such as holly, mokusei, camellia, butterflies, lilac, sapwood, chestnut, alder, etc., plant sap or extractables, aluminosilicates such as zeolite, sepiolite, silotile, barygorskite, lafrinite, etc. Activated humic acid, activated alumina,
Activated carbon can also be used. Also, a porous adsorbent such as a porous microcapsule powder can be used.

Among the above-mentioned deodorants, zinc compounds such as zinc oxide and zinc sulfate, silicon compounds such as silicon dioxide and silicon orthophosphate, aluminum compounds such as aluminum sulfate and aluminum potassium sulfate, compositions containing zinc compounds and silicon compounds , A composition containing a zinc compound and an aluminum compound, an organic acid, an iron (II) compound-organic acid composition, a porous adsorbent such as a porous microcapsule powder, and particularly preferably silicon dioxide and silicon orthophosphate. And a porous adsorbent such as a porous microcapsule powder and a composition containing a silicon compound, a zinc compound and a silicon compound. Further, from the viewpoint of the transparency of the resin composition, a porous adsorbent such as a porous microcapsule powder is particularly preferable.

The particle size of the deodorant (b) used in the present invention is 0.5 to 10 μm, more preferably 1 to 8 μm, further preferably 1 to 5 μm, and particularly preferably 1 to 5 μm. ４4 μm. When the particle size of the deodorant (b) exceeds 10 μm, the odor barrier properties and the transparency become insufficient. A method for producing such a deodorant having a small particle size is not particularly limited, but a method in which a commercially available deodorant is subjected to a pulverizing treatment is exemplified as a suitable method. When the deodorant (b) is a porous adsorbent such as a porous microcapsule powder, the adsorbent having the above particle size can be obtained by preparing the adsorbent by a sol-gel method. it can.

The particle size of the deodorant (b) in the present invention is determined by taking a photograph obtained by magnifying the adsorbent 1000 times with an electron microscope, and randomly selecting 20 adsorbents from the photograph. Was used to measure the particle size. This operation was repeated three times, and the average diameter of the adsorbent was determined from a total of 60 measurement results.

The resin composition of the present invention comprises the thermoplastic resin (a) and the deodorant (b). The resin composition comprises (a) 50 to 99.9% by weight and (b) 0.1% by weight.
Preferably, it consists of 〜50% by weight. When the content of the thermoplastic resin (a) exceeds 99.9% by weight and when the content of (b) is less than 0.1% by weight, the effect of suppressing odor becomes unsatisfactory. On the other hand, when the content of the thermoplastic resin is less than 50% by weight and (b)
If the content exceeds 50% by weight, the oxygen scavenging ability of the resin composition may be insufficient, and the resin composition may not be able to obtain sufficient transparency.

The resin composition of the present invention preferably contains a transition metal salt (c). The transition metal salt (c) is 1 to 10000 ppm, preferably 5 to 50 ppm in terms of a metal element.
It is contained at a rate of 00 ppm, more preferably 10 to 2000 ppm. Thereby, the oxygen oxidation reaction of the thermoplastic resin (a) can be promoted. For example, the thermoplastic resin (a) can efficiently react with oxygen present inside the packaging material obtained from the composition of the present invention and oxygen which is going to permeate the packaging material. as a result,
The oxygen barrier properties and the oxygen scavenging action of the resin composition of the present invention are improved. However, when the content of the transition metal salt (c) exceeds 10,000 ppm in terms of a metal element, the thermal stability of the resin composition of the present invention is reduced, and the generation of decomposition gas and the generation of a gel may become remarkable. There is. From such a viewpoint, the content of the transition metal salt (c) is preferably in the above range. The composition of the present invention, such as a gas barrier resin,
When a thermoplastic resin other than the thermoplastic resin (a) is contained, the transition metal salt (c) is contained in an amount of 1 to 5000 ppm, preferably 5 to 1000 ppm, more preferably 10 to 1000 ppm.
It is contained in the range of 500 ppm.

The metal used for the transition metal salt (c) is preferably selected from the first, second or third transition series of the periodic table. Suitable metals are manganese, iron,
Cobalt, nickel, copper, rhodium, titanium, chromium,
Vanadium and ruthenium include, but are not limited to. Preferred among these metals are iron, nickel, copper, manganese and cobalt, more preferably manganese and cobalt, and even more preferably cobalt.

The counter ion of the metal used for the transition metal salt (c) includes an anion derived from an organic acid or chloride. Organic acids include acetic acid, stearic acid, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, tollic acid, oleic acid, resin acid, capric acid, and naphthenic acid, It is not limited to this. Particularly preferred salts include cobalt 2-ethylhexanoate, cobalt neodecanoate and cobalt stearate. The metal salt may be a so-called ionomer having a polymeric counter ion.

The composition of the present invention contains, if necessary, a thermoplastic resin other than the thermoplastic resin (a). This thermoplastic resin may be, for example, a gas barrier resin (d) or a thermoplastic resin having another function.

As the gas barrier resin (d), 2
The oxygen permeation rate measured under the conditions of 0 ° C. and 65% relative humidity is 500 ml · 20 μm / m ² · day · at
m or less is preferred. This means that the volume of oxygen permeating through a film having an area of 1 m ² and a thickness of 20 μm per day is 500 ml or less under a pressure difference of 1 atm. Oxygen transmission rate is 500ml ・ 2
If it exceeds 0 μm / m ² · day · atm, the gas barrier performance will not be sufficiently exhibited. When it is necessary to obtain good gas barrier properties, it is preferable that the oxygen permeation rate of the gas barrier resin (d) is small. Preferably 100ml
20 μm / m ² · day · atm or less, more preferably 20 ml · 20 μm / m ² · day · atm or less, and still more preferably 5 ml · 20 μm / m ²
· Day · atm or less.

By blending the gas barrier resin (d) with the thermoplastic resin (a) having a carbon-carbon double bond, the oxygen scavenging effect of the resin (a) can be obtained in addition to the gas barrier effect of the resin (d). The resin composition is exhibited, and as a result, a resin composition having extremely high gas barrier properties can be obtained.

In order to obtain a resin composition having high transparency, the refractive index of the thermoplastic resin other than the thermoplastic resin (a) is preferably 1.50 to 1.56. If the ratio deviates from this range, the difference between the refractive index of the resin and the refractive index of the thermoplastic resin (a) increases, as described later, and the transparency of the obtained resin or resin composition decreases. Generally, since the refractive index of the thermoplastic resin (a) having a carbon-carbon double bond is often in the above range, other resins such as the thermoplastic resin (a) and the gas barrier resin (d) are used. It is easy to reduce the difference in the refractive index from the resin composition, and as a result, it is possible to obtain a resin composition having good transparency. In the above range, the refractive index of the gas barrier resin (d) is more preferably 1.51 or more, and further preferably 1.52 or more. Further, it is preferably 1.55 or less in the above range, and more preferably 1.54 or less.
It is as follows.

In the resin composition of the present invention, the thermoplastic resin
Gas barrier resin as thermoplastic resin other than fat (a)
When (d) is contained, the gas barrier resin (d)
Is not particularly limited. Oxygen transmission rate as above
The degree is 500ml ・ 20μm / m ^Two・ Day ・ atm or less
And the refractive index is 1.50 to 1.56
Examples of the gas barrier resin (d) satisfying the following conditions:
Polyvinyl alcohol resin (eg, EVOH), poly
Amides, polyvinyl chloride, polyacrylonitrile, etc.
Typical resins, but limited to these resins
Not done.

Among the gas barrier resins (d), polyvinyl alcohol resins are homopolymers of vinyl esters or copolymers of vinyl esters and other monomers (particularly copolymers of vinyl esters and ethylene). Is saponified using an alkali catalyst or the like.

As the vinyl ester, a typical compound is vinyl acetate, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used.

The degree of saponification of the vinyl ester component of the polyvinyl alcohol resin is preferably 90% or more, more preferably 95% or more, and even more preferably 97% or more.
% Or more. If the saponification degree is less than 90 mol%, the gas barrier properties under high humidity may be reduced. Further, in the case of an ethylene-vinyl alcohol copolymer (EVOH), the thermal stability is deteriorated, and the resulting molded article is liable to generate gels and bumps.

When the polyvinyl alcohol-based resin comprises a blend of two or more kinds of polyvinyl alcohol-based resins having different degrees of saponification, the average value calculated from the blending weight ratio is defined as the degree of saponification. The saponification degree of such a polyvinyl alcohol-based resin can be determined by a nuclear magnetic resonance (NMR) method.

As the polyvinyl alcohol-based resin used in the present invention, EVOH is preferable among the above-mentioned gas-barrier resins because it can be melt-molded and has good gas-barrier properties under high humidity.

The EVOH preferably has an ethylene content of 5 to 60 mol%. If the ethylene content is less than 5 mol%, the gas barrier properties under high humidity may decrease, and the melt moldability may also deteriorate. The ethylene content of the EVOH is preferably at least 10 mol%, more preferably 15 mol%.
As described above, it is optimally at least 20 mol%. If the ethylene content exceeds 60 mol%, it is difficult to obtain sufficient gas barrier properties. The ethylene content is preferably at most 55 mol%, more preferably at most 50 mol%. The ethylene content of EVOH can be determined by a nuclear magnetic resonance (NMR) method.

The EVOH preferably used has an ethylene content of 5 to 60 mol% and a saponification degree of 90% or more.

When the EVOH is composed of a blend of two or more EVOHs having different ethylene contents or saponification degrees, the average calculated from the blending weight ratio is defined as the ethylene content or saponification degree.

However, when two types of EVOH are blended, it is preferred that the difference in ethylene content between them is 15 mol% or less and the difference in saponification degree is 10% or less. If these conditions are not satisfied, the transparency of the resin composition layer is impaired. From the viewpoint of obtaining good transparency, the difference in ethylene content is more preferably 10 mol% or less, and still more preferably 5 mol% or less. Similarly, from the viewpoint of obtaining good transparency, the difference in the degree of saponification is more preferably 7% or less, and still more preferably 5% or less.

The polyvinyl alcohol-based resin, particularly EVOH, may contain a small amount of another monomer as a copolymer component, as long as the object of the present invention is not impaired. Examples of the monomer which can be a copolymerization component include α-olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene and 1-octene; itaconic acid, methacrylic acid, acrylic acid Carboxylic acids, such as maleic anhydride, salts thereof, partial or complete esters thereof, nitriles, amides, anhydrides thereof; vinylsilane compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof; alkylthiols And vinylpyrrolidones.

When EVOH contains 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymer component, the consistency of the melt viscosity with the base resin at the time of coextrusion molding or coinjection molding is improved. Improved and homogeneous moldings can be produced. Here, examples of the vinylsilane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropyltrimethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

Further, when a boron compound is added to EVOH, the melt viscosity of EVOH is improved, and this is effective in that a homogeneous co-extrusion or co-injection molded product can be obtained. Here, examples of the boron compound include boric acids, borate esters, borates, borohydrides, and the like.
Specifically, examples of boric acids include orthoboric acid, metaboric acid, tetraboric acid, and the like.Examples of borate esters include triethyl borate, trimethyl borate, and the like. Examples include alkali metal salts, alkaline earth metal salts of acids, borax, and the like.
The orthoboric acid of these compounds is preferred.

When a boron compound is added, its content is from 20 to 2000 ppm, preferably from 50 to 1000 ppm in terms of boron element. By being in this range, it is possible to obtain EVOH in which torque fluctuation during heating and melting is suppressed. If it is less than 20 ppm, such an effect is small, and if it exceeds 2,000 ppm, gelation is likely to occur, resulting in poor moldability.

It is also effective to add 5 to 5000 ppm of an alkali metal salt to EVOH in terms of an alkali metal element in order to improve interlayer adhesion and compatibility.

A more suitable addition amount of the alkali metal salt is 20 to 1000 ppm, preferably 30 to 500 ppm in terms of the alkali metal element. Examples of the alkali metal include lithium, sodium, and potassium.
Examples of the alkali metal salt include an aliphatic carboxylate, an aromatic carboxylate, a phosphate, and a metal complex of a monovalent metal. Examples include sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, and sodium salt of ethylenediaminetetraacetic acid. Among them, sodium acetate, potassium acetate and sodium phosphate are preferred.

Further, the EVOH used in the present invention is converted to a phosphoric acid compound at 20 to 500 pp in terms of phosphate group.
m, more preferably 30-300 ppm, optimally 50-300 ppm
It is also preferable to contain 200 ppm. By blending the phosphoric acid compound in the above range, the thermal stability of EVOH can be improved. In particular, it is possible to suppress the occurrence and coloring of gel-like bumps when performing melt molding for a long time.

The kind of the phosphoric acid compound to be mixed in the EVOH is not particularly limited. Various acids such as phosphoric acid and phosphorous acid and salts thereof can be used. The phosphate may be contained in any form of a first phosphate, a second phosphate, and a third phosphate, and the cationic species thereof is not particularly limited. And alkaline earth metal salts. Among them, it is preferable to add a phosphate compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

In addition, if necessary, a heat stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent, a filler, and other resins (polyamide, polyolefin, etc.) may be added to EVOH in advance.
Can also be blended. EV to which the above boron compound, alkali metal salt, phosphorus compound, etc. are added
OH is commercially available.

The suitable melt flow rate (MFR) of EVOH that can be used in the present invention (210 ° C., under a load of 2160 g, based on JIS K7210) is from 0.1 to 100.
g / 10 minutes, more preferably 0.5 to 50 g / 10 minutes, and still more preferably 1 to 30 g / 10 minutes.

In the present invention, a heat stabilizer, an ultraviolet absorber, an antioxidant, a coloring agent, a filler, a plasticizer, a filler, and other resins (polyolefin, etc.) are previously added as long as the object of the present invention is not impaired. It can also be blended with the gas barrier resin (d).

The resins other than the thermoplastic resin (a) which can be contained in the composition of the present invention and other than the above-mentioned polyvinyl alcohol-based resin include, for example, the following thermoplastic resins: ethylene Homopolymers and ethylene copolymers (copolymers of ethylene with the following monomers: α-olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; itaconic acid, methacrylic acid Acids, acrylic acid, unsaturated carboxylic acids such as maleic anhydride, salts thereof,
Its partial or complete esters, its nitriles, its amides, its anhydrides; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate,
Carboxylic acid vinyl esters such as vinyl dodecanoate, vinyl stearate, and vinyl arachidonate; vinyl silane compounds such as vinyl trimethoxy silane; unsaturated sulfonic acids or salts thereof; alkyl thiols; vinyl pyrrolidones, etc.), propylene homo Polymers and propylene copolymers (copolymers of propylene with the following monomers: ethylene, 1-butene, isobutene, 4
Α-olefins such as -methyl-1-pentene, 1-hexene and 1-octene; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride, salts thereof, partial and complete esters thereof, and nitriles thereof Carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate and vinyl arachidonate; vinyl trimethoxy Vinylsilane compounds such as silane; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidones, etc.), polyolefins such as poly-4-methylpentene-1 and polybutene-1; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphate Polyesters such as rate; poly ε- caprolactam, polyhexamethylene adipamide, polyamide such as poly-m-xylylene adipamide; polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonates, polyacrylates and the like. The choice of the thermoplastic resin depends on the structure and use of the molded article to be manufactured. Such selection factors are well known in structure and use.

When the composition of the present invention contains the thermoplastic resin (a) and a thermoplastic resin other than the resin, it is preferable to consider the miscibility of these resins. The miscibility of these resins can affect transparency, cleanliness, effectiveness as an oxygen scavenger, barrier properties, mechanical properties, product texture, and the like.

When the resin composition of the present invention contains a thermoplastic resin other than the thermoplastic resin (a), the content of each component is not particularly limited. Usually, the total amount of the thermoplastic resin (a), the deodorant (b) and the transition metal salt (c) is 99 to 1% by weight, and the thermoplastic resin other than the thermoplastic resin (a) is 1 to 99% by weight. It is. More preferably, the total amount of the resin (a), the deodorant (b) and the transition metal salt (c) is 90 to 10% by weight, and the thermoplastic resin other than the thermoplastic resin (a) is 10 to 90% by weight. is there.

When it is desired to obtain a composition having an excellent gas barrier property among the various aspects of the present invention, the oxygen-absorbing resin composition of the present invention contains a slightly large amount of the gas barrier resin. You. Usually, the thermoplastic resin (a) is used in an amount of 0.1 to 30.
The deodorant (b) was added in an amount of 0.1 to 10% by weight, and the gas barrier resin (d) was added in an amount of 99.8 to 99.8% by weight.
It is preferable to contain it in a proportion of 60% by weight.

The content ratio of the gas barrier resin (d) is 60
When the amount is less than the weight percentage, transparency and gas barrier properties such as oxygen gas or carbon dioxide gas in a molded article such as a multilayer container using the resin composition may be reduced. 9 content
When it exceeds 9.8% by weight, the content of the thermoplastic resin (a) is reduced, so that the oxygen absorption rate is reduced, and the oxygen gas barrier property and the oxygen scavenging property tend to be reduced. A preferable range of the content of the thermoplastic resin (a) in the resin composition is 1 to 20% by weight, and a more preferable range is 2 to 15% by weight. A more preferable range of the content ratio of the gas barrier resin (d) is 80 to 99% by weight,
A more preferred range is from 85 to 98% by weight.

On the other hand, when the oxygen absorption rate is more important than the gas barrier property, a mode in which the gas barrier resin (d) is not included is also a preferable mode.

In the resin composition of the present invention, in a composition containing a resin other than the thermoplastic resin (a) such as the gas barrier resin (d), the particles composed of the thermoplastic resin (a) A preferred embodiment is one in which the resin is dispersed in a matrix containing a resin other than (1) and various additives described below as necessary. For example, when the oxygen-absorbing resin composition of the present invention is made of a thermoplastic resin (a) and a gas barrier resin (d), particles made of the thermoplastic resin (a) form a matrix of the gas barrier resin (d). A distributed mode is recommended. In various molded articles made of the composition in such a state, oxygen scavenging properties and gas barrier properties are easily maintained,
This is preferable in that the functions of resins other than the thermoplastic resin (a) such as the gas barrier resin (d) can be imparted. Transparency is also good. At this time, the dispersed particle diameter of the particles made of the thermoplastic resin (a) is preferably 10 μm or less.
When the dispersion particle size exceeds 10 μm, the area of the interface between the thermoplastic resin (a) and the resin other than the thermoplastic resin (a) becomes small, and the oxygen gas barrier property decreases,
Oxygen scavenging performance may decrease. The average particle size of the dispersed thermoplastic resin (a) particles is more preferably 5 μm or less, from the viewpoints of oxygen scavenging properties, gas barrier properties, and transparency of molded articles such as multilayer containers using the resin composition.
μm or less is more preferable.

Among the resin compositions of the present invention, those containing a thermoplastic resin other than the thermoplastic resin (a), such as the gas barrier resin (d), have a refractive index and thermoplasticity of the thermoplastic resin (a). When the difference from the refractive index of the resin other than the resin (a) is 0.01 or less, the transparency of a molded article obtained from this composition is good. When the difference in refractive index exceeds 0.01, a molded article obtained from the resin composition tends to be slightly opaque. In order to obtain good transparency, the difference in the refractive index is preferably 0.007 or less,
More preferably, it is 0.005 or less. Examples of the resin having a refractive index difference of 0.01 or less with respect to the thermoplastic resin (a) include polyvinyl alcohol resins such as polyvinyl alcohol and poly (ethylene vinyl alcohol), polyamides,
Suitable are, but not limited to, polyvinyl chloride, polyacrylonitrile, and the like.

The resin composition of the present invention contains various additives as necessary. Examples of such additives include antioxidants, plasticizers, heat stabilizers (melt stabilizers), photoinitiators, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers And pigments, dyes, processing aids, flame retardants, anti-fogging agents, and other high molecular compounds, which can be contained within a range that does not impair the effects of the present invention.

Among the above additives, heat stabilizers (melt stabilizers)
As a hydrotalcite compound, a metal salt of a higher aliphatic carboxylic acid (for example, calcium stearate,
One or more of magnesium stearate and the like are used. These compounds are used in an amount of 0.1% in the entire resin composition.
It is preferable to contain it in a proportion of from 01 to 1% by weight.

When the resin composition of the present invention contains a hydrotalcite compound, it is possible to prevent gels and fish eyes which occur with time in a layer made of the resin composition, and to provide a long-term operation stability. Can be further improved.

When the resin composition contains a metal salt of a higher aliphatic carboxylic acid, a gel or a fish eye which is generated with time can be prevented, and the long-term operation stability is further improved. be able to.

The metal salt of a higher aliphatic carboxylic acid is a metal salt of a higher fatty acid having 8 to 22 carbon atoms. 8 to 2 carbon atoms
2 higher fatty acids include lauric acid, stearic acid,
And myristic acid. Examples of the metal constituting the salt include sodium, potassium, magnesium, calcium, zinc, barium, aluminum and the like.
Of these, alkaline earth metals such as magnesium, calcium and barium are preferred.

Among the above additives, a photoinitiator is used for starting or accelerating oxygen scavenging in a layered product or a packaging film made of a resin composition.

If the oxygen absorbing composition of the present invention contains an antioxidant, it is also recommended that the composition further contain one or more photoinitiators. By irradiating such a composition with light at a desired time, the initiation of the reaction between the thermoplastic resin (a) and oxygen is promoted, and as a result, the composition can exhibit an oxygen scavenging function. Becomes

Examples of suitable photoinitiators include, but are not limited to, the following compounds: benzophenone,
o-methoxybenzophenone, acetophenone, o-methoxyacetophenone, acenaphthenequinone, methyl ethyl ketone, valerophenone, hexanophenone, α-
Phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobenzophenone, benzoin, benzoin methyl ether, 4-o-
Morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone, α-tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthone, 3-acetylphenanthrene, 3-acetylindole, 9- Fluorenone, 1-indanone, 1,3,5-
Triacetylbenzene, thioxanthen-9-one, xanthen-9-one, 7-H-benz [de] anthracen-7-one, benzoin tetrahydropyranyl ether, 4,4'-bis- (dimethylamino) -benzophenone, 1'-acetonaphthone, 2'-acetonaphthone, acetonaphthone and 2,3-butanedione, benz [a] anthracene-7,12-dione, 2,2-dimethoxy-2-phenylacetophenone, α, α-diethoxyacetophenone, α , α-dibutoxyacetophenone and the like. Singlet oxygen generating photosensitizers such as rose bengal, methylene blue and tetraphenylporphyrin can also be used as photoinitiators. In addition to the monomer type photoinitiators described above, polymeric initiators can also be used, including poly- (ethylene carbon monoxide) and oligo- [2-hydroxy-2-methyl-
1- [4- (1-methylvinyl) -phenyl] -propanone] is included. In general, the use of a photoinitiator is preferred because a faster and more efficient initiation effect is obtained.

When a photoinitiator is included, exposure to radiation accelerates the initiation of the reaction between the thermoplastic resin (a) and oxygen. The amount of photoinitiator used will vary depending on various factors. The amount of the photoinitiator is appropriately determined according to the type of the thermoplastic resin (a) generally used, the wavelength and intensity of the radiation used, the nature and amount of the antioxidant used, and the type of the photoinitiator used. It is determined. The amount of the photoinitiator also depends on the form in which the oxygen-absorbing resin composition is used. For example, a molded article made of a composition containing a photoinitiator is a slightly opaque layered body, and when irradiated with radiation, a relatively large amount of initiator is required.

In general, when a photoinitiator is used, its amount is preferably in the range of 0.01 to 10% by weight of the whole composition.

The oxygen absorbing composition of the present invention containing the photoinitiator is exposed to radiation at the desired time, thereby initiating oxygen scavenging of the composition. Exposure to radiation significantly reduces or eliminates the induction period of oxygen scavenging of the oxygen absorbing composition, initiates oxygen scavenging,
Alternatively, oxygen scavenging can be promoted. The induction period is a time period until the oxygen-absorbing composition sufficiently starts capturing oxygen.

The radiation used is, for example, actinic radiation, for example, about 200 to 750 nm (n
m), ultraviolet or visible light having a wavelength of preferably about 200 to 400 nm is useful. Since actinic radiation has a relatively long wavelength, it is preferable from the viewpoints of cost, effects on the human body, and the like. In the case of exposure by radiation, it is preferable to expose the oxygen-absorbing composition to at least 0.1 joule per gram of the thermoplastic resin (a) contained in the composition. Typical amounts of exposure range from 10 to 100 Joules per gram of thermoplastic resin (a). The radiation may also be an electron beam at a dose of about 0.2 to 20 megarads, preferably about 1 to 10 megarads. Other radiation sources include ionizing radiation, such as gamma rays, x-rays, and corona discharges. Radiation exposure is preferably performed in the presence of oxygen. The duration of the exposure will vary depending on various factors. Factors include the amount and type of photoinitiator present, the shape of the article to be exposed (eg, layer thickness), the amount of any antioxidants present, and the wavelength and intensity of the radiation source. Including, but not limited to.

The exposure of the oxygen-absorbing resin composition of the present invention containing the above-mentioned photoinitiator to radiation may be in the course of the preparation, even after the composition has been prepared into a desired molded article or article. You may. For example, if the composition of the present invention is used for packaging oxygen-sensitive products, the exposure to radiation may be immediately before, during, or after packaging. However, the radiation exposure needs to be prior to the use of the molded article or article as an oxygen scavenger. For maximally uniform irradiation, the exposure should take place during a processing step in which the molded article or article is, for example, in the form of a flat sheet.

The oxygen-absorbing resin composition of the present invention has various excellent properties. For example, the oxygen-absorbing resin of the present invention preferably has an oxygen absorption rate of 0.01 ml / m 2.
^{It is 2} · day or more. Oxygen absorption rate is 0.05ml /
m ² · day or more, more preferably 0.1 m
More preferably, it is 1 / m ² · day or more. When the oxygen absorption rate is less than 0.01 ml / m ² · day, the molded article such as a multilayer container molded using the resin composition of the present invention does not have sufficient oxygen barrier properties and has an oxygen scavenging effect. Is often not enough.

The oxygen absorption rate is the volume of oxygen absorbed by the film per unit surface area per unit time when a film of the resin composition is left in a constant volume of air. A specific measuring method will be described in Examples described later.

When the resin composition or the resin of the present invention is used as an oxygen scavenger (particularly when no gas barrier resin is contained), the useful scavenging rate (oxygen absorption rate) is as follows:
20 ° C., under 1 atm, per day in air, carbon - a thermoplastic resin having a carbon-carbon double bond (a) layer 1 m ² per 0.
Preferably, it absorbs 5 ml of oxygen, more preferably 5 ml or more.

The oxygen scavenging capacity of the resin composition or resin of the present invention is preferably 1 ml or more per gram. More preferably, the oxygen scavenging capacity is 10 ml or more per gram, more preferably 50 ml or more per gram.

Suitable melt flow rate (MFR) (21) for the oxygen-absorbing resin composition or resin of the present invention
0 ° C., under a load of 2160 g, based on JIS K7210) is 0.1 to 100 g / 10 min, more preferably 0.5 to 100 g / 10 min.
５０50 g / 10 min, more preferably 1-30 g / 10 min. When the melt flow rate of the resin composition of the present invention is out of the range of 0.1 to 100 g / 10 minutes, workability at the time of performing melt molding often deteriorates.

The oxygen-absorbing resin composition or resin of the present invention is formed into various molded products according to the purpose.

The method of mixing and molding each component of the resin composition of the present invention is not particularly limited. The order of mixing the components is not particularly limited. For example, thermoplastic resin (a),
When a molded article is prepared by blending the deodorant (b) and the transition metal salt (c), these components may be mixed simultaneously, or the thermoplastic resin (a) and the deodorant (b) After preparing the blend, the transition metal salt (c) may be mixed.
Alternatively, when a molded article is prepared by blending a thermoplastic resin (a), a deodorant (b), a transition metal salt (c) and a gas barrier resin (d), these components may be mixed simultaneously. Then, after producing a blend of the thermoplastic resin (a) and the deodorant (b), the mixture is mixed with the gas barrier resin (d),
Further, a transition metal salt (c) may be mixed.

Each of the components of the composition may be melt-blended and formed into pellets and then subjected to molding, or may be dry-blended and directly subjected to molding.

As means for blending and kneading the above components, a method of dissolving each resin component using a solvent, mixing and evaporating the solvent, and melting and mixing at a temperature in the range of 50 ° C. to 300 ° C. Smelting method (melt blending method). The melt compounding method is preferred from the viewpoint of the simplicity of the process and the cost, but is not particularly limited. Examples of the means used for melt blending include a ribbon blender, a high-speed mixer, a co-kneader, a mixing roll, an extruder, a Banbury mixer, an intensive mixer and the like.

For example, each component of the composition of the present invention is kneaded with a Banbury mixer, a single-screw or twin-screw extruder, pelletized, and then subjected to melt molding. In order to prevent oxidation of the thermoplastic resin (a) from proceeding during the blending operation, it is desirable to seal the hopper port with nitrogen and extrude at a low temperature. Further, it is preferable to use an extruder having a high degree of kneading and to disperse each component finely and uniformly, in order to improve oxygen absorption performance and transparency and to prevent generation and mixing of gels and butter.

The kneading operation is important so that each component in the resin composition can be well dispersed. As a kneader for obtaining a composition having a high degree of dispersion, a continuous kneader such as a continuous intensive mixer or a kneading type twin screw extruder (in the same direction or a different direction) is most suitable. And a batch-type kneader such as an intensive mixer or a pressure kneader. As another continuous kneading device, a device using a rotating disk having a grinding mechanism such as a stone mill, for example, a KCK manufactured by KCK Co., Ltd.
A CK kneading extruder can also be used. Among those usually used as a kneader, a single-screw extruder provided with a kneading section (Dalmage, CTM, etc.) or a simple kneader such as a Brabender mixer can be mentioned.

Among them, the most preferred one for the purpose of the present invention is a continuous intensive mixer. As a commercially available model, Farrel
FCM, Japan Steel Works CIM or Co., Ltd.
There are Kobe Steel's KCM, LCM and ACM.
In practice, it is preferable to employ a device that has a single screw extruder below these kneaders and that simultaneously performs kneading and extrusion pelletization. Also, a twin-screw kneading extruder having a kneading disk or a kneading rotor, for example, TEX, Werner & Pfleiderer manufactured by Japan Steel Works, Ltd.
ZSK manufactured by Toshiba Machine Co., Ltd., PCM manufactured by Ikegai Iron Works Co., Ltd., etc. are also used for the purpose of kneading in the present invention.

In using these continuous kneaders, the shapes of the rotor and the disk play an important role.
In particular, the gap (chip clearance) between the mixing chamber and the rotor chip or disk chip is important.
If the composition is too narrow or too wide, a composition having good dispersibility cannot be obtained. The optimum chip clearance is 1 to 5 mm.

The rotation speed of the rotor of the kneader is 100 to 12
A range of 00 rpm, preferably 150 to 1000 rpm, and more preferably 200 to 800 rpm is employed. The inner diameter (D) of the kneader chamber is 30 mm or more, preferably 50 to 400 mm. The ratio L / D to the chamber length (L) of the kneader is preferably 4 to 30. Also, one kneader may be used, or two or more kneaders may be used in combination.

The longer the kneading time, the better the result. However, the kneading time is in the range of 10 to 600 seconds, preferably 15 to 200 seconds, from the viewpoint of preventing oxidation of the thermoplastic resin (a) or economical efficiency. Is 15 to 150 seconds.

The resin composition of the present invention is formed into various molded products, for example, films, sheets, containers and other packaging materials, oxygen absorbers of various shapes, etc. by appropriately employing the various molding methods described above. be able to.

For example, it can be formed into a film, sheet, pipe or the like by melt extrusion molding, into a container shape by injection molding, or into a bottle-like hollow container by hollow molding. Preferable examples of the hollow molding include extrusion hollow molding, in which a parison is formed by extrusion molding, and blow molding of the parison, and injection hollow molding, in which a preform is formed by injection molding and blown and molded. Although illustrated as an aspect, it is not limited to these.

The oxygen-absorbing resin composition of the present invention is suitably used as various packaging materials and containers as described above. It is also useful as an agent. The oxygen scavenger is obtained by molding the oxygen-absorbing resin composition or the resin of the present invention into an arbitrary shape.For example, by putting this into a packaging container filled with food, medicine, or the like, the packaging container can be effectively packed. Can scavenge the oxygen inside. When direct contact between the resin composition of the present invention and the content is not preferable, it is preferable to fill a molded article made of the resin composition of the present invention into a packaging material that blocks the content but allows gas to pass therethrough. . For example, if the contents are solid having a sufficient average particle size, an embodiment in which a molded article made of the resin composition of the present invention is filled in a packaging material made of a nonwoven fabric or the like is also suitable.

The shape of the oxygen scavenger is not particularly limited, but it is effective to increase the surface area per unit volume in order to efficiently exhibit the oxygen scavenging function. It is suitable.

In general, it is also preferable to coat the outer surfaces of various molded products obtained for the above-mentioned purposes with a thermoplastic resin other than the resin composition or resin of the present invention. For example,
In the case of a container for containing the content, in addition to suppressing the direct contact between the oxygen-absorbing resin composition and the content, the type and thickness of the covering thermoplastic resin controls the rate of entry of oxygen from the outside, and the present invention The rate at which the resin composition reacts with oxygen can be adjusted. By adjusting the oxygen absorption rate of the resin composition of the present invention by the method described above, it is possible to maintain the oxygen scavenging function of the resin composition of the present invention for a long period of time.

The method of coating the outer surface of the molded article made of the resin composition of the present invention with another thermoplastic resin or the like is not particularly limited. A method of laminating a thermoplastic resin or the like on at least one side of a layer composed of the resin composition of the present invention to form a multilayer body, or a multilayer structure having the resin composition of the present invention as an inner layer and another thermoplastic resin as an outermost layer Preferred embodiments include polymer particles.

In the present invention, the molded product obtained by the above-mentioned molding, for example, a film or a sheet may be a single layer, but may be a layer composed of other various resins, metals, papers, woven fabrics or non-woven fabrics. It is more preferable to use it as a laminate from the viewpoint that many functions can be imparted. When the resin composition of the present invention is used in a single layer, the duration of the oxygen scavenging function may be shortened due to the large area in contact with oxygen, and the mechanical strength may be further reduced after oxygen scavenging. . In addition, the oxygen barrier properties may be reduced due to moisture in the contents or outside air. To compensate for this, it is preferable to stack a layer made of the gas barrier resin (d) or to stack a layer having high mechanical strength.

In the present invention, by covering the outside of the oxygen-absorbing resin composition layer with another resin layer, the rate of entry of oxygen from the outside can be suppressed, and the oxygen scavenging function of the resin composition can be reduced. From the viewpoint that the structure can be maintained for a long time, a multilayer structure is preferable. The present invention also includes a multilayer structure or a multilayer container having a layer containing the oxygen-absorbing resin composition or the oxygen-absorbing resin.

[0152] Among the containers having a multilayer structure, an embodiment in which the innermost layer of the container is formed of the resin composition of the present invention is preferable from the viewpoint that the oxygen scavenging function in the container is promptly exhibited.

As a specific layer structure of the multilayer structure, a layer composed of a resin other than the thermoplastic resin (a), metal, paper, woven fabric or nonwoven fabric, etc. is a layer A, and a layer composed of the resin composition of the present invention. Is B layer and the adhesive resin layer is C layer, A / B, A
/ B / A, A / C / B, A / C / B / C / A, A / B /
Layer configurations such as A / B / A and A / C / B / C / A / C / B / C / A are exemplified, but it is absolutely not necessary to add other layers to these as appropriate. However, the present invention is not limited to this example. When a plurality of layers made of another resin are provided, they may be of different types or the same. Further, a layer using a collected resin made of scrap such as trim generated at the time of molding may be separately provided, or the collected resin may be blended with a layer made of another resin. Although there is no particular limitation on the thickness configuration of the multilayer structure, the thickness ratio of the B layer to the total layer thickness is preferably 2 to 20% in consideration of moldability, cost, and the like.

As a material for forming a resin layer to be laminated on a molded article of the oxygen-absorbing resin composition of the present invention, a thermoplastic resin is preferable from the viewpoint of processability and the like. Such thermoplastic resins include, but are not limited to, the following resins: ethylene homopolymers and ethylene copolymers (copolymers of ethylene and the following monomers:
Propylene, 1-butene, isobutene, 4-methyl-1
Α-olefins such as pentene, 1-hexene, 1-octene; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof; Vinyl anhydrides such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate, and vinyl aradoquinate; vinyl trimethoxy silane Vinylsilane-based compounds; unsaturated sulfonic acids or salts thereof; alkylthiols; vinylpyrrolidones, etc.), propylene homopolymers and propylene copolymers (copolymers of propylene with the following monomers: ethylene, 1-butene, isobutene, 4- Methyl-1-pentene 1-hexene, alpha-olefins such as 1-octene; itaconic acid, methacrylic acid, acrylic acid, unsaturated carboxylic acids such as maleic acid, its salts,
Its partial or complete esters, its nitriles, its amides, its anhydrides; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate,
Carboxylic acid vinyl esters such as vinyl dodecanoate, vinyl stearate, and vinyl arachidonate; vinyl silane compounds such as vinyl trimethoxy silane; unsaturated sulfonic acids or salts thereof; alkyl thiols; -Methylpentene-
1, polyolefins such as polybutene-1; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyamides such as poly ε-caprolactam, polyhexamethylene adipamide, and polymethaxylylene adipamide; polyvinylidene chloride, poly Vinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylate, etc. The layer laminated by such a thermoplastic resin may be unstretched or may be uniaxially or biaxially stretched or rolled.

Of these thermoplastic resins, polyolefins are preferred because they are excellent in moisture resistance, mechanical properties, economy, heat sealability and the like. Further, since the polyester has good transparency and excellent mechanical properties, the usefulness of laminating with the resin composition of the present invention having good transparency is great.

Examples of the material for forming the metal layer to be laminated with the resin composition of the present invention include steel and aluminum generally used for cans and the like.

In the present invention, an adhesive resin can be used for bonding the resin composition layer of the present invention to another resin layer. The adhesive resin is not particularly limited as long as it can bond the respective layers, but it may be a polyurethane-based or polyester-based one-part or two-part curable adhesive, an unsaturated carboxylic acid or its anhydride (maleic anhydride). An acid or the like) is preferably copolymerized or graft-modified with an olefin-based polymer or copolymer (carboxylic acid-modified polyolefin resin).

Among these, it is more preferable that the adhesive resin is a carboxylic acid-modified polyolefin resin from the viewpoint of the adhesion between the surface layer of polyolefin and the resin composition layer. Examples of such carboxylic acid-modified polyolefin resins include polyethylene @ low density polyethylene (LDPE) and linear low density polyethylene (LLDP).
E), very low density polyethylene (VLDPE)｝, polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate (methyl ester or ethyl ester) copolymer, etc. What was done.

When the molded article of the present invention is a multilayer product, the oxygen scavenging layer is a layer such as an “oxygen barrier material”, that is, the oxygen permeation rate is 200 cm ³ / m ² · d per atmosphere at 20 ° C.
It may be laminated with a layer made of ay or less, but is not necessarily limited to this. Typical oxygen barrier materials include poly (ethylene vinyl alcohol), polyacrylonitrile, polyvinyl chloride, poly (vinylidene dichloride), polyethylene terephthalate, silica, and polyamide. Copolymers containing one of the above monomers and metal foil layers can also be used.

The other layers may include one or more oxygen permeable layers. Particularly, as an example of a flexible packaging film for food, (i) an oxygen barrier layer, (i)
i) a layer containing the oxygen-absorbing resin composition of the present invention, and optionally (iii) a laminated packaging film containing an oxygen-permeable layer. This film is used for packaging with the layer (i) outside and the layer (iii) inside.
The oxygen barrier layer of (i) limits the invasion of oxygen from the outside into the layer of (ii), thereby increasing the time available for scavenging oxygen in the layer (ii). The oxygen-permeable layer of layer (iii) regulates the rate of permeation of oxygen inside, thereby increasing the time available for scavenging oxygen in layer (ii). This also helps extend the life of the oxygen scavenging material when handling the film before packaging. In addition, layer (iii) can block the transfer of thermoplastic resin (a), transition metal salt (c), other additives or by-products of scavenging into the package.
Further, layer (iii) can increase heat sealability, transparency and / or resistance to adhesion of the multilayer film.

Examples of the method for obtaining the multilayer structure include an extrusion lamination method, a dry lamination method, a solvent casting method, a co-injection molding method, and a co-extrusion molding method, but are not particularly limited. Coextrusion molding methods include coextrusion lamination, coextrusion sheet molding, coextrusion inflation molding,
Coextrusion blow molding and the like can be mentioned.

The sheet, film, parison, etc. of the multilayer structure thus obtained is reheated at a temperature not higher than the melting point of the contained resin, and is subjected to thermoforming methods such as drawing, roll stretching, pantograph stretching. A molded product stretched by uniaxial or biaxial stretching by the inflation stretching method, the blow molding method, or the like can also be obtained.

The transparency of the resin composition of the present invention is improved by appropriately selecting the type of the thermoplastic resin (a), the gas barrier resin (d), etc. contained therein in consideration of the refractive index. Therefore, by selecting a resin having excellent transparency as another resin to be laminated, a packaging container in which the contents are easily visible can be obtained. When it is desired to obtain a multilayer structure having excellent transparency, the internal haze is preferably 10% or less, more preferably 5%.
Hereinafter, it is more preferably set to 3% or less.

The oxygen-absorbing resin or the oxygen-absorbing resin composition of the present invention can be used as an oxygen absorbent in any shape. Also, molded articles such as containers using these, particularly multilayer structures, are used for various applications. Among them, the superiority of using the resin composition of the present invention, which is excellent in oxygen scavenging property and also excellent in oxygen barrier property, is greatly exhibited when used as various packaging containers. In particular, it is suitable as a packaging container for foods, pharmaceuticals, agricultural chemicals, etc., whose quality is likely to deteriorate due to the presence of oxygen. Further, the resin composition of the present invention is suitable for use as a packing (gasket) for a container, particularly as a gasket for a cap of a container. A cap provided with such a gasket has excellent gas barrier properties and oxygen scavenging properties.

Further, since the resin composition of the present invention can have good transparency by appropriately selecting a resin, it is also suitable for use as a packaging container in which the contents are easily visible. Among such packaging containers, the performance required for transparency is strict, and the use of the resin composition of the present invention is highly useful.
There are various embodiments.

That is, one is a container including a layer made of the oxygen-absorbing resin composition or the oxygen-absorbing resin of the present invention and having a total thickness of 300 μm or less, and the other is a container made of a multilayer film. It is a multilayer container comprising a layer made of the oxygen-absorbing resin composition or the oxygen-absorbing resin of the invention and a thermoplastic polyester layer. Hereinafter, these embodiments will be sequentially described.

Including a layer comprising the resin composition of the present invention,
A container made of a multilayer film having a total layer thickness of 300 μm or less is a flexible container made of a multilayer structure having a relatively small total layer thickness, and is usually processed into a form such as a pouch.

In general, as a container requiring good transparency, a container having a small overall thickness, in which the thickness of each resin layer constituting the multilayer structure is small, is manufactured. For example, when using a crystalline resin such as polyolefin, if the thickness is large, transparency often deteriorates due to scattering by crystals, whereas if the container is thin, good transparency is obtained. Property is obtained. In general, even if a resin that is crystallized without stretching has poor transparency, a resin that is crystallized by stretching orientation has good transparency. Such a uniaxially or biaxially stretched film is usually thin, and from this point of view, a thin multilayer structure often provides good transparency.

The transparency of the resin composition of the present invention becomes very good by selecting an appropriate resin. Therefore, it can be suitably used for a container made of a thin multilayer film, which often requires transparency. Such a thin film is relatively excellent in transparency even if the transparency deteriorates with time.

Although the thickness of the multilayer film is not particularly limited, it is preferably 300 μm or less, because good transparency can be easily maintained. More preferably 25
0 μm or less, and more preferably 200 μm or less. On the other hand, the lower limit of the thickness is not particularly limited, but considering the mechanical strength of the container, 10 μm
It is preferably at least 20 μm, more preferably at least 30 μm.

Although the layer constitution is not particularly limited,
A multilayer film can be obtained by multilayering the resin composition layer of the present invention and another thermoplastic resin layer by a method such as dry lamination or coextrusion lamination.

For dry lamination, non-stretched films, uniaxially stretched films, biaxially stretched films, and rolled films can be used. Among these, a biaxially oriented polypropylene film, a biaxially oriented polyethylene terephthalate film, and a biaxially oriented poly ε-caprolactam film are preferred from the viewpoints of strength, transparency and the like. Biaxially oriented polypropylene films are particularly preferred because of their good moisture resistance.

In order to seal the packaging container, it is preferable to provide a layer made of a heat-sealable resin on at least one outermost surface of the multilayer film constituting the packaging container. Examples of such a resin include polyolefins such as polyethylene and polypropylene.

After lamination, the multilayer film is reheated and stretched by uniaxial or biaxial stretching by a thermoforming method such as drawing, a roll stretching method, a pantograph stretching method, or an inflation stretching method. You can also get.

The multilayer film thus obtained is processed into a bag shape, and the contents can be filled into a packaging container. Since it is flexible and simple, and is excellent in transparency, gas barrier properties and oxygen scavenging properties, it is extremely useful for packaging of contents that are easily degraded by the presence of oxygen, especially foods and the like.

The multilayer container comprising the layer composed of the resin composition of the present invention and the thermoplastic polyester layer provides good transparency by appropriately selecting the resin, and is excellent in gas barrier properties and oxygen scavenging properties.

In general, a polyester resin has good transparency, and a multilayer structure having good transparency can be obtained by laminating the polyester resin with the resin composition of the present invention.

The form of the multilayer container comprising the layer comprising the resin composition of the present invention and the thermoplastic polyester layer is not particularly limited, and examples thereof include a bag-like container, a cup-like container and a hollow molded container. What is important is the hollow molded container. The method for producing the hollow molded container is not particularly limited, and examples thereof include blow molding and injection molding. Practically, blow molding is important, and in particular, a bottle-shaped container is important.

[0179] Blow-molded bottles made of thermoplastic polyester resin are now widely used as beverage containers. In such applications, it is necessary to prevent deterioration of the contents, and it is required that the beverage as the contents be sufficiently visible to consumers. In addition, when packaging contents such as beer that is extremely susceptible to flavor deterioration due to oxygen, it is desired to have extremely high gas barrier properties and oxygen scavenging performance. Is not easy.

The multilayer blow bottle composed of the layer composed of the resin composition of the present invention and the thermoplastic polyester layer is extremely excellent in the ability to maintain the quality of the contents while maintaining transparency. is there.

The polyester resin used in the multilayer container of the present invention comprising a layer made of the oxygen-absorbing resin composition or the oxygen-absorbing resin and a thermoplastic polyester layer mainly contains an aromatic dicarboxylic acid or an alkyl ester thereof and a diol. A condensation polymer as a component is used.
In particular, to achieve the object of the present invention, a polyester resin containing an ethylene terephthalate component as a main component is preferable.
In the polyester resin used in the present invention, the total ratio (mol%) of terephthalic acid units and ethylene glycol units is generally 70 mol% or more with respect to the total mol number of all structural units constituting the polyester. Is more preferable, and it is more preferable that it is 90 mol% or more. If the total proportion of terephthalic acid units and ethylene glycol units in the polyester is less than 70 mol%, the resulting polyester will be non-crystalline, so that when it is heated and filled (hot-filled) in a stretching container, the shrinkage is large and the heat resistance is poor. In addition, the strength also decreases. Furthermore, during solid phase polymerization performed to reduce the amount of oligomers contained in the resin, sticking due to softening of the resin is likely to occur, and production becomes difficult.

If necessary, the polyester resin may contain two units other than the terephthalic acid unit and the ethylene glycol unit.
The functional compound unit can be contained within a range that does not significantly impair workability, strength, heat resistance and the like. The ratio (mol%) is preferably 30 mol% or less, more preferably 20 mol% or less, and more preferably 10 mol% or less, based on the total mol number of all the structural units constituting the polyester. More preferably, there is.

The preferred bifunctional compound unit which can be contained is at least one unit selected from a dicarboxylic acid unit, a diol unit and a hydroxycarboxylic acid unit.
Species of bifunctional compound units. These are aliphatic 2
Any of a functional compound unit, an alicyclic bifunctional compound unit, and an aromatic bifunctional compound unit may be used.

From the viewpoint of moldability and transparency, it is sometimes preferred that the thermoplastic polyester has an ethylene terephthalate component as a main component and has a melting point of 240 to 250 ° C.

When the melting point exceeds 250 ° C., the crystallization rate of the polyester resin is high, so that crystallization due to heating tends to proceed during injection molding or blow molding, resulting in whitening of the resulting bottle. And transparency may be impaired. In addition, the draw orientation may decrease and the shapeability may deteriorate. Therefore, the range of manufacturing conditions that can obtain good products is narrowed,
The reject rate is likely to increase. The melting point is more preferably 248
It is below ° C.

On the other hand, when the melting point is lower than 240 ° C., the heat resistance of the multilayer container decreases. Further, since the crystallinity of the polyester resin is also reduced more than necessary, the stretch orientation is reduced and the strength is also reduced. Furthermore, the solid-state polymerization temperature must be lowered due to the lowering of the melting point, which causes a problem of a decrease in productivity due to a decrease in the reaction rate. The melting point is more preferably 24
2 ° C. or higher, and optimally 244 ° C. or higher.

To obtain a polyester resin having such a melting point, an appropriate amount of a copolymer component may be copolymerized with a polyester resin containing an ethylene terephthalate component as a main component. Specifically, it is preferable to contain 1 to 6 mol% of the copolymer component based on the total number of moles of all the structural units constituting the polyester. More preferably, it is 1.5 to 5 mol%, and most preferably 2 to 4 mol%.

A resin having a copolymerization amount in the above range can be obtained by adding a comonomer to a polyethylene terephthalate production system in consideration of the copolymerization amount of diethylene glycol by-produced during the production. The comonomer is not particularly limited, and various monomers mentioned as the above-mentioned bifunctional compound unit can be used. Among them, neopentyl glycol, cyclohexanedimethanol, cyclohexanedicarboxylic acid , Isophthalic acid and naphthalenedicarboxylic acid are preferred.

In particular, isophthalic acid is excellent in moldability of the obtained resin because the production conditions under which a good product can be obtained are wide when the obtained copolymerized polyester is used.
As a result, there is an advantage that the reject rate is low. Further, it is preferable from the viewpoint that whitening of a molded article due to suppression of the crystallization rate can be prevented.

The 1,4-cyclohexanedimethanol unit or 1,4-cyclohexanedicarboxylic acid is preferable also from the viewpoint that the molded article obtained therefrom has excellent drop strength.

Further, naphthalenedicarboxylic acid is preferable in that the resulting polyester has a high glass transition temperature, and as a result, the heat resistance of the finally obtained container is improved. Further, a polyester containing naphthalenedicarboxylic acid as a copolymer component is capable of absorbing ultraviolet rays, and is particularly useful when the contents are easily deteriorated by ultraviolet rays. For example, it is useful when the content is easily degraded by oxidation or ultraviolet light, such as beer.

In a co-injection stretch blow-molded container, when the purpose is to protect the contents from ultraviolet rays, the thermoplastic polyester contains 2,6-naphthalenedicarboxylic acid component in an amount of 0.5 to the total dicarboxylic acid component. ~ 15 mol%
Is preferably contained in the range, more preferably in the range of 1.0 to 10 mol%.

When a polycondensation catalyst is used in the production of the polyester resin, those usually used in the production of polyesters can be used. For example, antimony compounds such as antimony trioxide; germanium dioxide, germanium tetraethoxy And germanium compounds such as germanium tetra-n-butoxide; titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium; di-n-butyltin dilaurate, di- Examples thereof include tin compounds such as n-butyltin oxide and dibutyltin diacetate. These catalyst compounds may be used alone or in combination of two or more. Among these polymerization catalysts, a germanium compound is preferable from the viewpoint that the obtained polyester has good color tone, and an antimony compound is preferable from the viewpoint of catalyst cost. As the germanium compound, germanium dioxide is particularly preferable, and as the antimony compound, antimony trioxide is particularly preferable.
The polycondensation catalyst is used in an amount of 0.1 to 100 parts by weight of dicarboxylic acid.
Preferably, 002 to 0.8 parts by weight are added.

From the viewpoint of moldability, it is preferable to use a germanium compound rather than an antimony compound. That is, since the crystallization rate of a polyester polymerized using an antimony compound is generally faster than that of a polyester polymerized using a germanium compound, crystallization by heating easily proceeds during injection molding or blow molding, and the resultant is obtained. Whitening tends to occur in the bottle, and transparency is impaired. In addition, the draw orientation may decrease and the shapeability may deteriorate. Therefore, the range of manufacturing conditions under which a good product can be obtained is narrowed, and the defective product ratio is likely to increase.

Therefore, when polyethylene terephthalate containing no copolymerization component other than diethylene glycol as a by-product is used, the crystallization rate is higher than when polyethylene terephthalate modified in small amounts with other copolymerization components is used. Particularly, selection of a catalyst is important, and it is preferable to use a germanium compound.

The method for producing the polyester resin used for the thermoplastic polyester layer of the multilayer blow bottle of the present invention is not particularly limited. It is prepared by a usual method using the diol, dicarboxylic acid, polymerization catalyst and the like.

The production of a bottle-shaped container among the multilayer containers having the thermoplastic polyester layer will be described.

The method for producing such a container is not particularly limited, but it is preferable to use a co-injection blow molding method from the viewpoint of productivity and the like. In the co-injection blow molding method, a container precursor (parison) having a multilayer structure is usually subjected to a single mold clamping operation in a single mold using a molding machine having two injection cylinders, and the molten polyester resin (parison) is melted. PES) and the oxygen-absorbing resin composition of the present invention can be obtained by injecting alternately at different timings from the respective injection cylinders, simultaneously injecting into a concentric nozzle, or by using both together. For example, (1) PES for the inner and outer layers is first injected, and then the resin composition to be the intermediate layer is injected simultaneously with the inner and outer layers to obtain PES / resin composition / P
A method of making a three-layer container of ES; or (2) first injecting the PES for the inner and outer layers, then injecting the resin composition simultaneously with the inner and outer layers, and simultaneously or subsequently, the PES as the central layer At the same time as the above layers, and P
The inner layer is obtained by a general method of a bottomed parison completely enclosed in a PES layer, such as a method of producing a container having a five-layer structure of ES / resin composition / PES / resin composition / PES. It is not limited. In the above-mentioned layer structure, an adhesive resin layer may be provided between the PES layer and the resin composition layer, if necessary.

Conditions for injection molding of a bottomed parison are as follows:
PES is preferably injected in a temperature range of 250 ° C. to 330 ° C., more preferably in a temperature range of 270 ° C. to 320 ° C., and more preferably in a temperature range of 280 ° C. to 310 ° C. preferable. PES injection temperature is 2
If the temperature is lower than 50 ° C., the unmelted material (fish eye) is mixed into the molded product due to insufficient melting of the PES pellet, resulting in poor appearance. In addition, the strength of the molded article is thereby reduced. Further, in extreme cases, the screw torque increases and causes a failure of the molding machine. On the other hand, if the injection temperature of PES exceeds 330 ° C., the decomposition of PES becomes remarkable, and the strength of the molded article is reduced due to the reduction in molecular weight. In addition, not only the properties of the substance to be filled into the molded article are impaired by the gas such as acetaldehyde generated during the decomposition, but also the oligomer generated during the decomposition causes severe contamination of the mold and impairs the appearance of the molded article.

The oxygen-absorbing resin composition has a temperature of 170 to 250 ° C.
The temperature is preferably within the range of 180 to 240.
More preferably, the injection is performed within a temperature range of 190 ° C.
More preferably, injection is performed within a temperature range of 230 ° C.

When the injection temperature of the resin composition is lower than 170 ° C., the resin composition pellets are not sufficiently melted, so that an unmelted material (fish eye) is mixed into the molded product, resulting in poor appearance. Further, in extreme cases, the screw torque increases and causes a failure of the molding machine. On the other hand, when the injection temperature of the resin composition exceeds 250 ° C., the oxidation of the thermoplastic resin (a) progresses, and the oxygen absorbing capacity of the resin composition decreases, causing a decrease in gas barrier properties and oxygen scavenging properties. Cheap. At the same time, the appearance of the molded article may be poor due to coloring or gelling, or the fluidity may be non-uniform or impaired due to decomposed gas or gelling, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to the generation of a gel. In order to suppress the progress of oxidation during melting, it is also preferable to seal the raw material supply hopper with nitrogen.

The temperature of the hot runner portion into which PES and the resin composition flow is preferably in the range of 220 ° C. to 300 ° C., more preferably in the range of 240 ° C. to 280 ° C., and more preferably in the range of 250 ° C. More preferably, the injection is performed within the range of -270 ° C.

When the temperature of the hot runner portion is lower than 220 ° C., crystallization of PES occurs, and the PES is solidified in the hot runner portion, which makes molding difficult.
On the other hand, when the temperature of the hot runner portion exceeds 300 ° C., the oxidation of the thermoplastic resin (a) proceeds, the oxygen absorbing ability of the resin composition decreases, and the gas barrier property and the oxygen scavenging property are likely to decrease. . At the same time, the appearance of the molded article may be poor due to coloring or gelling, or the fluidity may be non-uniform due to the decomposition gas or gelling, or the fluidity may be impaired, resulting in a missing portion of the resin composition layer. In an extreme case, injection molding becomes impossible due to the generation of a gel.

In order to obtain good resistance to delamination (resistance to delamination) and transparency of a multilayer container obtained by stretch-blowing the bottomed parison, the PES of the parison and the gas barrier resin at the time of the injection molding are required. It is important to suppress the crystallization of (d) as much as possible. Thereby, uniform stretchability can be obtained, and a molded article excellent in delamination resistance, transparency, and shape can be obtained. In order to suppress the crystallization of the parison PES and the gas barrier resin (d), it is preferable to set the mold temperature within the range of 0 ° C. to 70 ° C.
C. to 50.degree. C., more preferably 10 to 3C.
More preferably, it is within the range of 0 ° C. Mold temperature is 0
If the temperature is lower than 0 ° C., the appearance of the parison is impaired due to condensation in the mold, and a good molded product cannot be obtained. If the mold temperature exceeds 70 ° C., the crystallization of the parison PES and the gas barrier resin (d) is promoted, so that uniform stretchability cannot be obtained. The delamination resistance is reduced, and it is difficult to obtain a molded article shaped into an intended shape. Furthermore, crystallization of PES impairs transparency.

As for the thickness of the parison, the total thickness is 2 to 2.
5 mm, the oxygen-absorbing resin composition layer is 10 to 500 in total
It is preferably μm.

The multilayer parison thus obtained is reheated to 75 to 150 ° C. directly at a high temperature or by a heating element such as a block heater or an infrared heater, and then sent to a stretching blow step. A multilayer polyester stretch blow container in which a PES resin layer and an oxygen-absorbing resin composition layer are uniaxially or biaxially stretched after being stretched 1 to 5 times in a longitudinal direction and then blow molded by 1 to 4 times with compressed air or the like. Is obtained.

In this case, if the temperature at the time of heating the multi-layer parison is too high, the polyester tends to crystallize, so that the stretch blow container becomes white and the appearance is impaired. Further, the occurrence of delamination of the stretch blow container is increased, which is not preferable.
On the other hand, if the temperature at the time of heating the multi-layer parison is too low, the polyester is crazed and becomes pearly, so that the transparency is impaired. For this reason, the temperature of the multilayer parison during heating is preferably from 85 to 140 ° C, more preferably from 90 to 130 ° C, and even more preferably from 95 to 120 ° C.

In the present invention, the total thickness of the container body of the blow container is generally 100 to 2000 μm, preferably 15 to 2000 μm.
It is 0 to 1000 μm, and can be properly used depending on the application. At this time, the total thickness of the oxygen-absorbing resin composition layer is 2
２００200 μm, preferably 5-100
More preferably, it is within the range of μm.

In this manner, a multilayer container comprising the thermoplastic resin composition or thermoplastic resin layer of the present invention and the thermoplastic polyester layer is obtained. This container can be prepared to have good transparency, and is extremely excellent in gas barrier properties and oxygen scavenging properties. Therefore, it is useful for packaging of contents that are easily degraded due to the presence of oxygen, for example, foods, pharmaceuticals, and the like. In particular, it is extremely useful as a container for beverages such as beer.

[0210]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited thereto. The analysis and evaluation in the following examples were performed as follows.

(1) Styrene content of thermoplastic resin (a), content of structural unit represented by structural formula (I) (vinyl bond content) and carbon-carbon double bond content: deuterated chloroform as solvent The thermoplastic resin (a) was measured by ¹ H-NMR (nuclear magnetic resonance) spectrum (measured by "JNM-GX-500 type" manufactured by JEOL Ltd.), and the structure of the resin was identified. Thereby, the content was calculated.

Here, the styrene content is the proportion (mol%) of styrene in all the monomers constituting the resin, and is the content of the structural unit represented by the structural formula (I) (vinyl bond content). The term “amount” refers to the ratio (%) of the structural unit represented by the structural formula (I) (that is, the ratio of the units forming a vinyl bond) to all diene monomers in the diene block. The content of the carbon-carbon double bond was determined by calculating the number of moles (eq / g) of the double bond contained in 1 g of the resin.

(2) Melt flow rate: Measured using a melt indexer L244 (manufactured by Takara Kogyo Co., Ltd.). Specifically, a sample resin (resin or resin composition) chip is filled into a cylinder having an inner diameter of 9.55 mm and a length of 162 mm, and is melted at 210 ° C. 2160g, 9.48m in diameter
The load was evenly applied by a plunger of m. The flow rate (g / 10 minutes) of the resin extruded from the orifice having a diameter of 2.1 mm provided at the center of the cylinder was measured, and the measured value was taken as the melt flow rate.

(3) Refractive index of resin: Film extruding was performed at an extrusion temperature of 210 ° C. using the resin to be measured.
An unstretched film having a thickness of 20 μm was obtained. Using the obtained film, an Abbe refractometer (4T manufactured by Atago Co., Ltd.)
The refractive index was measured using a mold, Toshiba Corporation's SL-Na-1 lamp.

(4) Haze value (cloudiness value): A resin or a resin composition to be measured was extruded to obtain a non-stretched film having a thickness of 20 μm. Using the obtained film, AST
According to MD1003-61, a poic integrating sphere type light transmittance / total light reflectance meter (“HR” manufactured by Murakami Color Research Laboratory)
The internal haze value was measured using a “-100 type”). The measurement was similarly performed for the multilayer film. Further, with respect to the multilayered bottle, the internal haze value was measured at each of four locations where the center of the bottle body was divided into four on the circumference, and the average value was taken as the haze value (cloudiness value) of the bottle.

(5) Main dispersion peak temperature of tan δ in the block derived from the resin diene compound: The resin or resin composition to be measured is extruded and has a thickness of 20 μm.
m of unstretched film was obtained. Using the obtained film, RHEOLOGY Co. , LTD “DVE R
HEOSSPECTORER DVE-V4 "
Frequency 11 Hz, displacement amplitude 10 μm, distance between chucks 2
0 mm, width 5 mm, measurement temperature range -150 ° C to 150
The main dispersion peak temperature of tan δ in the block derived from the resin diene compound was measured at a temperature of 3 ° C. and a temperature rising rate of 3 ° C./min.

(6) Ethylene content and degree of saponification of polyvinyl alcohol resin: The ethylene content and degree of saponification of polyvinyl alcohol resin were determined by ¹ H-NMR (nuclear magnetic resonance) using deuterated dimethyl sulfoxide as a solvent. ) Spectrum (JNM-GX-500 manufactured by JEOL Ltd.)
(Type).

(7) Content of each structural unit in polyester: The content of each structural unit in polyester is as follows:
Polyester with deuterated trifluoroacetic acid as solvent
^It was measured by ¹ H-NMR (nuclear magnetic resonance) spectrum (measured by “JNM-GX-500” manufactured by JEOL Ltd.).

(8) Phosphate content in polyvinyl alcohol-based resin: The phosphate content was obtained as a phosphate ion (PO ₄ ^3- ) content according to the following method. 10 g of a dried polyvinyl alcohol-based resin as a sample was added to 0.1 g.
The mixture was poured into 50 ml of a 1N aqueous hydrochloric acid solution and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to obtain a phosphate ion content. The chromatographic column is CI, manufactured by Yokogawa Electric Corporation.
Using S-A23, the eluent was an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium bicarbonate. Note that a calibration curve prepared with a phosphoric acid aqueous solution was used for the quantification.

(9) Content of Na, K, and Mg ions in polyvinyl alcohol resin: 10 g of a dry chip as a sample was put into 50 ml of a 0.01 N hydrochloric acid aqueous solution and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography, and the amounts of Na ions, K ions, and Mg ions were quantified. The chromatography column is ICS-Yokogawa Electric Co., Ltd.
C25 was used and the eluent was 5.0 mM tartaric acid and 1.0 mM
An aqueous solution containing mM 2,6-pyridinedicarboxylic acid was used. In the determination, a calibration curve prepared with an aqueous solution of sodium chloride, potassium chloride and magnesium chloride was used. From the amounts of Na ion, K ion and Mg ion thus obtained, the amounts of alkali metal salt and alkaline earth metal salt in the dried chip were obtained in terms of metal.

(10) Oxygen absorption rate (10-1) Oxygen absorption rate of resin composition (1): Extrusion molding was performed at an extrusion temperature of 210 ° C. using an oxygen-absorbing resin composition to form a film having a thickness of 20 μm. Obtained. The obtained single-layer film 0.01 m ² (0.1 mx 0.1 m; surface area 0.02 m ² ) was precisely weighed and wound into a roll one hour after the film was formed, and the film was heated at 20 ° C and 65% RH. The glass container was filled with air and had a capacity of 260 ml. The air in the glass container contains 21:79 by volume of oxygen and nitrogen. After sealing the mouth of the glass container with an epoxy resin using a multilayer sheet including an aluminum layer,
Left at ℃. After sealing, the air inside was sampled with a syringe over time, and the oxygen concentration of the air was measured using gas chromatography. The pores vacated in the multilayer sheet at the time of measurement were closed each time using an epoxy resin. From the volume ratio of oxygen to nitrogen obtained by gas chromatography, the amount of oxygen absorption of the composition was determined by calculating the amount of decrease in oxygen. From the results, the oxygen absorption rate (ml / m
² · day) was calculated from the slope of the graph. This method was employed in Example 1 and Comparative Examples 1 and 2. (10-2) Oxygen absorption rate of the resin composition (2): The resin composition was extruded at an extrusion temperature of 210 ° C to obtain a film having a thickness of 20 µm. The obtained single-layer film 0.9 m ² (0.2 m × 4.5 m; surface area 1.8 m ² ) was wound into a roll 5 hours after film formation, and was heated at 20 ° C.
375ml internal volume filled with 65% RH air
Into an Erlenmeyer flask. The air in the Erlenmeyer flask contains 21:79 by volume oxygen and nitrogen. The mouth of the Erlenmeyer flask was sealed with an epoxy resin using a multilayer sheet containing an aluminum layer, and then left at 20 ° C. At 96 hours, 168 hours and 336 hours after encapsulation, the air inside was sampled with a syringe, and the oxygen concentration of this air was measured using gas chromatography. The pores vacated in the multilayer sheet at the time of measurement were closed each time using an epoxy resin. The measurement is based on the volume ratio of oxygen and nitrogen obtained by gas chromatography, and the amount of oxygen reduction (oxygen absorption)
Was calculated. 4 days to 14 days later 1
By dividing the amount of oxygen reduction in 0 days by the number of days and the surface area, the oxygen absorption rate of the resin composition (ml / m ² · da)
y) was calculated. This method was employed in Example 2, Comparative Examples 3 and 4.

(11) Intrinsic viscosity of polyester: A film layer of a sample was cut out of the polyester layer of the body of the multilayer container and dissolved in a mixed solvent of an equal weight of phenol and tetrachloroethane. The viscosity of the obtained solution was measured at 30 ° C. using an Ubbelohde viscometer (“HRK-3” manufactured by Hayashi Seisakusho).

(12) Glass transition temperature and melting point of polyester: A sample film layer (sample) was cut out from the polyester layer of the body of the multilayer container, and was subjected to differential thermal analysis (DSC) as follows according to JIS K7121. A measurement was made. Using a differential scanning calorimeter (DSC) model RDC220 / SSC5200H manufactured by Seiko Electronics Co., Ltd., the sample was held at a temperature of 280 ° C. for 5 minutes, and then cooled to a temperature of 30 ° C. at a rate of 100 ° C./min. After holding for 5 minutes, the measurement was carried out at a heating rate of 10 ° C./min.
However, indium and lead were used for temperature calibration. Also,
The glass transition point in the present invention refers to the midpoint glass transition temperature (Tmg) in the JIS, and the melting point in the present invention refers to the melting peak temperature (Tpm) in the JIS.
Say.

(13) Oxygen Permeation Amount of Multilayer Container: In the form of the obtained bottle, the outside of the bottle was kept
0 ° C-65% RH, 20 ° C-100% RH inside the bottle
After adjusting the temperature and humidity, the oxygen permeation amount measurement device (OX-TRAN-10 / 50A manufactured by Modern Control Co., Ltd.)
Oxygen permeation amount per container 10 days after molding (ml /
container / day / atm) was measured.
Thereafter, the outside of the bottle is stored for 3 months in a 20 ° C.-65% RH air atmosphere, and the inside of the bottle is stored for 20 months in a 20 ° C.-100% RH nitrogen atmosphere. Further, the oxygen permeation amount (ml / container. day · atm) was measured.

Example 1 A thermoplastic resin (a) to which an antioxidant was added was prepared by the following method.

In a stirred autoclave purged with dry nitrogen, 600 parts by volume of cyclohexane, N, N,
N ', N'-tetramethylethylenediamine (TMED
A) 0.16 parts by volume, n-BuLi0.0 as initiator
94 parts by volume were charged. After raising the temperature to 50 ° C., 4.25 parts by volume of a styrene monomer was fed and polymerized for 1.5 hours. Next, the temperature was lowered to 30 ° C., and then 120 parts by volume of isoprene was fed to carry out polymerization for 2.5 hours. Then, the temperature was raised again to 50 ° C., and 4.25 parts by volume of the styrene monomer was fed and polymerized for 1.5 hours.

The obtained reaction solution was treated with 2-oxidant as an antioxidant.
tert-butyl-6- (3-tert-butyl-2-
Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and pentaerythritol tetrakis (3-laurylthiopropionate) were added at 0.15 pp based on the total weight of styrene and isoprene, respectively.
hr. The reaction solution was poured into methanol to precipitate a triblock copolymer. This was dried and used as a thermoplastic resin (a) to which an antioxidant was added.

The number average molecular weight of the obtained triblock copolymer was 85,000, the molecular weight of the styrene block in the copolymer was 8,500, and the styrene content was 14 mol.
%, Vinyl bond content in the isoprene block is 55%
And the content of the structural unit represented by the structural formula (I) is 5
5%. The content of carbon-carbon double bonds in the obtained triblock copolymer was 0.014 eq / g, and the melt flow rate was 7.7 g / 10 minutes.
In the resin, 2-tert-butyl-6- (3-t
tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate 0.12% by weight
And 0.12% by weight of pentaerythritol tetrakis (3-laurylthiopropionate).

Thermoplastic resin (a) containing the above antioxidant
The refractive index and the haze value (cloudiness value) of the sample were 1.531 and 1.0%, respectively. Further, when the main dispersion peak temperature of tan δ in a block derived from a diene compound of this resin was measured, it was -3 ° C.
Met.

97 parts by weight of the above thermoplastic resin, 0.8484 parts by weight of cobalt (II) stearate (0.0800 parts by weight as a cobalt atom), and a particle diameter of 3.0 μm
Deodorant (b) (porous microcapsule powder; deodorant capsule "G20007" manufactured by Micron Corporation)
Were dry blended into a 30 mmφ twin screw extruder (TEX-30SS-30CRW-2, Japan Steel Works, Ltd.).
V) at 210 ° C. and a screw rotation speed of 300 rpm
m, and extruded under the conditions of an extruded resin amount of 25 kg / hour, pelletized, and dried under reduced pressure at 30 ° C. for 16 hours to obtain an oxygen-absorbing resin composition. The melt flow rate of this resin composition (210 ° C.-2160 g load) is 6.7 g / 1.
It was 0 minutes.

Using the above resin composition, at an extrusion temperature of 21
Extrusion was performed at 0 ° C. to obtain a film having a thickness of 20 μm. The internal haze of this film was measured.
7%. Further, the oxygen absorption rate of the resin composition (1)
When the oxygen absorption amount of the film was measured by the measuring method described above, the results shown in FIG. 1 were obtained. As a result, the oxygen absorption rate of the resin composition was 69 ml / m ² · day.

On both sides of a film (oxygen-absorbing film) obtained using the above resin composition, a stretched polypropylene film having a thickness of 20 μm (OP- # 2 manufactured by Tocelo Co., Ltd.)
0U-1), and a urethane-based adhesive (manufactured by Toyo Morton, trade name: AD335A, and a curing agent (manufactured by Toyo Morton,
Bonding was performed using a toluene / methyl ethyl ketone mixed solution (trade name: Cat-10) (weight ratio: 1: 1) to prepare a laminated film. The haze of this laminated film was 8.9%.

The above laminated film 0.05 m ² (0.1 m
× 0.5 m; surface area 0.1 m ² )
After an hour, the mixture was wound into a roll and placed in a screw-tube glass bottle having an internal capacity of 260 ml and filled with air at 20 ° C. and 65% RH. The air in the glass bottle has a volume ratio of 21:
Contains 79 oxygen and nitrogen. The mouth of the screw tube glass bottle was sealed with a polyethylene screw cap using a multilayer sheet containing an aluminum layer as an inner lid, and then left at 40 ° C. for 4 hours. After the standing, the screw cap of the screw tube glass bottle was opened as soon as possible so as not to cool the bottle, and when the smell of the film was smelled, a slight odor was felt.

Comparative Example 1 100 parts by weight of the thermoplastic resin used in Example 1 and cobalt (II) stearate
0.8484 parts by weight (0.0800 as cobalt atom)
(Parts by weight) to obtain a resin composition in the same manner as in Example 1. The melt flow rate of this resin composition (210 ° C.
-2160 g load) was 7.1 g / 10 min.

Using the above resin composition, at an extrusion temperature of 21
Extrusion was performed at 0 ° C. to obtain a film having a thickness of 20 μm. When the internal haze of this film was measured, it was found to be 0.
5%. Further, the oxygen absorption rate of the resin composition (1)
When the oxygen absorption amount of the film was measured by the measuring method described above, the results shown in FIG. 1 were obtained. As a result, the oxygen absorption rate of the resin composition was 78 ml / m ² · day.

Using the above resin composition, a laminated film was obtained in the same manner as in Example 1. The haze of this laminated film was 2.0%.

Using the above-mentioned laminated film, a film was placed in a screw-tube glass bottle in the same manner as in Example 1.
After standing at 4 ° C. for 4 hours, the odor of the film was smelled, and a clear odor was felt.

Comparative Example 2 The thermoplastic resin (a) used in Example 1 was extrusion molded at an extrusion temperature of 210 ° C. to obtain a film having a thickness of 20 μm. When the internal haze of this film was measured, it was 0.4%. Also,
According to the method of measuring the oxygen absorption rate (1) of the resin composition (10-1), the oxygen absorption rate of the thermoplastic resin (a) was 0 ml when the oxygen absorption amount of the film was measured.
/ M ² · day.

Using the single-layer film made of the thermoplastic resin (a) produced above, a laminated film was obtained in the same manner as in Example 1. The haze of this laminated film was 1.8%.

Using the above laminated film, a film was placed in a screw-tube glass bottle in the same manner as in Example 1.
After standing at 4 ° C. for 4 hours, when the odor of the film was smelled, a very slight odor was felt.

The results of the above test are shown in Table 1 below.

[0242]

[Table 1]

(Example 2) In the same manner as in Example 1, a thermoplastic resin (a) containing an antioxidant was prepared. EVOH, which is a polyvinyl alcohol-based resin, was used as the gas barrier resin (d). This EVOH had an ethylene content of 44 mol%, a saponification degree of 99.5%, and a melt flow rate (210 ° C.-2160 g load) of 13 g / 10 min. The phosphate content of this EVOH and Na, K, Mg
When the ion content was measured, each was 100 pp.
m, 20 ppm, 60 ppm, and 20 ppm. Further, when the refractive index of this EVOH was measured, it was 1.52
It was 8.

5 parts by weight of the above thermoplastic resin (a), EV
OH 92 parts by weight, cobalt (II) stearate 0.21
Dry blending of 21 parts by weight (0.0200 parts by weight as a cobalt atom) and 3 parts by weight of a deodorant (b) (porous microcapsule powder; deodorant capsule "G20007" manufactured by Micron Co., Ltd.) having a particle diameter of 3.0 μm 30mmφ twin screw extruder (Nippon Steel Works TEX Co., Ltd.)
Using -30SS-30CRW-2V), the mixture was extruded at 210 ° C. under the conditions of a screw rotation speed of 300 rpm and an extruded resin amount of 25 kg / hour, pelletized, and then dried under reduced pressure at 30 ° C. for 16 hours to obtain a resin composition pellet. Obtained. The melt flow rate of this resin composition (210 ° C.-2160
g load) was 10 g / 10 min. Observation of the fracture surface of the resin composition pellets with an electron microscope revealed that the triblock copolymer, which is a thermoplastic resin (a), was roughly 1
Particles of about μm were dispersed in a matrix composed of EVOH.

An extrusion temperature of 2 was obtained using the obtained resin composition.
Film extrusion was performed at 10 ° C. to obtain a film having a thickness of 20 μm. When the internal haze of the obtained single-layer film was measured, it was 7.8%. Next, when the oxygen absorption amount of the film was measured, the result shown in FIG. 2 was obtained. The oxygen absorption rate of the resin composition calculated from the measurement results after 4 days (96 hours) and 14 days (336 hours) was 1.744 ml / m ² · day.

A 20 μm-thick single-layer film 1.0 m ² (0.2 mx 5.0 m; surface area 2.0 m ² ) made of the above resin composition was wound into a roll 5 hours after the film was formed, and was heated at 20 ° C. , 65% RH in a 260 ml screw-cap glass bottle filled with air. The air in the vial contains 21:79 by volume of oxygen and nitrogen. The mouth of the screw tube glass bottle was sealed with a polyethylene screw cap using a multilayer sheet containing an aluminum layer as an inner lid, and then left at 40 ° C. for 4 hours. After the standing, the screw cap of the screw tube glass bottle was opened as soon as possible so as not to cool the bottle, and when the smell of the film was smelled, a slight odor was felt.

A stretched polypropylene film having a thickness of 20 μm (OP- # 20 U-1 manufactured by Tosello Co., Ltd.) was laminated on both sides of the film produced using the above resin composition.
Urethane adhesive (manufactured by Toyo Morton, trade name: AD33)
5A and a curing agent (manufactured by Toyo Morton, trade name: Cat-1)
And a mixed solution of toluene and methyl ethyl ketone (weight ratio of 1: 1) with 0) to form a laminated film. The haze of this laminated film was 9.7%.

Next, co-injection blow molding was performed using the above resin composition and a thermoplastic polyester resin produced by the following method to form a multilayer blow bottle.

As the thermoplastic polyester resin, a resin prepared by using germanium dioxide as a polymerization catalyst was used. When the content of each structural unit of the polyester resin was measured by NMR, the content of terephthalic acid unit, ethylene glycol unit and diethylene glycol unit in this polyester was 50.0 mol% and 48.9 mol, respectively.
Mol%, and 1.1 mol%.

The intrinsic viscosity, melting point and glass transition temperature were 0.83 dl / g, 252 ° C. and 80 ° C., respectively.

In co-injection blow molding, Nissei ASB
Co-Injection Stretch Blow Molding Machine (ASB-50HT Model 750)
ml, 2 pieces), and the PES side injection machine temperature 290
℃, thermoplastic resin composition side injection machine temperature 220 ℃, PES
Injection molding is performed at a hot runner block portion 260 ° C. where the resin composition and the resin composition merge, an injection mold core temperature of 15 ° C., and an injection mold cavity temperature of 15 ° C., resulting in two types of PES / resin composition / PES. To obtain three layers of parison.

Thereafter, the surface temperature of the parison was heated to 105 ° C., stretch blow molding was performed, and the average thickness of the body was 200 μm for the inner layer PES, 20 μm for the intermediate layer resin composition,
A three-layer, multi-layer co-injection blow-molded bottle composed of two kinds of resins and having an outer PES of 70 μm was obtained.

Using the obtained bottle, the haze of the body of the bottle and the oxygen permeation amount of the bottle after storage for 10 days and after storage for 3 months were measured.
0.00cc / container-day-atm and 0.00cc / container-day-at
m.

(Comparative Example 3) EVOH used in Example 2
95 parts by weight of the thermoplastic resin (a) 5 obtained in Example 1
Parts by weight, and 0.212 cobalt (II) stearate
Using 1 part by weight (0.0200 part by weight as a cobalt atom), a resin composition was obtained in the same manner as in Example 2. The melt flow rate of this resin composition (210 ° C.-2160
g load) was 11 g / 10 minutes. Observation of the fracture surface of the obtained resin composition pellets with an electron microscope revealed that particles of about 1 μm of the triblock copolymer as the thermoplastic resin (a) were dispersed in a matrix composed of EVOH.

The obtained resin composition was subjected to film extrusion molding at an extrusion temperature of 210 ° C. to obtain a film having a thickness of 20 μm. When the internal haze of the obtained single-layer film was measured, it was 1.7%. Next, when the oxygen absorption amount of the film was measured, the result shown in FIG. 1 was obtained. 4
The oxygen absorption rate of the resin composition calculated from the measurement results after 1 day and 14 days was 1.894 ml / m ² · day.

A thickness of 20 prepared using the above resin composition
Using a single-layer film of μm, the film was left in a screw-tube glass bottle at 40 ° C. for 4 hours in the same manner as in Example 2, and then the odor of the film was smelled.

Using the obtained resin composition and the same thermoplastic polyester resin as in Example 2, co-injection blow molding was performed in the same manner as in Example 1 to form a multilayer blow bottle. The average thickness in the body is 200 μm of the inner layer PES, 20 μm of the intermediate layer resin composition, and 70 μm of the outer layer PES.
A three-layer multi-layer co-injection blow-molded bottle consisting of two resins was obtained.

Using the obtained bottle, the haze of the body of the bottle and the oxygen permeation amount of the bottle after storage for 10 days and after storage for 3 months were measured.
%, 0.00cc / container ・ day ・ at
m and 0.00cc / container.day.
atm.

Comparative Example 4 A film having a thickness of 20 μm was obtained by extruding a film at an extrusion temperature of 210 ° C. using the EVOH resin used in Example 2 alone. When the internal haze of the obtained single-layer film was measured,
0.7%. Further, when the oxygen absorption amount of the film was measured, the results shown in FIG. 1 were obtained. The oxygen absorption rate of the EVOH resin calculated from the measurement results after 4 days and 14 days was 0.000 ml / m ² · day.

Next, a laminated film was produced in the same manner as in Example 2. The haze of this laminated film was 2.0%.

Using the above EVOH resin and the same thermoplastic polyester resin as in Example 2, co-injection blow molding was performed in the same manner as in Example 2 to form a multilayer blow bottle. A three-layer multi-layer co-injection blow-molded bottle made of two kinds of resins having an average thickness in the body of 200 μm for the inner layer PES, 20 μm for the intermediate layer EVOH, and 70 μm for the outer layer PES was obtained.

Using the obtained bottle, the haze of the body of the bottle and the oxygen permeation amount of the bottle after storage for 10 days and after storage for 3 months were measured to be 2.4.
%, 0.02cc / container-day-at
m and 0.02 cc / container day.
atm.

Table 2 below summarizes the results of the above test.

[0264]

[Table 2]

Example 3 From the film (oxygen-absorbing film) produced in Example 1, a laminated film was produced as follows. On one side of this film, a thickness of 20
A μm-stretched polypropylene film (OP- # 20 U-1 manufactured by Tocelo Co., Ltd.) is laminated, and a urethane-based adhesive (manufactured by Toyo Morton, trade name: AD335A, and a curing agent (manufactured by Toyo Morton, trade name: Cat-10)) Using a mixed solution of toluene / methyl ethyl ketone (weight ratio: 1: 1). Then, on the other side of the film, a thickness of 15
μm oxygen barrier film (Eval Film EF-F # 15 manufactured by Kuraray Co., Ltd.) and a stretched polypropylene film having a thickness of 20 μm (OP- # 20U manufactured by Tocelo Co., Ltd.)
-1) were sequentially laminated and bonded using the urethane-based adhesive described above. Thus, the stretched polypropylene film layer / urethane-based adhesive layer / oxygen barrier film layer /
A laminated film having a layer configuration of urethane-based adhesive layer / oxygen-absorbing film layer / urethane-based adhesive layer / stretched polypropylene film layer was obtained.

The laminated film was punched into a gasket shape so as to fit a polypropylene screw cap body having an outer diameter of 65 mm and a bottom thickness of 1.2 mm, and the cap side / stretched polypropylene film layer / urethane adhesive It was attached so as to have a layer structure of an agent layer / oxygen barrier film layer / urethane-based adhesive layer / oxygen-absorbing film layer / urethane-based adhesive layer / stretched polypropylene film layer / content side. Next, the obtained cap with a gasket is supplied to a mold of a gasket molding machine for compression molding, and an ethylene-1-butene copolymer (“POLYBUTYLENE 8240” manufactured by Shell Chemical Co., Ltd.) is supplied to the gasket molding machine for compression molding.
Butene (99 mol% or more), ethylene (1 mol% or less)
Copolymer product, density 0.908 g / cm ³ , MFR = 2.0
g / 10 minutes (210 ° C., 2160 g load)).
A cap with a multilayer gasket was produced by compression molding. At this time, the cylinder temperature of the compression molding machine was 24.
The temperature was adjusted to 5 ° C., the nozzle temperature to 235 ° C., and the mold temperature to 30 ° C.

The sealing properties of the thus prepared cap container were evaluated as follows.

200 ml of water was put into a cylindrical polyester blow bottle having an inner volume of 500 ml, a screw-type cap was attached, and the cap was tightened as shown in the following evaluation method. After that, the user held the bottle body by hand and shook it up and down 20 times. As a result, the state of liquid leakage was observed and evaluated and classified in the following four stages. A: Even if it is lightly tightened with a fingertip, there is no leakage at all. B: Leaking only by lightly tightening with a fingertip leaks the screw part of the cap. C: Leakage occurs when the fingertip is lightly tightened, and water scatters outside the cap, but does not leak when tightened strongly. D: It leaks even if tightened strongly. As a result of the evaluation, it was “A”, indicating good sealing properties.

[0269]

According to the present invention, a resin composition or a resin having excellent oxygen absorbability can be obtained. Such a resin or resin composition is easy to handle and can be prepared into a molded article of any shape. Molded articles prepared using these, for example, films and containers, are excellent in oxygen absorption, gas barrier properties, and low odor, and good transparency can be obtained by appropriately selecting a resin. Therefore, the resin composition or resin of the present invention is useful as a container for storing articles that are susceptible to deterioration by oxygen, such as foods and pharmaceuticals. Further, because of its excellent oxygen scavenging function, low odor, and easy handling, it is also useful as an oxygen scavenger.

A multilayer structure using the above resin or resin composition, for example, a packaging material formed of a multilayer film is also preferably used because it has the above excellent performance. In particular, a container made of a multilayer film having a total thickness of 300 μm or less,
Alternatively, a multilayer container formed by laminating a thermoplastic polyester layer is suitably used for a container requiring transparency in addition to the above-described oxygen absorbing or gas barrier properties and low odor.

[Brief description of the drawings]

FIG. 1 is a diagram in which the oxygen absorption amount of a single-layer film made of the oxygen-absorbing resin composition of Example 1, Comparative Example 1, and Comparative Example 2 is plotted against time.

FIG. 2 shows EVO of Example 2, Comparative Example 3 and Comparative Example 4.
It is the figure which plotted the oxygen absorption amount of H resin or EVOH resin composition with respect to time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B65D 81/26 B65D 81/26 J 4J100 C08F 36/04 C08F 36/04 C08K 3/00 C08K 3/00 5 / 09 5/09 5/098 5/098 C08L 53/02 C08L 53/02 F term (reference) 3E067 AA03 AA11 AB01 AB26 AB81 BA03A BB14A BB25A CA05 CA06 FA01 FC01 GB13 GB15 3E084 HA01 HB03 HC03 HD01 3E086 AD04 AD23 BA04 BA15 BA35 BA40 BB01 BB02 BB05 BB15 CA01 CA28 4F100 AK01A AK07 AK12A AK12J AK28A AK28J AL02A AT00B BA01 BA02 CA30A GB15 GB16 GB23 JB16A YY00A 4J002 AA031 BC051 BL011 BL021 BP011 DD076 DD077 DD086 DE106 DE246 DF036 DG046 DH046 DJ006 DJ016 EF016 EF076 EF116 EG046 EG047 EG056 FA086 FD060 FD070 FD150 FD206 GG00 4J100 AB00Q AB02Q AB04Q AB07Q AS02P AS03P BC04Q BC43Q CA01 CA04 DA01 DA36 JA58

Claims (8)

[Claims] The compound having a number average molecular weight in the range of 1,000 to 500,000 and having a structural formula (I): [Wherein, R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, or an alkoxy group, and R ₂ and R ₃ each represent a hydrogen atom and 1 to 10 carbon atoms.
Alkyl group, substituted aryl group, unsubstituted aryl group,
COOR ₄ , —OCOR ₅ , a cyano group, or a halogen atom, wherein R ₄ and R ₅ each independently have 1 to 1 carbon atoms.
10, alkyl groups, aryl groups, alkylaryl groups,
Or an alkoxy group], a thermoplastic resin containing at least 0.0001 eq / g of a carbon-carbon double bond in the structural unit. An oxygen-absorbing resin composition comprising a), a deodorant (b) and a transition metal salt (c). 2. An oxygen absorption rate of 0.01 ml / m ² · d
The resin composition according to claim 1, which is at least ay. 3. A compound having a number average molecular weight in the range of 1,000 to 500,000 and having the structural formula (I): [Wherein, R ₁ is an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, or an alkoxy group, and R ₂ and R ₃ each represent a hydrogen atom and 1 to 10 carbon atoms.
Alkyl group, substituted aryl group, unsubstituted aryl group,
COOR ₄ , —OCOR ₅ , a cyano group, or a halogen atom, wherein R ₄ and R ₅ each independently have 1 to 1 carbon atoms.
10, alkyl groups, aryl groups, alkylaryl groups,
Or an alkoxy group], and a thermoplastic resin (a) containing at least one structural unit represented by the formula (1), wherein a carbon-carbon double bond in the structural unit is contained at a ratio of 0.0001 eq / g or more. An oxygen-absorbing resin composition comprising the deodorant (b) and having an oxygen absorption rate of 0.01 ml / m ² · day or more. 4. The thermoplastic resin (a) has a structural formula (I)
The resin composition according to any one of claims 1 to 3, wherein the resin composition is mainly composed of a polyisoprene block containing polystyrene and a polystyrene block. 5. The thermoplastic resin (a) 50 to 99.9.
The oxygen-absorbing resin composition according to any one of claims 1 to 4, which is composed of parts by weight and 0.1 to 50% by weight of the deodorant (b). 6. A multilayer structure having a layer made of the oxygen-absorbing resin composition according to any one of claims 1 to 5. 7. A layer comprising the oxygen-absorbing resin composition according to claim 1 and having a total layer thickness of 30.
A multilayer container comprising a multilayer film having a thickness of 0 μm or less. 8. A cap provided with a gasket comprising the oxygen-absorbing resin composition according to claim 1.