JP5087392B2 - Oxygen-absorbing resin composition and molded article and laminate using the same - Google Patents

Description

  The present invention relates to an oxygen-absorbing resin composition having oxygen-absorbing ability, and a molded article and a laminate using the same.

  Conventionally, a gas barrier resin excellent in oxygen and / or carbon dioxide gas barrier properties and capable of being melt-molded is combined with a thermoplastic resin excellent in moisture resistance and mechanical properties, for example, as a multilayer plastic packaging material. It is used. Examples of the gas barrier resin include ethylene-vinyl alcohol copolymer (EVOH), and examples of the thermoplastic resin include polyolefin and polyester. However, it is usually difficult to completely prevent gas permeation in the gas barrier resin, and a non-negligible amount of gas permeates the resin. For this reason, a resin composition having oxygen absorptivity may be used for the purpose of reducing the permeation amount of oxygen that is a gas that permeates the resin, particularly a gas that greatly affects the quality of the packaged contents. . The oxygen-absorbing resin composition is also used for the purpose of reducing oxygen already present inside the package when the contents are packaged.

  As an oxygen-absorbing resin composition, Japanese Patent Laid-Open No. 5-115776 (Document 1) discloses a composition containing an ethylenically unsaturated hydrocarbon and a transition metal catalyst.

  In JP-A-2001-106866 (Reference 2), JP-A-2001-106920 (Reference 3) and JP-A-2002-146217 (Reference 4), as an oxygen-absorbing resin composition, a specific carbon- A thermoplastic resin containing a structural unit having a carbon double bond in the side chain is disclosed, which is shown to be preferably used in combination with EVOH. The resin can be melt-molded together with EVOH and is suitable for use as various packaging materials.

  Japanese Unexamined Patent Publication No. 2003-113311 (Document 5) discloses an oxygen-absorbing resin composition containing a polyether unit, specifically, a polyalkylene ether unit as a main chain or branched chain constituent unit.

  US Pat. No. 6,746,622 (Document 6) discloses an oxygen-absorbing resin composition having a cyclic ether derived from tetrahydrofuran (THF) bonded to the main chain via an ester bond and a methylene group in the side chain. ing.

  However, in the resin compositions disclosed in Documents 1 to 4, the decomposition of the resin composition progresses as oxygen is absorbed, and a low molecular weight substance is generated to generate an unpleasant odor. The generation of such an odor is desirably suppressed as much as possible particularly when the oxygen-absorbing resin composition is used as a packaging material.

  In the oxygen-absorbing resin compositions disclosed in Documents 5 and 6, it is considered that the ether bond is cleaved along with the absorption of oxygen. In particular, in the composition of Document 5, the main chain or the branched chain is cleaved. In particular, the production of low-molecular substances is likely to proceed. In the composition of Reference 6, although the main chain is not broken due to oxygen absorption, its thermal stability is inferior. For example, coloring may occur during processing into a sheet by melt molding.

  It is an object of the present invention to provide an oxygen-absorbing resin composition that is different in structure from these conventional compositions, has an excellent oxygen-absorbing ability, and suppresses the generation of unpleasant odors during use (during oxygen absorption). And

  The oxygen-absorbing resin composition of the present invention (hereinafter also simply referred to as “resin composition”) comprises a polymer (A) having a structural unit represented by formula (I) and an oxygen absorption accelerator (B). Including.

In the above formula (I), X represents an alkylene group having 1 to 4 carbon atoms which may have a substituent. Z represents a single bond or a methylene group which may have a substituent. R ¹ and R ² represent hydrogen, an alkyl group which may have a substituent, or an aryl group which may have a substituent. In the above formula (I), the carbon atom adjacent to the oxygen atom has at least one hydrogen atom.

  By using such a resin composition, it is possible to obtain an oxygen-absorbing resin composition that is excellent in oxygen absorption (oxygen scavenging) and that suppresses the generation of unpleasant odors during use (during oxygen absorption). it can.

  The oxygen-absorbing resin composition of the present invention may further contain a gas barrier resin (C).

  The molded article of the present invention includes a portion made of the oxygen-absorbing resin composition of the present invention.

  The laminate of the present invention includes a layer comprising the oxygen-absorbing resin composition of the present invention.

  The oxygen-absorbing resin composition of the present invention can be used in various applications, and is particularly suitable as a container for storing articles such as foods and cosmetics that are easily deteriorated by oxygen and emphasize fragrance. The said container should just contain the part and / or layer which consist of an oxygen absorptive resin composition of this invention at least in part. That is, the container is composed of the molded product of the present invention or the laminate of the present invention.

  The oxygen-absorbing resin composition of the present invention is also useful as an oxygen scavenger because of its excellent oxygen-absorbing ability and ease of handling.

It is a graph which shows an example of the result of having measured the oxygen absorption ability of the oxygen absorptive resin composition of this invention and a comparative example. It is a graph which shows another example of the result of having measured the oxygen absorptivity of the oxygen absorptive resin composition of this invention and the comparative example.

  Embodiments of the present invention will be described below. In the following description, specific substances are exemplified as substances exhibiting a specific function, but the present invention is not limited thereto. In addition, the exemplified substances may be used alone or in combination of two or more unless otherwise specified.

  As used herein, “oxygen scavenging” refers to reducing or reducing the amount of oxygen in the environment by absorbing or consuming oxygen.

  The resin composition of the present invention contains a polymer (A) having a structural unit represented by the following formula (I) and an oxygen absorption accelerator (B).

In the above formula (I), X represents an alkylene group having 1 to 4 carbon atoms which may have a substituent. Z represents a single bond or a methylene group which may have a substituent. R ¹ and R ² represent hydrogen, an alkyl group which may have a substituent, or an aryl group which may have a substituent. The carbon atom adjacent to the oxygen atom has at least one hydrogen atom, that is, forms a covalent bond with at least one hydrogen atom.

The term “single bond” as used herein refers to a main chain carbon in which an oxygen atom and R ² are bonded to each other without any atom such as a carbon atom in the portion represented by “Z” in the above formula (I). A direct single bond with an atom. That is, when Z is a single bond, the formula (I) can be expressed as the following formula (V).

  In the structural unit represented by the formula (I), an ether bond that reacts when absorbing oxygen is present in the molecule as a cyclic ether. Since the cyclic ether has a high reaction rate with oxygen, the polymer (A) can efficiently react with oxygen and obtain high oxygen absorption ability. In addition, the presence of an ether bond constituting the cyclic ether in the structural unit outside the main chain is also a factor that can improve the reaction rate with oxygen. For example, with a linear ether polymer having an ether bond in the main chain of the polymer, it is difficult to obtain a high reaction rate as in the polymer (A).

  In the polymer (A), even when the ether bond is cleaved due to absorption of oxygen, the main chain is not cleaved unlike the linear ether polymer, so that a low molecular weight decomposition product that causes odor is generated. , Molecular weight reduction can be suppressed.

  When a linear polyether unit is present as a branched chain from the polymer main chain as in the composition disclosed in Document 5, the oxygen absorption capacity can be made relatively high, but branched chain ether bonds are formed by oxygen absorption. When cleaves, a low molecular weight decomposition product that causes odor is produced. On the other hand, in the polymer (A), since the bond with the main chain is maintained even when the ether bond is cleaved, the generation of the low molecular weight decomposition product can be suppressed.

  When the cyclic ether is bonded to the main chain through an ester bond or the like as in the composition disclosed in Document 6, a part of the cyclic ether is separated from the main chain at the time of molding such as melting and heating. In addition to the deterioration, the separated cyclic ether may absorb oxygen and cleave to produce a low molecular weight decomposition product. On the other hand, in the polymer (A), since the cyclic ether is incorporated in the main chain, deterioration during molding can be suppressed, and generation of a low molecular weight decomposition product can be suppressed.

  X in the formula (I) is an alkylene group having 1 to 4 carbon atoms which may have a substituent, and Z is a methylene group which may have a single bond or a substituent. Examples of the substituent that X and Z may have include an alkyl group (X) that may have a substituent, an aryl group (X) that may have a substituent, and a substituent. Or an alkylaryl group (X) or a halogen atom.

  The alkyl group (X) preferably has 1 to 5 carbon atoms, the aryl group (X) preferably has 6 to 10 carbon atoms, and the alkylaryl group (X) preferably has 7 carbon atoms. ~ 11. Examples of the alkyl group (X) include a methyl group, an ethyl group, a propyl group, and a butyl group, examples of the aryl group (X) include a phenyl group, examples of the alkylaryl group (X) include a tolyl group, Examples of the halogen atom include a chlorine atom.

  The position of the substituent in X and Z is not particularly limited, but from the viewpoint of ensuring reactivity with oxygen, the carbon atom adjacent to the oxygen atom shown in formula (I) must have at least one hydrogen atom, Substituents need to be positioned to satisfy this condition. Since the reactivity with oxygen can be further improved, that is, the oxygen absorption capacity and / or the oxygen absorption rate as the oxygen-absorbing resin composition can be improved, in formula (I), the carbon atom adjacent to the oxygen atom is a substituent. In other words, it is preferable that the carbon atom has two hydrogen atoms.

R ¹ and R ² in Formula (I) are hydrogen, an alkyl group that may have a substituent, or an aryl group that may have a substituent. The substituents that R ¹ and R ² may have are the same as the substituents that X and Z may have and the preferable substituents.

  Since the reactivity with oxygen can be further improved, the number of carbon atoms of the substituent present in the ring structure part of the structural unit represented by formula (I) is preferably small, and the number of substituents present in the ring structure part is also Less is preferable.

More specifically, in the formula (I), X is an alkylene group represented by the following formula (II), formula (III) or formula (IV), Z is a single bond, R ¹ and R ² Is preferably hydrogen. In this case, the reactivity with oxygen can be further improved. Such a structural unit is represented by the following formula (VI), formula (VII), formula (VIII) and formula (IX).

  The polymer (A) may be a furan derivative polymer, and is particularly preferably a poly (dihydrofuran) represented by the following formula (X). In this case, the reactivity with oxygen can be further improved. The poly (dihydrofuran) represented by the formula (X) has a structural unit represented by the above formula (VI).

  The polymer (A) may be a polymer of a pyran derivative, and among them, polydihydropyran or poly (4-methyldihydropyran) is preferable. In this case, the reactivity with oxygen can be further improved.

  “N” in the formula (X) is a value determined by the molecular weight of the polymer (A) when the polymer (A) is not a copolymer.

  The polymer (A) can be said to have a cyclic ether group in its main chain, and the amount of the cyclic ether group contained in the polymer (A) is preferably 0.001 eq / g (equivalent / g) or more. 0.005 eq / g or more is more preferable, and 0.01 eq / g or more is more preferable. When the content of the cyclic ether group is less than 0.001 eq / g, the reactivity with oxygen is lowered, and sufficient oxygen absorbing ability as an oxygen absorbing resin composition may not be obtained.

  The number average molecular weight of the polymer (A) is preferably 500 to 500,000, more preferably 1000 to 250,000. When the molecular weight is less than 500 or exceeds 500,000, molding processability and handling properties as a resin composition, or mechanical properties such as strength and elongation when the resin composition is used as a molded product are deteriorated. Sometimes. Further, when the polymer (A) and a gas barrier resin (C) described later are used in combination, the dispersibility of the polymer (A) is excessively lowered, and the gas barrier property and oxygen absorption in the obtained composition are reduced. Performance may be reduced.

  The oxygen-absorbing resin composition of the present invention may contain two or more types of polymers (A).

  The polymer (A) may have a structural unit other than the structural unit represented by the above formula (I), for example, a structural unit derived from an olefin such as ethylene or propylene, styrene, vinyl acetate, vinyl chloride or the like. And a structural unit derived from a vinyl compound, a structural unit derived from a (meth) acrylic acid derivative such as (meth) acrylic acid, methyl (meth) acrylate, and the like.

  The proportion of the structural unit represented by the above formula (I) in all the structural units of the polymer (A) is preferably as large as possible in order to obtain a resin composition having a high oxygen-absorbing capacity, usually 5 mol%. It is sufficient if it is above, 50 mol% or more is preferable, and 80% or more is more preferable.

  The polymer (A) may be formed by a general method, for example, by polymerization of a cyclic ether having an ethylenically unsaturated bond in the ring (hereinafter also simply referred to as “unsaturated cyclic ether”). . In the polymerization, if necessary, a monomer (monomer) other than the unsaturated cyclic ether may coexist.

  More specifically, when the polymer (A) is poly (dihydrofuran), for example, 2,3-dihydrofuran as an unsaturated cyclic ether is dissolved in xylene as a polymerization solvent, and iron chloride or the like is used as a catalyst. A Lewis acid catalyst may be added and cationic polymerization may be performed according to a conventional method.

  The polymer (A) may be combined with other substances, for example, an antioxidant, if necessary. When the polymer (A) is combined with an antioxidant, the reaction between the polymer (A) and oxygen during storage or melt molding of the polymer (A) can be suppressed, and before use as a resin composition It is possible to suppress a decrease in oxygen absorption capacity.

  The antioxidant is not particularly limited. For example, the following compounds may be used: 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-p-cresol, 4,4′- Thiobis- (6-tert-butylphenol), 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ', 5'-di-tert-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- (tert-butyl) -4-me Le phenol (BHT), 2,2-methylenebis - (6-tert-butyl -p- cresol), triphenyl phosphite, phosphorous acid tris - (nonylphenyl), dilauryl thiodipropionate.

  The amount of the antioxidant to be combined with the polymer (A) is appropriately determined in consideration of the type and content of each component in the resin composition of the present invention, or the purpose of use and storage conditions of the resin composition of the present invention. Just decide. Based on the total weight of the polymer (A) and the antioxidant, the antioxidant is usually about 0.01 to 1% by weight, preferably about 0.02 to 0.5% by weight. . When the amount of the antioxidant is excessively large, the reaction between the polymer (A) and oxygen is excessively suppressed, and sufficient oxygen absorption ability as an oxygen-absorbing resin composition may not be obtained. On the other hand, when the amount of the antioxidant is too small, depending on the storage conditions or melt molding conditions of the polymer (A), the oxygen absorption capacity may already be reduced at the start of use as the oxygen-absorbing resin composition. is there.

  For example, when the polymer (A) is stored at a relatively low temperature or in an inert gas atmosphere, the amount of the antioxidant combined with the polymer (A) may be reduced. The same applies to the case where the polymer (A) is melt-molded and melt-kneaded in a nitrogen-sealed state. When the resin composition of the present invention contains a large amount of an oxidation catalyst for accelerating the oxidation of the polymer (A), it is satisfactory even if the amount of the antioxidant combined with the polymer (A) is increased. A resin composition having oxygen absorbing ability can be obtained.

  The oxygen absorption promoter (B) contained in the resin composition of the present invention has an action of promoting the reaction between the polymer (A) and oxygen and improving the oxygen absorption ability of the resin composition.

  The oxygen absorption promoter (B) may be at least one selected from, for example, a transition metal salt (B-1), a radical generator (B-2), and a photocatalyst (B-3).

  When the oxygen absorption promoter (B) is a transition metal salt (B-1), the transition metal constituting the transition metal salt (B-1) is not particularly limited. For example, iron, nickel, copper, manganese, cobalt And at least one selected from rhodium, titanium, chromium, vanadium and ruthenium. Especially, since it is excellent in the effect which accelerates | stimulates the said reaction, at least 1 sort (s) chosen from iron, nickel, copper, manganese, and cobalt is preferable, at least 1 sort (s) chosen from manganese and cobalt is more preferable, and cobalt is further more preferable.

  In other words, the transition metal salt (B-1) is preferably at least one selected from iron salts, nickel salts, copper salts, manganese salts and cobalt salts, and more preferably at least one selected from manganese salts and cobalt salts. Cobalt salts are preferred and even more preferred.

  The counter ion of the transition metal constituting the transition metal salt (B-1) is not particularly limited, and may be, for example, an anion derived from an organic acid or an anion derived from chloride. Examples of organic acids include acetic acid, stearic acid, acetylacetone, dimethyldithiocarbamic acid, palmitic acid, 2-ethylhexanoic acid, neodecanoic acid, linoleic acid, toluic acid, oleic acid, resin acid, capric acid, and naphthenic acid. Can be mentioned. Particularly preferred salts include, for example, cobalt 2-ethylhexanoate, cobalt neodecanoate, cobalt acetate and cobalt stearate. The transition metal salt (B-1) may be a so-called ionomer having a polymeric counter ion.

  The content of the transition metal salt (B-1) in the resin composition of the present invention is preferably 1 to 50000 ppm (weight ratio; the same applies hereinafter) in terms of metal element based on the polymer (A). The content is more preferably 5 to 10,000 ppm, and still more preferably 10 to 5000 ppm. When the content is less than 1 ppm, the effect of promoting the reaction between the polymer (A) and oxygen may not be sufficiently obtained. On the other hand, when the content exceeds 50000 ppm, the thermal stability as the resin composition is lowered, and a decomposition gas may be generated during molding such as melt molding, and the generation of gels and blisters may be significant. .

  When the oxygen absorption accelerator (B) is a radical generator (B-2), the radical generator (B-2) is not particularly limited. For example, N-hydroxysuccinimide, N-hydroxymaleimide, N, N′-dihydroxycyclohexanetetracarboxylic acid diimide, N-hydroxyphthalimide, N-hydroxytetrachlorophthalimide, N-hydroxytetrabromophthalimide, N-hydroxyhexahydrophthalimide, 3-sulfonyl-N-hydroxyphthalimide, 3-methoxycarbonyl- N-hydroxyphthalimide, 3-methyl-N-hydroxyphthalimide, 3-hydroxy-N-hydroxyphthalimide, 4-nitro-N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide, 4-methoxy-N-hydroxy Phthalimide, 4-dimethylamino-N-hydroxyphthalimide, 4-carboxy-N-hydroxyhexahydrophthalimide, 4-methyl-N-hydroxyhexahydrophthalimide, N-hydroxyhetic imide, N-hydroxyhymic imide, N -Hydroxytrimellitic acid imide, N, N-dihydroxypyromellitic acid diimide or the like may be used. Among them, N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N′-dihydroxycyclohexanetetracarboxylic diimide, N-hydroxyphthalimide (NHPI), N-hydroxytetrabromophthalimide, N— Hydroxytetrachlorophthalimide is preferred.

  When the oxygen absorption accelerator (B) is a photocatalyst (B-3), the photocatalyst (B-3) is not particularly limited. For example, titanium dioxide, tungsten oxide, zinc oxide, cerium oxide, strontium titanate, niobium Potassium acid or the like may be used. These are usually used in the form of a powder. Among these, titanium dioxide is preferable because it has a high photocatalytic function, is certified as a food additive, is safe and inexpensive. Especially, since it has a high photocatalytic action, anatase type titanium dioxide is preferable, and the ratio of anatase type in titanium dioxide contained in the resin composition of the present invention as a photocatalyst (B-3) is 30% by weight or more (more preferably). 50% by weight or more) is preferable.

  In the resin composition of the present invention, the oxygen absorption promoter (B) has the effect of promoting the oxidation reaction of the polymer (A) and improving the oxygen absorption capacity. For example, the oxygen absorption promoter (B) promotes the reaction between oxygen present in the packaging material using the resin composition of the present invention and oxygen that attempts to permeate the packaging material and the polymer (A). Thus, the oxygen barrier property and the oxygen absorbing ability as a packaging material can be improved.

  The oxygen absorption rate in the resin composition of the present invention is 0.01 ml / (g · day) or more by adjusting the type and content of the polymer (A) and / or the oxygen absorption accelerator (B). It can also be 0.05 ml / (g · day) or more. Here, the “oxygen absorption rate” refers to the weight of oxygen absorbed by the film per unit time when the film made of the resin composition is left in a certain volume of air per unit weight of the film. This is a value obtained by conversion. A specific method for measuring the oxygen absorption rate will be described in the examples described later.

  The resin composition of the present invention is preferably composed of the polymer (A) and the oxygen absorption accelerator (B) described above when the oxygen absorption rate is important.

  The resin composition of the present invention may contain a substance other than the polymer (A) and the oxygen absorption accelerator (B), for example, a resin other than the polymer (A), more specifically a gas barrier resin. (C) may further be included. The resin composition of the present invention containing the gas barrier resin (C) is excellent in oxygen absorption capacity and has high gas barrier properties, and can be molded into various shapes, for example, as a packaging material for foods and cosmetics. Suitable for use.

The oxygen permeation rate of the gas barrier resin (C) at 20 ° C. and 65% RH (relative humidity) is preferably 500 ml · 20 μm / (m ² · day · atm) or less. This value is obtained by measuring the volume of oxygen permeating through a film having an area of 1 m ² and a thickness of 20 μm in a day when there is an oxygen differential pressure of 1 atm when measured in an environment of 20 ° C. and 65% RH. , 500 ml or less. In the case of the resin (C) having an oxygen transmission rate exceeding 500 ml · 20 μm / (m ² · day · atm), the gas barrier property of the resulting resin composition may be insufficient. The oxygen permeation rate of the gas barrier resin (C) is preferably 100 ml · 20 μm / (m ² · day · atm) or less, more preferably 20 ml · 20 μm / (m ² · day · atm) or less, and 5 ml · 20 μm / ( m ² · day · atm) or less is more preferable. By combining such a gas barrier resin (C) and the polymer (A), it is possible to obtain a resin composition that is excellent in oxygen absorption capability and gas barrier properties, and as a result, has extremely high gas barrier properties. It can be set as a resin composition.

The gas barrier resin (C) is not particularly limited, and for example, at least one selected from polyvinyl alcohol resins, polyamide resins, polyvinyl chloride resins, and polyacrylonitrile resins may be used. These resins usually have an oxygen transmission rate at 20 ° C. and 65% RH of 500 ml · 20 μm / (m ² · day · atm) or less.

  The polyvinyl alcohol-based resin can be formed, for example, by saponifying a vinyl ester homopolymer or a copolymer of vinyl ester and another monomer with an alkali catalyst or the like. For example, EVOH can be formed by saponifying a copolymer of vinyl ester and ethylene. Representative vinyl esters include vinyl acetate, but fatty acid vinyl esters other than vinyl acetate such as vinyl propionate and vinyl pivalate may also be used.

  The saponification degree of the vinyl ester component in the polyvinyl alcohol resin is preferably 90% or more, more preferably 95% or more, and still more preferably 96% or more. When the degree of saponification is less than 90%, the gas barrier property under high humidity in the obtained resin composition may be lowered. Further, when the polyvinyl alcohol-based resin is EVOH and the saponification degree is less than 90%, the obtained resin composition has insufficient thermal stability, and a gel is formed when a molded product is molded from the resin composition. , Bumps and the like are likely to occur.

  When the polyvinyl alcohol resin is composed of a mixture of two or more types of polyvinyl alcohol resins having different saponification degrees, the average value of the saponification degree calculated from the mixing weight ratio may be used as the saponification degree of the mixture. .

  As the polyvinyl alcohol-based resin, EVOH is preferable because it has excellent melt moldability and good gas barrier properties under high humidity.

  As for the ratio of the ethylene unit to all the structural units of EVOH, 5-60 mol% is preferable. When the ratio of the ethylene unit is less than 5 mol%, the gas barrier property under high humidity may be lowered and the melt moldability may be deteriorated. From this viewpoint, the proportion of ethylene units is preferably 10 mol% or more, more preferably 15 mol% or more, and further preferably 20 mol% or more. On the other hand, if the proportion of ethylene units exceeds 60 mol%, sufficient gas barrier properties may not be obtained. From this viewpoint, the proportion of ethylene units is preferably 55 mol% or less, and more preferably 50 mol% or less.

  EVOH more preferable as the gas barrier resin (C) is EVOH in which the proportion of ethylene units in the total structural units is 5 to 60 mol% and the saponification degree is 90% or more. In the case of forming a laminate including a layer composed of the resin composition of the present invention, when impact peel resistance is required for the laminate, the proportion of ethylene units in all the structural units is 25 to 55 mol%. In addition, EVOH having a saponification degree of 90% or more and less than 99% is preferably used as the gas barrier resin (C).

  When EVOH is composed of a mixture of two or more types of EVOH having different ethylene unit ratios, the average value calculated from the mixing weight ratio may be the ethylene unit ratio in the mixture. In this case, it is preferable that the difference in the proportion between the EVOHs having the most distant ethylene units is 30 mol% or less and the difference in the degree of saponification is 10% or less. When deviating from these conditions, the transparency as the resin composition layer may be impaired. The difference in the proportion is more preferably 20 mol% or less, and further preferably 15 mol% or less. The difference in the saponification degree is more preferably 7% or less, and further preferably 5% or less.

  In the case of forming a laminate including a layer comprising the resin composition of the present invention, in order to obtain a laminate having a higher level of impact resistance and gas barrier properties, the proportion of ethylene units is 25 to 55. EVOH (c1) having a saponification degree of 90% or more and less than 99%, and EVOH (c2) having an ethylene unit ratio of 25 to 55 mol% and a saponification degree of 99% or more. May be mixed so that the weight ratio c1 / c2 is in the range of 5/95 to 95/5 to obtain a gas barrier resin (C).

  The proportion of ethylene units and the degree of saponification in EVOH can be determined by a nuclear magnetic resonance (NMR) method.

  As long as the effects of the present invention can be obtained, EVOH may contain a small amount of monomers other than ethylene and vinyl alcohol as a copolymerization component. Examples of such a monomer include α-olefins such as propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, and 1-octene. The monomer includes unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid and maleic anhydride, and salts thereof, partial esters thereof, complete esters thereof, nitriles thereof, amides thereof and anhydrides thereof. There may be. In addition, the monomer may be a vinylsilane compound such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and the like. It may be an acid or a salt thereof, an alkyl thiol, a vinyl pyrrolidone or the like.

  EVOH may contain 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymerization component. In this case, when the resin composition of the present invention containing the EVOH is co-extruded or co-injected with a resin to be a base material (for example, thermoplastic polyester resin: PES) to form a laminate, The consistency of melt viscosity between the resin composition of the present invention and the base resin can be improved, and a laminate having a more homogeneous structure can be formed. As the vinyl silane compound, vinyl trimethoxy silane and vinyl triethoxy silane are suitable.

  The melt viscosity of EVOH can also be improved by adding a boron compound to EVOH, and a molded product having a more homogeneous structure can be obtained. Examples of the boron compound added to EVOH include boric acids, boric acid esters, borates, borohydrides, and the like. Specifically, as the boric acid, for example, orthoboric acid, metaboric acid, tetraboric acid, etc. may be used, and as the boric acid ester, triethyl borate, trimethyl borate, etc. may be used. An alkali metal salt, an alkaline earth metal salt, borax, or the like of boric acid may be used. Of these boron compounds, orthoboric acid is preferably used.

  When a boron compound is added to EVOH, the content of the boron compound in EVOH after the addition of the compound is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element. In this case, it is possible to obtain EVOH in which torque fluctuation during heating and melting during molding is suppressed. When the content is less than 20 ppm, the effect of adding a boron compound may be insufficient. On the other hand, when the said content exceeds 2000 ppm, EVOH after addition becomes easy to gelatinize and the moldability as a resin composition may fall.

  In order to improve interlayer adhesion and compatibility, an alkali metal salt may be added to EVOH. The content of the alkali metal salt in EVOH after adding the metal salt is preferably 5 to 5000 ppm, more preferably 20 to 1000 ppm, and still more preferably 30 to 500 ppm in terms of alkali metal elements. The alkali metal salt to be added may be, for example, an aliphatic carboxylate, an aromatic carboxylate, a phosphate, a metal complex or the like such as lithium, sodium, or potassium. Specifically, for example, sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate, sodium salt of ethylenediaminetetraacetic acid, sodium acetate, potassium acetate, Sodium phosphate is preferred.

  A phosphate compound may be added to EVOH, and the content of the phosphate compound in EVOH after the addition of the compound is preferably 20 to 500 ppm, more preferably 30 to 300 ppm, and more preferably 50 to 200 ppm in terms of phosphate radical. Is more preferable. By adding a phosphoric acid compound to EVOH, the thermal stability of EVOH can be improved. In particular, when a resin composition is melt-molded over a long period of time, the occurrence of coloring, gels, and defects can be suppressed.

  The phosphoric acid compound added to EVOH is not specifically limited, For example, what is necessary is just various acids, such as phosphoric acid and phosphorous acid, and its salt. The phosphate may be in any form of primary phosphate, secondary phosphate, and tertiary phosphate. The cationic species of the phosphate is not particularly limited, but the cationic species is preferably an alkali metal or alkaline earth metal. Specifically, it is preferable to add a phosphoric acid compound to EVOH in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, or dipotassium hydrogen phosphate.

  The melt flow rate (MFR) of EVOH as the gas barrier resin (C) (at 210 ° C. under 2160 g load, based on JIS K7210) is preferably 0.1 to 100 g / 10 min, and 0.5 to 50 g / 10 min. Is more preferable, and 1 to 30 g / 10 min is even more preferable.

  The polyamide resin used as the gas barrier resin (C) is not particularly limited. For example, polycaproamide (nylon-6), polyundecanamide (nylon-11), polylaurolactam (nylon-12), polyhexamethylene adipa Aliphatic polyamide homopolymers such as amide (nylon-6,6), polyhexamethylene sebacamide (nylon-6,10); caprolactam / laurolactam copolymer (nylon-6 / 12), caprolactam / aminoundecane Acid copolymer (nylon-6 / 11), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), caprolactam / hexamethylene adipamide copolymer (nylon-6 / 6,6), caprolactam / Hexamethylene adipamide / Hexamethylene sebacamide copolymer (Nai Aliphatic polyamide copolymers such as N-6 / 6, 6/6, 10); polymetaxylylene adipamide (MX-nylon), hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (nylon) Aromatic polyamide such as 6T / 6I) may be used. These polyamide resins may be used alone or in combination of two or more. Among these, polycaproamide (nylon-6) and polyhexamethylene adipamide (nylon-6, 6) are preferable because good gas barrier properties can be obtained.

  The polyvinyl chloride resin used as the gas barrier resin (C) is not particularly limited. For example, vinyl chloride or vinylidene chloride homopolymer, vinyl chloride or vinylidene chloride, vinyl acetate, maleic acid derivative, higher alkyl vinyl ether, etc. And a copolymer thereof may be used.

  The polyacrylonitrile resin used as the gas barrier resin (C) is not particularly limited. For example, a copolymer of acrylonitrile and an acrylate ester may be used in addition to a homopolymer of acrylonitrile.

  As the gas barrier resin (C), one kind selected from the various resins described above may be used, or two or more kinds may be mixed and used. Especially, it is preferable to use a polyvinyl alcohol-type resin as a gas barrier resin (C), and it is preferable to use EVOH especially. As described above, EVOH is preferably a copolymer having an ethylene unit ratio of 5 to 60 mol% and a saponification degree of 90% or more in all structural units.

  When the resin composition of the present invention further contains a gas barrier resin (C), the ratio of the weight of the polymer (A) to the total weight of the polymer (A) and the gas barrier resin (C) is 1 to 30. % Is preferred. That is, it is preferable that the ratio of the gas barrier resin (C) in the total is 70 to 99%.

  When the ratio of the gas barrier resin (C) in the total is less than 70%, the gas barrier property as the resin composition may be lowered. On the other hand, if it exceeds 99%, the oxygen absorption capacity as the resin composition may be lowered. The proportion of the gas barrier resin (C) in the total is preferably 80 to 98%, more preferably 85 to 97%. That is, the proportion of the polymer (A) in the total is preferably 2 to 20%, more preferably 3 to 15%.

  As long as the effects of the present invention are obtained, the gas barrier resin (C) and the resin composition of the present invention are made of a heat stabilizer, an ultraviolet absorber, an antioxidant, a colorant, a filler, or a resin such as polyamide or polyolefin. May be included.

  When the resin composition of the present invention further contains a gas barrier resin (C), it is preferable to consider miscibility between the polymer (A) and the gas barrier resin (C). The miscibility between the two may affect the transparency, cleanliness, oxygen absorption capacity, gas barrier properties, mechanical properties, texture, etc. of the resin composition and a molded product using the resin composition. The resin composition of the present invention further comprises a compatibilizing agent (D) that improves the compatibility between the polymer (A) and the gas barrier resin (C) in order to improve the miscibility between the two. But you can.

  The compatibilizer (D) is a compound that improves the compatibility between the polymer (A) and the gas barrier resin (C) and stabilizes the form of the resulting resin composition. The type of the compatibilizer (D) is not particularly limited and may be appropriately selected according to the combination of the polymer (A) and the gas barrier resin (C).

  When the gas barrier resin (C) is a highly polar resin such as a polyvinyl alcohol resin, the compatibilizer (D) may be a hydrocarbon polymer having a polar group or ethylene-vinyl alcohol copolymer. Coalescence is preferred. For example, in a hydrocarbon-based polymer having a polar group, the affinity of the compatibilizer (D) and the polymer (A) can be improved by the hydrocarbon part serving as the base of the polymer, and Due to the polar group of the coalescence, the compatibility between the compatibilizer (D) and the gas barrier resin (C) can be improved, and the compatibility between the polymer (A) and the gas barrier resin (C) can be improved. Can be improved.

  The hydrocarbon part serving as the base of the hydrocarbon polymer may include, for example, the following monomers: ethylene, propylene, 1-butene, isobutene, 3-methylpentene, 1-hexene, 1-octene. Α-olefins such as: styrene, α-methylstyrene, 2-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl- Styrenes such as 4-benzylstyrene, 4- (phenylbutyl) styrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, tert-butoxystyrene, etc .: 1-vinyl Vinyl such as naphthalene and 2-vinylnaphthalene Naphthalenes: Vinylene group-containing aromatic compounds such as indene and acenaphthylene: Conjugated diene compounds such as butadiene, isoprene, 2,3-dimethylbutadiene, pentadiene and hexadiene.

  The said hydrocarbon part may consist of 1 type chosen from these monomers, and may consist of 2 or more types.

  More specifically, the hydrocarbon part serving as the base of the hydrocarbon polymer is composed of, for example, the following polymers. The following polymers can be formed from the above monomers: polyethylene (regardless of ultra-low density, low density, linear low density, medium density, high density), ethylene- (meth) acrylate (methyl) Esters, ethyl esters, etc.) Olefin polymers such as copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polypropylene, ethylene-propylene copolymers: polystyrene, styrene-acrylonitrile copolymers, Styrene-acrylonitrile-butadiene copolymer, styrene-diene block copolymer (styrene-isoprene-block copolymer, styrene-butadiene copolymer, styrene-isoprene-styrene block copolymer, etc.), or these Styrene polymers such as hydrogenated products: polymethyl acrylate (Meth) acrylic ester polymers such as polyethyl acrylate and polymethyl methacrylate: Halogenated vinyl polymers such as polyvinyl chloride and vinylidene fluoride: Semi-aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate: Polyvalero Aliphatic polyesters such as lactone, polycaprolactone, polyethylene succinate, polybutylene succinate: etc. Of these, styrene-diene block copolymers or styrene polymers such as hydrogenated products thereof are preferred.

Although the polar group which a compatibilizer (D) has is not specifically limited, it is preferable that the said polar group has an oxygen atom. Specifically, polar groups that contain active hydrogen-containing polar groups (such as —SO ₃ H, —SO ₂ H, —SOH, —CONH ₂ , —CONHR, —CONH—, —OH, etc.) and no active hydrogen. Groups (—NCO, —OCN, —NO, —NO ₂ , —CONR ₂ , —CONR—, etc.), epoxy groups, carbonyl group-containing polar groups (—CHO, —COOH, —COOR, —COR,> C═O , -CSOR, -CSOH, etc.), phosphorus-containing polar groups (-P (OR) ₂ , -PO (OR) ₂ , -PO (SR) ₂ , -PS (OR) ₂ , -PO (SR) (OR) , -PS (SR) (OR), etc.), a boron-containing polar group, etc. Here, “R” in the above general formula represents an alkyl group, a phenyl group, or an alkoxy group.

The method for producing a hydrocarbon polymer having a polar group is not particularly limited. For example, it may be formed by the method shown in the following (1) to (4):
(1) A method of copolymerizing a monomer capable of forming a hydrocarbon part serving as a base and a monomer having a polar group (or a group capable of forming the polar group):
(2) A method of using an initiator having a polar group (or a group capable of forming the polar group) or a chain transfer agent in the polymerization of a monomer capable of forming a hydrocarbon part serving as a base :
(3) Living polymerization of a monomer capable of forming a hydrocarbon part serving as a base, and in this case, a monomer having a polar group (or a group capable of forming the polar group) is used as a terminator (terminal treatment agent). Method used as:
(4) A polymer capable of forming a hydrocarbon part serving as a base is polymerized to form a polymer, and a reactive group in the formed polymer, for example, a carbon-carbon double bond part is attached to a polar group ( Or the method which introduce | transduces the monomer which has the group which can form the said polar group by reaction.

  The copolymerization in the method (1) may be any polymerization method such as random copolymerization, block copolymerization, and graft copolymerization.

  When the compatibilizer (D) is a hydrocarbon polymer having a polar group, carboxyl groups such as a carboxyl group, a carboxylic acid anhydride group, and a carboxylate group: boronic acid group, boron and the like are particularly preferable polar groups. And boron-containing polar groups such as acid ester groups, boronic acid anhydride groups, and boronic acid groups.

  In particular, when the polar group is a carboxyl group, a resin composition having high thermal stability can be formed. As described above, when the transition metal salt (B-1) is excessively contained as the oxygen absorption accelerator (B) in the resin composition, the thermal stability of the resin composition may be lowered. When the compatibilizer (D) having a carboxyl group is contained together with the metal salt (B-1), it is possible to suppress a decrease in the thermal stability of the resin composition. The reason why such an effect is obtained is not clear, but it is considered that some interaction occurs between the compatibilizer (D) having a carboxyl group and the transition metal salt (B-1).

  When the polar group is a boron-containing polar group, the compatibility between the polymer (A) and the gas barrier resin (C) can be further increased, and a resin composition having a more stable form can be formed.

  The compatibilizing agent (D) having such a polar group is disclosed in detail in, for example, JP-A-2002-146217. Among the compatibilizers disclosed in the publication, it is preferable to use a styrene-hydrogenated diene block copolymer having a boronic ester group.

  As the compatibilizer (D), an ethylene-vinyl alcohol copolymer may be used. In particular, when the gas barrier resin (C) is EVOH, the compatibilizer (D) is preferably an ethylene-vinyl alcohol copolymer, and the polymer (A) and the gas barrier resin (C) The effect | action which improves the compatibility between becomes larger. Among these, an ethylene-vinyl alcohol copolymer having an ethylene structural unit content of 70 to 99 mol% and a saponification degree of 40% or more is preferable from the viewpoint of further improving the compatibility. 72-96 mol% is more preferable and, as for content of the ethylene structural unit in the said copolymer, 72-94 mol% is further more preferable. When the content of the ethylene structural unit is less than 70 mol%, the affinity with the polymer (A) may be lowered. On the other hand, when the content of the ethylene structural unit exceeds 99 mol%, the affinity with EVOH as the gas barrier resin (C) may be lowered. Further, the saponification degree in the copolymer is more preferably 45% or more. The upper limit of the saponification degree is not particularly limited, and the saponification degree may be substantially 100%. When the degree of saponification is less than 40%, the affinity with EVOH which is a gas barrier resin (C) may be lowered.

  In the resin composition of this invention, 1 type of compatibilizers (D) may be included and 2 or more types may be included.

  When the resin composition of the present invention contains the gas barrier resin (C) and the compatibilizer (D), the weight of the polymer (A), the gas barrier resin (C) and the compatibilizer (D) The proportion of each weight in the total is as follows: the polymer (A) is 1 to 29.9%, the gas barrier resin (C) is 70 to 98.9%, and the compatibilizer (D) is 0.1 to 29. %. When the ratio of the weight of the gas barrier resin (C) in the total is less than 70%, the gas barrier property as the resin composition may be reduced. When the ratio exceeds 98.9%, the polymer (A) and Since the ratio of the compatibilizer (D) is excessively decreased, the oxygen absorption capacity of the resin composition may be decreased, and the form stability may be impaired. The ratio for the gas barrier resin (C) is more preferably 80 to 97.5%, and further preferably 85 to 96%. The proportion of the polymer (A) is more preferably 2 to 19.5%, further preferably 3 to 14%. The proportion of the compatibilizer (D) is more preferably 0.5 to 18%, and further preferably 1 to 12%.

  When the resin composition of the present invention contains a gas barrier resin (C) and a compatibilizer (D) and the oxygen absorption accelerator (B) is a transition metal salt (B-1), a transition metal The content of the salt (B-1) is preferably 1 to 50000 ppm in terms of metal element, based on the total weight of the polymer (A), the gas barrier resin (C) and the compatibilizer (D), 5-10000 ppm is more preferable, and 10-5000 ppm is more preferable. When the content of the transition metal salt (B-1) is less than 1 ppm, the oxygen absorption capacity of the resin composition may be excessively decreased, and when it exceeds 50000 ppm, the thermal stability of the resin composition is decreased. In the case of molding such as melt molding, a decomposition gas may be generated, and the generation of gels and blisters may become significant.

  As long as the effects of the present invention are obtained, the resin composition of the present invention may contain a polymer (E) other than the polymer (A), the gas barrier resin (C), and the compatibilizer (D). The polymer (E) is not particularly limited. For example, the polyolefin resin (E), more specifically, polyethylene, polypropylene, an ethylene-propylene copolymer, a copolymer of ethylene and another monomer, Or what is necessary is just a copolymer of a propylene and another monomer. Examples of other monomers include α-olefins such as 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene; itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, and the like. Unsaturated carboxylic acids, salts thereof, partial esters thereof, complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof; vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate Carboxylic acid vinyl esters such as vinyl stearate and vinyl arachidonate; vinyl silane compounds such as vinyl trimethoxysilane; unsaturated sulfonic acids and salts thereof; alkyl thiols; vinyl pyrrolidones and the like. Further, as the polymer (E), polyolefins such as poly-4-methyl-1-pentene and poly-1-butene; polyesters such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate; polystyrene, polycarbonate and polyacrylate may be used. Good. When the resin composition of the present invention contains a polymer (E), the resin composition may or may not contain a gas barrier resin (C) and / or a compatibilizer (D). Also good.

  When the resin composition of the present invention contains the polymer (E) and the oxygen absorption accelerator (B) is a transition metal salt (B-1), the content of the transition metal salt (B-1) is Based on the total weight of the polymer (A) and the polymer (E), 1 to 50000 ppm is preferable in terms of metal element, 5 to 10000 ppm is more preferable, and 10 to 5000 ppm is more preferable.

  Similarly, the resin composition of the present invention contains at least one material selected from a gas barrier resin (C), a compatibilizer (D) and a polymer (E), and an oxygen absorption accelerator (B). Is a transition metal salt (B-1), the content of the transition metal salt (B-1) is converted to a metal element based on the total weight of the polymer (A) and the at least one material. Is preferably 1 to 50000 ppm, more preferably 5 to 10000 ppm, and even more preferably 10 to 5000 ppm.

  As long as the effects of the present invention can be obtained, the resin composition of the present invention may contain an antioxidant. The antioxidant may be the same as the above-described antioxidant that can be combined with the polymer (A). 0.001 to 1 weight% is preferable and, as for content of antioxidant in the resin composition of this invention, 0.01 to 0.5 weight% is more preferable.

  As long as the effects of the present invention are obtained, the resin composition of the present invention may contain various additives. Examples of such additives include plasticizers, heat stabilizers (melt stabilizers), photoinitiators, deodorants, UV absorbers, antistatic agents, lubricants, colorants, fillers, desiccants, fillers, Examples include pigments, dyes, processing aids, flame retardants, antifogging agents, and other polymer compounds, which are disclosed in detail in, for example, JP-A-2002-146217.

  The resin composition of the present invention may have a structure in which particles composed of the polymer (A) are dispersed in the gas barrier resin (C). By using a resin composition in which particles of the polymer (A) are dispersed in a matrix of the gas barrier resin (C), a molded product or a laminate having good transparency, gas barrier properties, and oxygen absorption ability can be formed. The average particle size of the polymer (A) particles is preferably 10 μm or less. When the average particle size exceeds 10 μm, the area of the interface between the polymer (A) and other components (gas barrier resin (C), etc.) becomes excessively small, and the gas barrier property and oxygen absorption of the resin composition Performance may be reduced. The average particle diameter of the polymer (A) particles is more preferably 5 μm or less, and further preferably 2 μm or less.

  The “average particle diameter” of the polymer (A) particles may be obtained by the following method. First, a resin composition sample is carefully cut with a microtome, and platinum is vapor-deposited in a reduced pressure atmosphere on a cross section exposed by the cutting. Next, the cross section on which platinum is deposited is photographed at a magnification of about 10,000 using a scanning electron microscope (SEM). What is necessary is just to measure the maximum diameter of the particle | grains observed in the obtained photograph, and let the average value be an average particle diameter. Note that the number of particles to be measured may be about 20 or more.

  The melt flow rate (MFR) (210 ° C., under a load of 2160 g, based on JIS K7210) of the resin composition of the present invention is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min. 1-30 g / 10 min is more preferable. When the MFR is out of the above range, workability during molding such as melt molding may be deteriorated.

  The resin composition of the present invention can be formed by mixing the components described above. The method and order for mixing the components are not particularly limited. For example, when the polymer (A), the oxygen absorption accelerator (B), the gas barrier resin (C) and the compatibilizer (D) are mixed, these may be mixed simultaneously, or the polymer (A) The oxygen absorption accelerator (B) and the compatibilizer (D) may be mixed and then mixed with the gas barrier resin (C). Further, after the polymer (A) and the compatibilizer (D) are mixed, they may be mixed with the oxygen absorption accelerator (B) and the gas barrier resin (C), or the oxygen absorption accelerator (B) and After mixing the gas barrier resin (C), it may be mixed with the polymer (A) and the compatibilizer (D). Furthermore, the polymer (A), the gas barrier resin (C) and the compatibilizer (D) may be mixed and then mixed with the oxygen absorption accelerator (B), or the oxygen absorption accelerator (B). And the compatibilizer (D) may be mixed and then mixed with the polymer (A) and the gas barrier resin (C). A mixture obtained by mixing the polymer (A), the gas barrier resin (C) and the compatibilizer (D), and a mixture obtained by mixing the oxygen absorption accelerator (B) and the gas barrier resin (C) And may be mixed. The same applies when the resin composition of the present invention does not contain a compatibilizer (D).

  The mixing method is not particularly limited, but the melt-kneading method is preferable from the viewpoints of process simplicity and cost. In the melt-kneading method, using an apparatus that can achieve a high degree of kneading, by dispersing each component as finely and uniformly as possible, the oxygen absorption capacity and transparency of the resin composition can be improved, a gel to the resin composition, Mixing of debris can be suppressed.

  Examples of the kneader include continuous intensive mixers, kneading type twin screw extruders (in the same direction or in different directions), mixing rolls, and kneaders: high speed mixers, Banbury mixers, intensive mixers, pressure kneaders. Batch type kneaders such as: KCK Kneader Extruder manufactured by KCK Corporation, etc. Equipment using a rotating disk having a grinding mechanism such as a stone mill: A single screw extruder provided with a kneading part (Dalmage, CTM, etc.) Apparatus: A simple kneader such as a ribbon blender or a Brabender mixer may be used. Of these, a continuous kneader is preferable. Examples of commercially available continuous intensive mixers include FCM manufactured by Farrel, CIM manufactured by Nippon Steel Works, Ltd., KCM, LCM, and ACM manufactured by Kobe Steel Corporation. It is preferable to employ a device in which a single-screw extruder is installed under these kneaders, and kneading and extrusion pelletization are simultaneously performed. Examples of the twin-screw kneading extruder having a kneading disc or a kneading rotor include TEX manufactured by Nippon Steel, ZSK manufactured by Werner & Pfleiderer, TEM manufactured by Toshiba Machine Co., Ltd., and PCM manufactured by Ikekai Iron Works Co., Ltd. It is done. One kneader may be used, or two or more kneaders may be connected and used.

  The kneading temperature may be usually 50 to 300 ° C. In order to suppress the oxidation of the polymer (A), it is preferable that the hopper port is sealed with nitrogen and extruded at a low temperature. The kneading time is preferably longer, but from the viewpoint of suppressing the oxidation of the polymer (A) and improving the production efficiency, it is usually about 10 to 600 seconds, preferably about 15 to 200 seconds, and preferably 15 to 150 seconds. The degree is more preferred.

  The resin composition of the present invention can be molded into various molded products, for example, packaging materials such as films, sheets, and containers, by selecting a molding method. A molded article including a portion made of the resin composition of the present invention is excellent in oxygen absorbing ability and can suppress generation of unpleasant odor during use (at the time of oxygen absorption). The molded product may consist entirely of the resin composition of the present invention.

  Similarly, the resin composition of the present invention containing the gas barrier resin (C) can be molded into various molded products, and the molded product including a portion made of the resin composition further has high gas barrier properties.

  When the resin composition of the present invention is molded, the resin composition may be once molded into pellets, or may be directly molded by dry blending each component constituting the resin composition.

  The resin composition of the present invention can be molded into a molded product such as a film, sheet, or pipe by melt extrusion molding, can be molded into a container by injection molding, and can be molded into a hollow container such as a bottle by hollow molding. A preferable example of hollow molding is extrusion hollow molding in which a parison is formed by extrusion molding and blown to form. Another preferred example of hollow molding is injection hollow molding in which a preform is molded by injection molding and blown to perform molding.

  You may form the laminated body containing the layer which consists of the said resin composition from the resin composition of this invention. By appropriately selecting the layers constituting the laminate together with the layer comprising the resin composition of the present invention, a laminate having various properties such as mechanical properties, water vapor barrier properties, further oxygen barrier properties and the like is obtained. be able to.

  The layer structure of the laminate is not particularly limited. When the layer made of a material other than the resin composition of the present invention is an x layer, the layer of the resin composition of the present invention is a y layer, and the adhesive resin layer is a z layer, for example, x / y, x / y / x , X / z / y, x / z / y / z / x, x / y / x / y / x, x / z / y / z / x / z / y / z / x I just need it. When the laminate has a plurality of x layers, the types of the x layers may be the same or different. Further, a layer using a collected resin made of scrap such as trim generated during molding may be further formed, or the collected resin may be blended with a layer made of another resin. The thickness of each layer in the laminate is not particularly limited, but from the viewpoint of moldability and cost, the thickness of the y layer in the total thickness is preferably about 2 to 20%.

  The material used for the x layer is preferably a thermoplastic resin from the viewpoint of processability. For example, the following resins may be used: polyethylene, polypropylene, ethylene-propylene copolymer, copolymer having ethylene or propylene as a structural unit. Polymers, polyolefins such as poly-4-methyl-1-pentene, poly-1-butene: polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate: poly ε-caprolactam, polyhexamethylene adipamide, polymetaxylylene azide Polyamides such as pamide: polyvinylidene chloride, polyvinyl chloride, polystyrene, polyacrylonitrile, polycarbonate, polyacrylate. Here, examples of constituent units other than ethylene or propylene in the copolymer having ethylene or propylene as constituent units include 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, and 1-octene. α-olefin: unsaturated carboxylic acid such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride, its salt, its partial ester, its complete ester, its nitrile, its amide, its anhydride: vinyl formate, vinyl acetate, Carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate, vinyl octanoate, vinyl dodecanoate, vinyl stearate, vinyl arachidonate: vinyl silane compounds such as vinyl trimethoxysilane: unsaturated sulfonic acid, its salts : Alkylthiols: Bi Rupiroridon such as long, and the like.

  The x layer made of polyolefin is excellent in moisture resistance, mechanical properties, economy, heat sealability and the like. The x layer made of polyester is excellent in mechanical properties, heat resistance, and the like.

  The x layer made of a polymer may be unstretched, may be uniaxially or biaxially stretched, or may be rolled.

  The adhesive resin used for the z layer is not particularly limited as long as the layers constituting the laminate can be bonded to each other. For example, polyurethane or polyester one-component or two-component curable adhesives, carboxylic acid-modified polyolefin resins, or boron-containing boronic acid groups, boronic acid ester groups, boronic acid anhydride groups, boronic acid groups, etc. A hydrocarbon-based polymer having a polar group may be used. The carboxylic acid-modified polyolefin resin is an olefin polymer or copolymer containing an unsaturated carboxylic acid or an anhydride thereof (such as maleic anhydride) as a copolymerization component, or an unsaturated carboxylic acid or an anhydride thereof as an olefin polymer. Or it is a graft copolymer obtained by grafting to a copolymer.

  Among these, a z layer made of a carboxylic acid-modified polyolefin resin is preferable. In particular, when the x layer is a polyolefin resin, the adhesiveness between the x layer and the y layer can be improved by making the z layer a carboxylic acid-modified polyolefin resin layer. Examples of carboxylic acid-modified polyolefin resins include polyethylene (including low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE)), polypropylene, copolymer polypropylene, and ethylene-vinyl acetate. Examples thereof include resins obtained by modifying a copolymer and an ethylene- (meth) acrylic acid ester (methyl ester or ethyl ester) copolymer with a carboxylic acid.

  The method for forming the laminate is not particularly limited, and for example, an extrusion lamination method, a dry lamination method, a co-injection molding method, a co-extrusion molding method, or the like may be used. As the coextrusion molding method, for example, a coextrusion lamination method, a coextrusion sheet molding method, a coextrusion inflation molding method, a coextrusion blow molding method, or the like may be used.

  Laminate sheets, films, parisons, etc. formed by these methods are reheated at a temperature below the melting point of each material constituting the laminate, thermoforming methods such as drawing, roll stretching methods, pantograph type stretching methods, etc. A stretched laminate can be formed by uniaxially or biaxially stretching by an inflation stretching method, a blow molding method, or the like.

  Molded products using these laminates are used in various applications (for example, multilayer containers). A laminate in which layers having a high water vapor barrier property are arranged on both sides of the layer made of the resin composition of the present invention or on a high humidity side can extend the duration of the oxygen absorption capacity, and therefore a high gas barrier property is required for a long time. Suitable for use. The laminate having the layer made of the resin composition of the present invention in the innermost layer is suitable for applications requiring rapid oxygen absorption capability, for example, applications requiring rapid absorption of oxygen in the container.

  The resin composition of this invention can improve the transparency by selecting an appropriate gas barrier resin (C). Such a resin composition is suitable for use as a packaging container in which the contents are easily visible.

  Among the packaging containers, the requirement for transparency is strict, and the following two forms can be mentioned as forms having a large effect when the resin composition of the present invention is used. A 1st form is a container which consists of a laminated body (for example, multilayer film) containing the layer which consists of a resin composition of this invention. The total layer thickness of the container is preferably 300 μm or less. A 2nd form is a container containing the layer which consists of a resin composition of this invention, and a thermoplastic polyester (PES) layer at least 1 layer, respectively. Hereinafter, the first and second embodiments will be described in detail.

  The first container is a flexible multilayer container made of a laminate having a relatively thin overall thickness, and is usually processed into a form such as a pouch. This container is excellent in gas barrier properties, has a continuous oxygen absorption capacity, and is easy to manufacture. Therefore, it is extremely useful for packaging products that are highly sensitive to oxygen and easily deteriorate. Moreover, in the resin composition of this invention, since generation | occurrence | production of the unpleasant odor at the time of use is suppressed, the said container is very useful for the packaging of the product which attaches importance to fragrance.

  The thickness of the first container (total thickness of the laminate) is not particularly limited, but is preferably 300 μm or less, more preferably 250 μm or less, and even more preferably 200 μm or less in order to ensure transparency and flexibility. On the other hand, considering the mechanical properties of the container, the thickness of the laminate is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more.

  As described above, the resin composition of the present invention can exhibit high transparency by appropriate selection of components. For this reason, it can be suitably used for the first container, which often requires transparency.

  Although the manufacturing method of a 1st container is not specifically limited, For example, when forming with a dry lamination method, an unstretched film, a uniaxially stretched film, a biaxially stretched film, a rolled film etc. can be used for a thermoplastic resin layer. Among these, a biaxially stretched polypropylene film, a biaxially stretched polyethylene terephthalate film, and a biaxially stretched poly ε-caprolactam film are preferable from the viewpoint of mechanical strength. From the viewpoint of moisture resistance, a biaxially stretched polypropylene film is preferable. When an unstretched film or a uniaxially stretched film is used for the thermoplastic resin layer, the entire layer is reheated after laminating each layer constituting the laminate, a thermoforming method such as drawing, a roll stretching method, a pantograph stretching method, Uniaxial or biaxial stretching may be performed by an inflation stretching method or the like. In this case, a stretched laminate can be obtained.

  When forming the bag-shaped first container, in order to seal the inside of the container, a layer made of a heat-sealable resin may be disposed on the surface of at least one outermost layer in the manufacturing process of the laminate. Good. Examples of the heat-sealable resin include polyolefins such as polyethylene and polypropylene. By processing the laminate into a bag shape, a packaging container for filling the contents is obtained, and the packaging container has excellent gas barrier properties and oxygen scavenging properties, and also suppresses the generation of unpleasant odors. It is extremely useful for contents that are easily deteriorated by the presence of oxygen, especially for packaging foods.

  The second container is excellent in gas barrier properties and oxygen absorption capacity, and generates less unpleasant odor during use. Moreover, it can also be set as the container which has high transparency by selecting suitably the component of the resin composition of this invention. The second container is used in various forms such as a bag-shaped container, a cup-shaped container, and a hollow molded container. Among these, hollow molded containers, particularly bottles, are important. Specifically, it is useful as a container for contents that easily deteriorate due to the presence of oxygen, for example, foods and pharmaceuticals, and as a food, it is useful as a container for beverages such as beer.

  As the PES (thermoplastic polyester) used for the second container, a condensation polymer containing aromatic dicarboxylic acids or their alkyl esters and diol as main components may be used. Of these, PES mainly composed of an ethylene terephthalate component is preferable. Specifically, the total proportion (mol%) of terephthalic acid units and ethylene glycol units in all the structural units constituting PES is preferably 70 mol% or more, and more preferably 90 mol% or more. By making the said ratio 70 mol% or more, the fall of the mechanical strength of a container, the increase in heat shrink, and the fall of productivity can be suppressed. In addition, as long as the effect of the present invention is obtained, the PES is optionally a bifunctional compound unit other than a terephthalic acid unit and an ethylene glycol unit, such as a neopentyl glycol unit, a cyclohexanedimethanol unit, a cyclohexanedicarboxylic acid unit, An isophthalic acid unit and a naphthalenedicarboxylic acid unit may be included. There is no restriction | limiting in the manufacturing method of such PES, For example, a well-known method is applicable.

  Although the manufacturing method of a 2nd container is not specifically limited, For example, what is necessary is just to use co-injection blow molding. Co-injection blow molding is preferred from the standpoint of productivity. In co-injection blow molding, a container can be produced by stretch blow molding a container precursor (parison) obtained by co-injection molding.

In co-injection molding, the resin that constitutes each layer of the laminate is usually led from two or more injection cylinders into a concentric nozzle, and simultaneously or at different timings, alternately in a single mold. Molding is performed by injecting and performing a single clamping operation. A specific method of co-injection molding is not particularly limited, and a known method may be used.
(1) First, PES for inner layer and outer layer are injected, and then the resin composition of the present invention to be an intermediate layer is injected to form a three-layer molded container of “PES / resin composition / PES”. Method of Obtaining (2) First, PES for inner layer and outer layer is injected, then the resin composition of the present invention is injected, and at the same time or after that, PES is injected again, and “PES / resin composition / PES / A method of obtaining a molded container having a five-layer structure of “resin composition / PES” may be used. At this time, an adhesive resin layer may be disposed between the resin composition layer and the PES layer.

  The injection temperature of PES is usually 250 to 330 ° C, preferably 270 to 320 ° C, more preferably 280 to 310 ° C. When the injection temperature of PES is less than 250 ° C., PES is not sufficiently melted, and an unmelted product (fish eye) is mixed into the molded product, resulting in poor appearance, and the mechanical strength of the obtained molded product is reduced. Sometimes. In extreme cases, the screw torque becomes excessive, which may cause a failure of the molding machine. On the other hand, when the injection temperature of PES exceeds 330 ° C., the decomposition of PES becomes remarkable, and the mechanical strength of the molded product may be decreased due to the decrease in molecular weight. In addition, the properties of the molded product are impaired by a gas such as acetaldehyde generated at the time of decomposition, and the mold formed by the molding machine may become heavily soiled by the oligomer generated at the time of decomposition, and the appearance of the molded product may be impaired.

  The injection temperature of the resin composition of the present invention is usually 170 to 250 ° C, more preferably 180 to 240 ° C, and further preferably 190 to 230 ° C. If the injection temperature is too low, the same problem as in the case of PES may occur. When the injection temperature is excessively high, the oxidation of the polymer (A) is excessively promoted, and the gas barrier property and oxygen absorption ability of the resin composition may be lowered, and the appearance may be poor due to coloring or gel formation. Or a part of the resin composition layer may be lost. In extreme cases, injection molding itself cannot be performed. In order to suppress excessive oxidation of the resin composition during melting, the resin composition supply hopper may be sealed with nitrogen.

  The resin composition may be supplied to the molding machine in the form of pellets obtained by melting and blending each component constituting the composition, or each component may be dry blended and supplied to the molding machine. .

  The parison thus obtained has a total thickness of 2 to 5 mm, for example, and a total thickness of the resin composition layer of the present invention is 10 to 500 μm.

  The parison is sent to the stretch blow process at a high temperature, or is reheated by a block heater or an infrared heater and then sent to the stretch blow process. After the heated parison is stretched 1 to 5 times in the longitudinal direction in the stretch blow step, a multilayer container can be produced by stretch blow molding 1 to 4 times with compressed air or the like. The temperature of the parison is usually 75 to 150 ° C, for example, 85 to 140 ° C, or 90 to 130 ° C, or 95 to 120 ° C. When the temperature of the parison exceeds 150 ° C., PES tends to be crystallized, and the obtained container may be whitened to deteriorate its appearance, or peeling between layers constituting the container may increase. On the other hand, when the temperature of the parison is less than 75 ° C., crazing occurs in the PES, and the transparency may be impaired due to a pearly tone.

  The thickness of the body of the second container is generally 100 to 2000 μm, preferably 150 to 1000 μm, but may be adjusted according to the application. At this time, 2-200 micrometers is preferable and, as for the total thickness of the resin composition layer of this invention, 5-100 micrometers is more preferable.

  In addition, as a molded article including the part which consists of a resin composition of this invention, the lid | cover (cap) of containers, such as a bottle, is mentioned, for example. Specifically, the cap gasket may be made of the resin composition of the present invention. Such caps have excellent gas barrier properties and oxygen scavenging properties, and are less likely to cause unpleasant odors when used, so they are extremely sensitive to oxygen and easily deteriorated products, especially for food and cosmetic containers. Useful.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. Analysis and evaluation in the following examples were performed as follows.

(1) Molecular structure of polymer (A) The molecular structure of polymer (A) is determined by ¹ H-NMR (nuclear magnetic resonance) measurement of polymer (A) (“JNM-GX-500” manufactured by JEOL Ltd.). Was carried out using deuterated chloroform as a solvent, and the spectrum obtained by the measurement was evaluated.

(2) Number average molecular weight of polymer (A) The number average molecular weight of polymer (A) was determined as a polystyrene equivalent value by gel permeation chromatography (GPC).

(3) Ethylene unit content and saponification degree of EVOH as gas barrier resin (C) Ethylene unit content of EVOH used as gas barrier resin (C) (ratio of ethylene units in all constituent units of EVOH) and saponification The degree was evaluated from a spectrum obtained by performing a ¹ H-NMR measurement (using “JNM-GX-500 type” manufactured by JEOL Ltd.) on EVOH using deuterated dimethyl sulfoxide as a solvent.

(Synthesis of polymer used in polymer (A) and comparative example 1)
The polymers used in the following Examples and Comparative Example 1 were synthesized as follows.

(Synthesis Example 1)
Synthesis of sample 1 (poly (dihydrofuran)) 2,3-dihydrofuran (70 g, 1 mol) and methylene chloride (100 g) were placed in a three-necked flask (300 ml) equipped with a reflux tube, a thermometer and a mechanical stirrer. The inside was replaced with nitrogen. Next, 1.62 g (10 mmol) of anhydrous iron chloride was added as a catalyst in the flask, and the mixture was stirred at 40 ° C. for 3 hours. Next, 200 g of 1N hydrochloric acid was added to the reaction solution after stirring, and after further stirring, the upper layer in the flask was removed. After repeating the operations of adding hydrochloric acid, stirring and removing the upper layer twice, 200 g of water was added to the flask, and after further stirring, the upper layer was removed to obtain an organic layer in the flask. The solvent was removed from the obtained organic layer by evaporation to obtain 64 g of poly (dihydrofuran) represented by the following formula (X) as Sample 1. When the number average molecular weight of the obtained poly (dihydrofuran) was evaluated by GPC, it was about 22,000.

(Synthesis Example 2)
Synthesis of Sample 2 (Poly (dihydropyran)) As in Synthesis Example 1, except that 84 g of 2,3-dihydro-4H-pyran was used instead of 70 g of 2,3-dihydrofuran, the following formula was obtained as Sample 2. 81 g of poly (dihydropyran) shown in (XI) was obtained. When the number average molecular weight of the obtained poly (dihydropyran) was evaluated in the same manner as in Synthesis Example 1, it was about 23,000.

(Synthesis Example 3)
Synthesis of Sample 3 (Poly (4-methyldihydropyran)) As in Synthesis Example 1 except that 98 g of 4-methyl-2,3-dihydro-4H-pyran was used instead of 70 g of 2,3-dihydrofuran. Thus, 91 g of poly (4-methyldihydropyran) represented by the following formula (XII) was obtained as Sample 3. When the number average molecular weight of the obtained poly (4-methyldihydropyran) was evaluated in the same manner as in Synthesis Example 1, it was about 21,000.

(Synthesis Example 4)
Synthesis of Comparative Example Sample A (Styrene-Isoprene-Styrene Block Copolymer) In a stirred autoclave substituted with dry nitrogen, 600 parts by volume of cyclohexane, N, N, N ′, N′-tetramethylethylenediamine (TMEDA) ) 0.16 parts by volume and 0.094 parts by volume of n-butyllithium as an initiator were added. Next, the temperature in the autoclay part was set to 50 ° C., 4.25 parts by volume of styrene monomer was added to the mixture of the above materials, and polymerization was performed for 1.5 hours. Next, the temperature was lowered to 30 ° C., 120 parts by volume of isoprene was further added, and polymerization was performed for 2.5 hours. Next, the temperature was again set to 50 ° C., and 4.25 parts by volume of styrene monomer was further added, and polymerization was performed for 1.5 hours. To the reaction solution obtained by the above polymerization, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and pentaerythritol tetrakis (3 -Laurylthiopropionate) was added in an amount of 0.15 parts by weight per 100 parts by weight of the total amount of styrene and isoprene. Next, the reaction solution to which the antioxidant is added is poured into methanol to precipitate the product, which is separated and dried, and the styrene-isoprene-styrene triblock copolymer to which the antioxidant is added (Comparative Example). Sample A) was obtained.

  When evaluated by GPC, in Comparative Sample A, the number average molecular weight was 85000, the molecular weight of the styrene block was 8500, the content of styrene constituent units was 14 mol%, and the carbon in the side chain occupying all the carbon-carbon double bonds. The proportion of carbon double bonds was 55%. Moreover, content of the carbon-carbon double bond in Sample A was 0.014 eq / g, and MFR (210 ° C., 2160 g load) of Sample A was 7.7 g / 10 min. Sample A contained 0.12% by weight of each of the two compounds as antioxidants.

(Gas barrier resin (C))
In Examples and Comparative Examples below, EVOH having the following composition and physical properties was used as the gas barrier resin (C) except for Examples 4 to 8.

Ethylene constitutional unit content: 32 mol%
Saponification degree: 99.6%
MFR: 3.1 g / 10 min (210 ° C., 2160 g load)
Phosphoric acid compound content: 100ppm (phosphate group conversion)
Sodium salt content: 65 ppm (sodium equivalent)
Melting point: 183 ° C
Oxygen permeation rate (20 ° C., 65% RH): 0.4 ml · 20 μm / (m ² · day · atm)

Example 1
7 g of sample 1 (poly (dihydrofuran)) synthesized in Synthesis Example 1 as the polymer (A), 0.59 g of cobalt stearate (poly (dihydrofuran) and gas barrier resin (C) as the transition metal salt (B-1)) ) And EVOH added as a gas barrier resin (C) are dry blended with 63 g of EVOH, and a roller mixer (LABO PLASTOMIL MODEL R100 manufactured by Toyo Seiki Co., Ltd.) While the inside of the mixer chamber was purged with nitrogen, it was melt-kneaded for 5 minutes under the conditions of 200 ° C. and screw rotation speed of 60 rpm. Next, the lump obtained by melt kneading was formed into pellets to form a resin composition (resin composition 1).

(Evaluation of oxygen absorption capacity)
The formed resin composition 1 was molded into a sheet shape at an extrusion temperature of 200 ° C. with a compression molding machine (manufactured by Shinfuji Metal Industry Co., Ltd.) to form a sheet (single layer sheet 1) having a thickness of 100 μm. When the cross section of this sheet was observed with a transmission electron microscope (SEM), it had a structure in which particles made of poly (dihydrofuran) (particle size of about 1 to 2 μm) were well dispersed in the EVOH matrix. It was.

Separately from the observation by SEM, a part (0.1 g) of the single-layer sheet 1 was cut out, and after 5 hours from forming into a sheet, it was wound into a roll and air at 23 ° C. and 50% RH ( It was accommodated in a standard bottle (internal volume 260 ml) filled with N ₂ : O ₂ = 79: 21 by volume ratio. Next, 5 ml of water was added to the bottle, and the opening was sealed with a multilayer sheet having an aluminum layer and an epoxy resin, and left in an environment of 60 ° C. and 23 ° C., respectively. The atmosphere inside the bottle can be estimated to be 60 ° C. and 100% RH and 23 ° C. and 100% RH, respectively.

  After sealing the opening, the gas inside the bottle was sampled with a syringe over time, and the oxygen concentration of the sampled gas was measured by gas chromatography (GC). In addition, the pore formed in the multilayer sheet at the time of sampling was sealed with an epoxy resin each time. Next, from the oxygen concentration obtained by the measurement, the amount of oxygen decrease after the opening of the bottle was sealed was calculated, and the oxygen absorption amount of the single-layer sheet 1 (resin composition 1) was determined. Changes in oxygen absorption with respect to the number of days that have passed since the opening was sealed are shown in FIGS. FIG. 1 shows the results under an atmosphere of 60 ° C. and 100% RH (2 days, 7 days, and 14 days have passed since the opening was sealed), and FIG. , 23 ° C., 100% RH atmosphere (points of 3 days, 7 days, 14 days, 21 days, and 28 days have passed since the opening was sealed).

  Further, from the obtained results, the oxygen absorption rate in a period from 2 days to 7 days in an atmosphere of 60 ° C. and 100% RH was evaluated and found to be 1.0 ml / (g · day). Similarly, when the oxygen absorption rate in the period from 3 days to 7 days in an atmosphere of 23 ° C. and 100% RH was evaluated, it was 0.5 ml / (g · day).

(Evaluation of oxygen permeation in the laminate)
A stretched polypropylene (PP) film (OP- # 20 U-1 manufactured by Tosero Co., Ltd .: thickness 20 μm) is laminated on both surfaces of the single-layer sheet 1 formed as described above, and each layer is bonded to a urethane-based adhesive ( Adhesion was performed with a toluene / methyl ethyl ketone (1: 1 weight ratio) solution of Toyo Morton, AD335A) and a curing agent (Toyo Morton, Cat-10), and “stretched PP layer / adhesive layer / single layer sheet 1” A laminated sheet (laminated sheet 1) having a layer configuration of “/ adhesive layer / stretched PP layer” was formed.

  Next, using two laminated sheets 1 formed as described above, a pouch (pouch 1), which is a multilayer container having a size of 30 cm × 30 cm, was formed by heat sealing. In the formed pouch, the oxygen permeation amount after 10 days and 1 month after the formation was evaluated by a nondestructive oxygen concentration meter (PreSense, Fibox 3). Even at the time point, it was 0.00 cc / day · atm.

(Odor evaluation)
A part (1 g) of the single-layer sheet 1 formed as described above was cut out, wound into a roll shape after 5 hours from forming into a sheet shape, and filled with air at 23 ° C. and 50% RH. It was accommodated in a bottle (content 85 ml). Next, 1 ml of water was added to the bottle, and the opening was sealed with a multilayer sheet having an aluminum layer and an epoxy resin, and left in an environment at 60 ° C. for 2 weeks. The atmosphere inside the bottle can be estimated to be 60 ° C. and 100% RH.

  After two weeks had passed since the opening was sealed, when five subjects evaluated the odor inside the bottle, almost no odor was felt.

(Elution evaluation)
After containing water (3 cc) inside the pouch 1 formed as described above, the pouch 1 was sealed by heat sealing and stored for 60 days in an environment of 30 ° C. and 80% RH. After elapse of 60 days, the eluate into water in the pouch 1 was analyzed by gas chromatography mass spectrometry (GC-MS), but the eluate was not confirmed.

(Example 2)
A sheet having a thickness of 100 μm (single layer sheet 2) was formed in the same manner as in Example 1 except that Sample 2 (poly (dihydropyran)) synthesized in Synthesis Example 2 was used instead of Sample 1. When the cross section of this sheet was observed by SEM, it had a structure in which particles (particle size of about 1 to 2 μm) made of poly (dihydropyran) were well dispersed in the EVOH matrix.

(Evaluation of oxygen permeation in the laminate)
Using the single-layer sheet 2 formed as described above, a laminated sheet (laminated sheet 2) having a structure in which the single-layer sheet 2 was sandwiched between a pair of stretched PP films was formed in the same manner as in Example 1. . Next, two laminated sheets 2 were used to form a pouch (pouch 2) in the same manner as in Example 1. In the formed pouch, the oxygen permeation amount after 10 days and one month after the formation was evaluated in the same manner as in Example 1. As a result, the oxygen permeation amount in the entire pouch was 0.00 cc / day at any time point.・ It was atm.

(Odor evaluation and dissolution evaluation)
When the odor evaluation and elution evaluation were performed in the same manner as in Example 1 using the single-layer sheet 2 and the pouch 2 formed as described above, almost no odor was felt and no eluate was confirmed.

(Example 3)
A sheet having a thickness of 100 μm (single layer sheet 3) is formed in the same manner as in Example 1 except that sample 3 (poly (4-methyldihydropyran)) synthesized in Synthesis Example 3 is used instead of Sample 1. did. When the cross section of this sheet was observed by SEM, it had a structure in which particles (particle size of about 1 to 2 μm) made of poly (4-methyldihydropyran) were well dispersed in the EVOH matrix.

(Evaluation of oxygen permeation in the laminate)
Using the single-layer sheet 3 formed as described above, a laminated sheet (laminated sheet 3) having a structure in which the single-layer sheet 3 was sandwiched between a pair of stretched PP films was formed in the same manner as in Example 1. . Next, using two laminated sheets 3, a pouch (pouch 3) was formed in the same manner as in Example 1. In the formed pouch, the oxygen permeation amount after 10 days and one month after the formation was evaluated in the same manner as in Example 1. As a result, the oxygen permeation amount in the entire pouch was 0.00 cc / day at any time point.・ It was atm.

(Odor evaluation and dissolution evaluation)
When the odor evaluation and elution evaluation were performed in the same manner as in Example 1 using the single layer sheet 3 and the pouch 3 formed as described above, almost no odor was felt and no eluate was confirmed.

Example 4
40 g of poly (dihydrofuran) synthesized in Synthesis Example 1 as the polymer (A) and 0.34 g of cobalt stearate as the transition metal salt (B-1) (the weight ratio of Co to poly (dihydrofuran) is about 800 ppm. And the like were melt blended (under a nitrogen purge atmosphere) at 150 ° C. to form a solid. Next, the formed solid was pulverized by a mixer and passed through a 60-80 mesh sieve to form a powdery resin composition (resin composition 4).

(Confirmation of oxygen absorption capacity)
The resin composition 4 formed as described above was accommodated in a standard bottle (internal volume of 260 ml) filled with air (volume ratio of N ₂ : O ₂ = 79: 21) at 23 ° C. and 50% RH. Next, 5 ml of water was added to the bottle, and the opening was sealed with a multilayer sheet having an aluminum layer and an epoxy resin, and left in an environment of 60 ° C. and 23 ° C., respectively. The atmosphere inside the bottle can be estimated to be 60 ° C. and 100% RH and 23 ° C. and 100% RH, respectively.

  After sealing the opening, the gas inside the bottle was sampled with a syringe over time, and when the oxygen concentration of the sampled gas was measured with GC, the oxygen concentration in the gas decreased over time, and the resin The oxygen absorption capacity of the composition 4 was confirmed.

(Odor evaluation)
A part (1 g) of the resin composition formed as described above was weighed and placed in a standard bottle (internal volume 85 ml) filled with air at 23 ° C. and 50% RH. Next, 1 ml of water was added to the bottle, and the opening was sealed with a multilayer sheet having an aluminum layer and an epoxy resin, and left in an environment at 60 ° C. for 2 weeks. The atmosphere inside the bottle can be estimated to be 60 ° C. and 100% RH.

  After two weeks had passed since the opening was sealed, when five subjects evaluated the odor inside the bottle, a slight odor was felt.

(Example 5)
The resin composition (resin composition 5) was the same as in Example 1 except that 63 g of polycaproamide (nylon-6, 1030B manufactured by Ube Industries, Ltd.) was used as the gas barrier resin (C) instead of EVOH. And the sheet | seat (single layer sheet | seat 5) of thickness 100micrometer which consists of the resin composition 5 was formed.

(Confirmation of oxygen absorption capacity)
A part (0.1 g) of the single-layer sheet 5 formed as described above was cut out and formed into a sheet shape, and then wound in a roll shape after 5 hours, and air (volume at 23 ° C. and 50% RH). It was accommodated in a standard bottle (with an internal volume of 260 ml) filled with a ratio of N ₂ : O ₂ = 79: 21). Next, 5 ml of water was added to the bottle, and the opening was sealed with a multilayer sheet having an aluminum layer and an epoxy resin, and left in an environment of 60 ° C. and 23 ° C., respectively. The atmosphere inside the bottle can be estimated to be 60 ° C. and 100% RH and 23 ° C. and 100% RH, respectively.

  After sealing the opening, the gas inside the bottle was sampled with a syringe over time, and the oxygen concentration of the sampled gas was measured with GC. As a result, the oxygen concentration in the gas decreased with time. The oxygen absorption capacity of the layer sheet 5 was confirmed.

(Odor evaluation)
When the odor evaluation was performed on the single layer sheet 5 in the same manner as in Example 1, the odor was hardly felt.

(Example 6)
Resin composition (resin composition 6) and resin in the same manner as in Example 1 except that 63 g of polyacrylonitrile (Valex 1000 manufactured by Mitsui Chemicals, Inc.) was used as the gas barrier resin (C) instead of EVOH. A 100 μm-thick sheet (single layer sheet 6) made of the composition 6 was formed.

(Confirmation of oxygen absorption capacity)
The oxygen absorption capacity of the single layer sheet 6 formed as described above was confirmed in the same manner as in Example 5. As a result, the oxygen concentration in the sampled gas decreased with time, and the oxygen in the single layer sheet 6 decreased. Absorbability was confirmed.

(Odor evaluation)
When the odor evaluation was performed on the single layer sheet 6 in the same manner as in Example 1, the odor was hardly felt.

(Example 7)
As the gas barrier resin (C), a resin composition (resin composition 7) was obtained in the same manner as in Example 1 except that 63 g of polyvinyl chloride (Esmedica V6142E manufactured by Sekisui Chemical Co., Ltd.) was used instead of EVOH. And the sheet | seat (single layer sheet | seat 7) of thickness 100micrometer which consists of the resin composition 7 was formed.

(Confirmation of oxygen absorption capacity)
The oxygen absorption capacity of the single-layer sheet 7 formed as described above was confirmed in the same manner as in Example 5. As a result, the oxygen concentration in the sampled gas decreased with time, and the oxygen in the single-layer sheet 7 decreased. Absorbability was confirmed.

(Odor evaluation)
When the odor evaluation was performed on the single layer sheet 7 in the same manner as in Example 1, the odor was hardly felt.

(Example 8)
The same as Example 1 except that 63 g of low density polyethylene (Novatec LA320, manufactured by Nippon Polyethylene Co., Ltd.) was used as the polymer (E) (polyolefin resin (E)) instead of EVOH as the gas barrier resin (C). Thus, a resin composition (resin composition 8) and a sheet (single layer sheet 8) made of the resin composition 8 and having a thickness of 100 μm were formed.

(Confirmation of oxygen absorption capacity)
The oxygen absorption capacity of the single layer sheet 8 formed as described above was confirmed in the same manner as in Example 5. As a result, the oxygen concentration in the sampled gas decreased with time, and the oxygen in the single layer sheet 8 decreased. Absorbability was confirmed.

(Odor evaluation)
When the odor evaluation was performed on the single layer sheet 8 in the same manner as in Example 1, a slight odor was felt.

Example 9
As an oxygen absorption accelerator (B), instead of cobalt stearate which is a transition metal salt (B-1), titanium dioxide powder which is a photocatalyst (B-3) (P-25 manufactured by Nippon Aerosil Co., Ltd .: anatase type 73) The resin composition (resin composition 9) and the thickness composed of the resin composition 9 are the same as in Example 1 except that 0.70 g (comprising 0.5 wt% and rutile type 26.5 wt%) is used. A 100 μm thick sheet (single layer sheet 9) was obtained.

(Confirmation of oxygen absorption capacity)
The oxygen absorption capacity of the single layer sheet 9 formed as described above was confirmed in the same manner as in Example 5. As a result, the oxygen concentration in the sampled gas decreased with time, and the oxygen in the single layer sheet 9 decreased. Absorbability was confirmed.

(Odor evaluation)
When the odor evaluation was performed on the single-layer sheet 9 in the same manner as in Example 1, the odor was hardly felt.

(Example 10)
40.5 g of a mixed solution of water / methanol (30/70 by weight) and 4.5 g of EVOH were collected in a beaker, and the whole was heated to 80 ° C. with good stirring to obtain an EVOH solution having a concentration of 10% by weight. Formed. Then, the formed EVOH solution, polymer and poly (dihydrofuran) 0.5 g synthesized in Synthesis Example 1 as (A), radical generator (B-2) as N- hydroxy phthalimidine bromide (NHPI) 0 .05 g was added and the whole was uniformly dissolved at room temperature under a nitrogen atmosphere to form a mixed solution. Next, the formed mixed solution was applied onto a commercially available PET film having a corona-treated surface using a bar coat, and then the solvent was removed with a vacuum dryer. In this way, a film (film 10) on which a film having a thickness of about 10 μm was formed was formed.

(Confirmation of oxygen absorption capacity)
When the oxygen absorption capacity of the film 10 formed as described above was confirmed in the same manner as in Example 5, the oxygen concentration in the sampled gas decreased with time, and the oxygen absorption capacity of the film 10 was confirmed. did it.

(Odor evaluation)
When the odor evaluation was performed on the film 10 in the same manner as in Example 1, almost no odor was felt.

(Example 11)
40.5 g of a mixed solution of water / methanol (30/70 by weight) and 4.5 g of EVOH were collected in a beaker, and the whole was heated to 80 ° C. with good stirring to obtain an EVOH solution having a concentration of 10% by weight. Formed. Next, 0.5 g of the poly (dihydrofuran) synthesized in Synthesis Example 1 and a commercially available cobalt acetate solution as the transition metal salt (B-1) were added to the formed EVOH solution, with EVOH and poly (dihydrofuran). The mixture was added so that the weight ratio of Co to the total weight was about 400 ppm, and the whole was uniformly dissolved at room temperature under a nitrogen atmosphere to form a mixed solution. Next, the formed mixed solution was applied onto a commercially available PET film having a corona-treated surface using a bar coat, and then the solvent was removed with a vacuum dryer. In this way, a film (film 11) on which a film having a thickness of about 10 μm was formed was formed.

(Confirmation of oxygen absorption capacity)
When the oxygen absorption capacity of the film 11 formed as described above was confirmed in the same manner as in Example 5, the oxygen concentration in the sampled gas decreased with time, and the oxygen absorption capacity of the film 11 was confirmed. did it.

(Odor evaluation)
When the odor evaluation was carried out on the film 11 in the same manner as in Example 1, almost no odor was felt.

(Comparative Example 1)
A single layer sheet (single layer) made of a resin composition in the same manner as in Example 1 except that the polymer (A) was replaced with the comparative sample A synthesized in Synthesis Example 4 instead of poly (dihydrofuran). Sheet A) was formed. When the cross section of this sheet was observed by SEM, it had a structure in which particles (particle size of about 1 to 2 μm) made of a styrene-isoprene-styrene block copolymer were dispersed in an EVOH matrix.

(Evaluation of oxygen absorption capacity)
The single-layer sheet A formed as described above was evaluated for oxygen absorption ability in the same manner as in Example 1. The evaluation results are shown in FIGS.

  The oxygen absorption rate during the period from the lapse of 2 days to the lapse of 7 days in an atmosphere of 60 ° C. and 100% RH was evaluated from the obtained results, and found to be 0.6 ml / (g · day). Similarly, when the oxygen absorption rate in the period from 3 days to 7 days in an atmosphere of 23 ° C. and 100% RH was evaluated, it was 0.9 ml / (g · day).

(Evaluation of oxygen permeation in the laminate)
Using the single-layer sheet A formed as described above, a laminated sheet (laminated sheet A) having a structure in which the single-layer sheet A is sandwiched by a pair of stretched PP films is formed in the same manner as in Example 1. did. Next, using two laminated sheets A, a pouch (pouch A) was formed in the same manner as in Example 1. In the formed pouch, the oxygen permeation amount after 10 days and one month after the formation was evaluated in the same manner as in Example 1. As a result, the oxygen permeation amount in the entire pouch was 0.00 cc / day.atm.

(Odor evaluation)
When the odor evaluation was performed in the same manner as in Example 1 using the single-layer sheet A formed as described above, an odor (burning odor) was felt, and the intensity of the odor was higher than that in Examples 4 and 8. It was clearly strong.

(Comparative Example 2)
A single-layer sheet (single-layer sheet B) made of the resin composition in the same manner as in Example 1 except that linolenic acid (Comparative Example Sample B) was used as the polymer (A) instead of poly (dihydrofuran). ) When the cross section of this sheet was observed by SEM, linolenic acid having a particle diameter of 5 μm or more was dispersed in the EVOH matrix, and the dispersibility was not good.

(Evaluation of oxygen absorption capacity)
The single layer sheet B formed as described above was evaluated for oxygen absorption ability in the same manner as in Example 1. The evaluation results are shown in FIGS.

  The oxygen absorption rate during the period from the lapse of 2 days to the lapse of 7 days in an atmosphere of 60 ° C. and 100% RH was evaluated based on the obtained results and found to be 0.4 ml / (g · day). Similarly, when the oxygen absorption rate in the period from 3 days to 7 days in an atmosphere of 23 ° C. and 100% RH was evaluated, it was 0.2 ml / (g · day).

(Evaluation of oxygen permeation in the laminate)
Using the single-layer sheet B formed as described above, a laminated sheet (laminated sheet B) having a structure in which the single-layer sheet B is sandwiched between a pair of stretched PP films is formed in the same manner as in Example 1. did. Next, two laminated sheets B were used to form a pouch (pouch B) in the same manner as in Example 1. In the formed pouch, the oxygen permeation amount after 10 days and one month after the formation was evaluated in the same manner as in Example 1. As a result, the oxygen permeation amount in the entire pouch was 0.00 cc / day.atm.

(Odor evaluation and dissolution evaluation)
When the odor evaluation was performed in the same manner as in Example 1 using the single-layer sheet B formed as described above, an odor (burning odor) was felt, and the strength of the odor was higher than that in Examples 4 and 8. It was clearly strong.

  Moreover, when the elution evaluation was performed like Example 1 using the pouch B formed as mentioned above, the elution of linolenic acid was confirmed.

(Comparative Example 3)
In Comparative Example 3, as the polymer (A), instead of poly (dihydrofuran), a polyester polyether block copolymer (Comparative Example) described in Examples of JP-A No. 2003-113311 (Reference 5) Sample C) was used. Comparative Sample C is a copolymer having polybutylene terephthalate as a hard segment and polytetramethylene glycol having a number average molecular weight of 1000 as a soft segment. The content of polytetramethylene glycol in Comparative Sample C is 60% by weight.

(Confirmation of oxygen absorption capacity)
A single layer sheet (single layer sheet C) made of the resin composition was formed in the same manner as in Example 1 except that Comparative Sample C was used instead of poly (dihydrofuran) as the polymer (A).

  The oxygen absorption capacity of the formed single layer sheet C was confirmed in the same manner as in Example 5. As a result, the oxygen concentration in the sampled gas decreased with time, and the oxygen absorption capacity of the single layer sheet C was confirmed. did it.

(Odor evaluation)
Using the single-layer sheet C formed as described above, the odor was evaluated in the same manner as in Example 1. As a result, odor was felt, and the strength of the odor was clearly stronger than in Examples 4 and 8. It was.

(Comparative Example 4)
In Comparative Example 4, as the polymer (A), polytetrahydrofurfuryl methacrylate (Comparative Example Sample D) described in Example 1 of US Pat. No. 6,746,622 (Document 6) was used instead of poly (dihydrofuran). Using.

  In the same manner as in Example 1 except that 4 g of Comparative Sample D was used instead of poly (dihydrofuran) (Sample 1) as the polymer (A), a resin composition (Resin Composition D), and A single layer sheet (single layer sheet D) made of the resin composition D was obtained. However, because the thermal stability of the comparative sample D is inferior, the resin composition D deteriorated during melt molding, and a single-layer sheet D having a brown color was formed.

(Confirmation of oxygen absorption capacity)
The oxygen absorption capacity of the formed single layer sheet D was confirmed in the same manner as in Example 5. As a result, the oxygen concentration in the sampled gas decreased with time, and the oxygen absorption capacity of the single layer sheet D was confirmed. did it.

(Odor evaluation)
When the odor evaluation was performed in the same manner as in Example 1 using the single-layer sheet D formed as described above, the odor was felt, and the strength of the odor was clearly stronger than in Examples 4 and 8. It was.

(Volatilization test during production)
As in Example 1, each of Samples 1 to 3 and Comparative Sample B as the polymer (A), cobalt stearate as the transition metal salt (B-1), and EVOH as the gas barrier resin (C). After dry blending, it was melt blended at 200 ° C. for 5 minutes. In melt blending, in order to remove impurities, deaeration was performed from the vent portion of the blending apparatus using a vacuum pump, and the pressure inside the apparatus was reduced to 266 Pa (2 mmHg). A single-layer film was prepared from the resin composition thus formed, and its oxygen absorption capacity was evaluated in the same manner as in Example 1. As a result of the evaluation, Comparative Example Sample 2 using linolenic acid could not obtain sufficient oxygen absorption ability because linolenic acid was volatilized from the vent part during melt blending. On the other hand, in Samples 1 to 3, such volatilization was not observed, and oxygen absorption ability equivalent to that of the resin composition (single layer sheet) formed by melt blending while using nitrogen purge was shown.

(Summary of evaluation results)
Table 1 below shows a list of components used in Examples 1 to 11 and Comparative Examples 1 to 4. In addition, in the column of the polymer (A) in Comparative Examples 1 to 4, each component (Comparative Example Samples A to D) used instead of the polymer (A) is shown. In the column of gas barrier resin (C) in Example 8, low density polyethylene which is polymer (E) (polyolefin resin (E)) is shown.

  The evaluation results of oxygen absorption capacity, odor, and elution in each Example and Comparative Example are shown in Table 2 below. In Table 2, “−” is shown for items that were not evaluated in each Example and Comparative Example. In the odor evaluation of Table 2, “A” indicates that almost no odor is felt, “B” indicates that the odor is felt to some extent, and “C” indicates that the odor is clearly felt. . Moreover, the result of the volatilization test at the time of manufacture is shown in the column of the Example (comparative example) corresponding to each sample used for evaluation.

  As shown in Table 2, in Examples 1 to 11 compared to Comparative Examples 1 to 4, the generation of odor during use could be suppressed.

  The evaluation results (corresponding to FIGS. 1 and 2) of the oxygen absorption capacity (oxygen absorption amount, oxygen absorption rate) in Example 1, Comparative Example 1 and Comparative Example 2 are shown in Tables 3 and 4 below. Table 3 shows the evaluation results in an atmosphere of 60 ° C. and 100% RH, and Table 4 shows the evaluation results in an atmosphere of 23 ° C. and 100% RH.

  The present invention can be applied to other embodiments without departing from the spirit and essential characteristics thereof. The embodiments disclosed in this specification are illustrative in all respects and are not limited thereto. The scope of the present invention is shown not by the above description but by the appended claims, and all modifications that fall within the meaning and scope equivalent to the claims are embraced therein.

  The oxygen-absorbing resin composition of the present invention can be applied to a wide range of uses such as an oxygen-absorbing material or a packaging material. In particular, it is suitably used as a packaging material for articles, such as foods, medicines, medical equipment, machine parts, and clothing, which are greatly affected by deterioration due to oxygen. In addition, since the oxygen-absorbing resin composition of the present invention can suppress the generation of unpleasant odor during use, the oxygen-absorbing composition of the present invention is preferable as a packaging material for articles in which fragrance is important.

Claims (18)

See containing the polymer (A) having a structural unit represented by formula (I), the oxygen absorption promoter and (B),
The oxygen-absorbing resin composition, wherein the oxygen absorption accelerator (B) is at least one selected from cobalt salt, N-hydroxyphthalimide, and titanium dioxide .

In the formula (I),
X shows the C1-C4 alkylene group which may have a substituent.
Z represents a single bond or a methylene group which may have a substituent.
R ¹ and R ² represent hydrogen, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
The carbon atom adjacent to the oxygen atom has at least one hydrogen atom. X is an alkylene group represented by formula (II), formula (III), or formula (IV);
Z is a single bond,
The oxygen-absorbing resin composition according to claim 1, wherein R ¹ and R ² are hydrogen.

  The oxygen-absorbing resin composition according to claim 1, wherein the polymer (A) is a furan derivative polymer.   The oxygen-absorbing resin composition according to claim 3, wherein the polymer (A) is poly (dihydrofuran).   The oxygen-absorbing resin composition according to claim 1, wherein the polymer (A) is a polymer of a pyran derivative.   The oxygen-absorbing resin composition according to claim 5, wherein the polymer (A) is poly (dihydropyran).   The oxygen-absorbing resin composition according to claim 5, wherein the polymer (A) is poly (4-methyldihydropyran). Oxygen-absorbing resin composition of claim 1 wherein said oxygen absorbent accelerator (B) child Baltic salt.   The oxygen-absorbing resin composition according to claim 1, further comprising a gas barrier resin (C). 10. The oxygen-absorbing resin composition according to claim 9 , wherein the gas barrier resin (C) has an oxygen permeation rate at 20 ° C. and 65% RH of 500 ml · 20 μm / (m ² · day · atm) or less. The oxygen-absorbing resin composition according to claim 9 , wherein the gas barrier resin (C) is at least one selected from the group consisting of polyvinyl alcohol resins, polyamide resins, polyvinyl chloride resins, and polyacrylonitrile resins. . 10. The oxygen according to claim 9 , wherein the gas barrier resin (C) is an ethylene-vinyl alcohol copolymer having a proportion of ethylene units in the total structural units of 5 to 60 mol% and a saponification degree of 90% or more. Absorbent resin composition. The oxygen-absorbing resin composition according to claim 9 , wherein a ratio of the weight of the polymer (A) to the total weight of the polymer (A) and the gas barrier resin (C) is 1 to 30%. . The oxygen-absorbing resin composition according to claim 9 , wherein the particles made of the polymer (A) have a structure dispersed in the gas barrier resin (C).   The oxygen-absorbing resin composition according to claim 1, further comprising a polyolefin resin (E).   The molded article containing the part which consists of an oxygen absorptive resin composition of Claim 1.   The laminated body containing the layer which consists of an oxygen absorptive resin composition of Claim 1. The laminate according to claim 17 , further comprising a thermoplastic polyester layer.

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